JPH10329281A - Translucent composite - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To apply a material made of a fluoropolymer having excellent adhesion to a substrate to a light-transmitting substrate while maintaining transparency without requiring a complicated process. A light-transmitting composite material comprising: Further, a light-transmitting composite material having excellent heat resistance, non-adhesion, antifouling properties, chemical resistance, weather resistance, scattering prevention, slidability and water repellency is obtained. SOLUTION: (a) at least one of a functional group-containing fluorine-containing ethylenic monomer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylate, a carboxyester group and an epoxy group; One to 0.05 to 30 mol% of one monomer and (b) 70 to 99.95 mol% of at least one monomer of the fluorine-containing ethylenic monomer having no functional group are used. A translucent composite material which maintains transparency by applying a material comprising a functional group-containing fluorine-containing ethylenic polymer obtained by polymerization to a translucent substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to heat resistance, weather resistance,
Fluoropolymers with excellent non-tackiness, antifouling properties, chemical resistance, slidability, water repellency, etc. and especially adhesion to translucent substrates such as glass The present invention relates to a light-transmitting composite material applied to

[0002]

2. Description of the Related Art Transparent base materials such as glass and polycarbonate are used not only for architectural window glasses and automobile windshields, but also for cookware such as microwave ovens and gas tables, light bulbs, bulbs and the like. It is used in various applications such as chemical bottles, and it is desired to impart performance such as weather resistance, antifouling property, heat resistance, non-adhesion, anti-scattering property, and chemical resistance according to each application. ing.

On the other hand, fluorine-containing resins are particularly excellent in heat resistance, antifouling properties, non-adhesion, chemical resistance, and weather resistance. Films and coatings formed of coatings using them are the most suitable materials. .

However, the fluorine-containing resin has an essential problem that its adhesiveness to a substrate such as glass or synthetic resin is not sufficient due to its excellent non-adhesiveness.

When a fluororesin paint is adhered to a glass substrate or the like that requires transparency, the surface of the substrate is treated with a silane coupling agent, or a silicone resin is added to the fluororesin paint to adhere. (JP-B-54-42366, JP-A-5-1777)
No. 68), but the adhesion is insufficiently improved, and the heat resistance is reduced.
Easy to color.

[0006] In particular, Japanese Patent Publication No. 3-80741 discloses a bulb coated with a powder of a fluorine-containing resin.
The application of a primer such as a silane coupling agent and the application of a fluorine-containing resin powder containing glass fiber are complicated, and there are problems such as roughening, reduction in light transmission due to glass fiber, and coloring of the primer. In the first place, the adhesive force itself is insufficient.

On the other hand, as a fluorine-containing resin paint, those obtained by copolymerizing a hydrocarbon (non-fluorine) monomer containing a functional group such as a hydroxyl group or a carboxyl group have been studied. And heat resistance (for example, 200 to 350
° C) and non-adhesiveness, chemical resistance and slidability are difficult to use.

That is, when a hydrocarbon (non-fluorine) monomer containing a functional group is copolymerized, thermal decomposition is apt to occur from the monomer component during processing or use at a high temperature, and the coating film is destroyed. In addition, coloring, foaming, peeling, and the like occur, the transparency is reduced, and the excellent performance of the fluororesin is lowered, so that the purpose of the fluororesin coating cannot be achieved.

Further, fluoropolymers generally have insufficient mechanical strength and dimensional stability and are expensive in price.
Therefore, in order to minimize these disadvantages and maximize the advantages inherent in the fluoropolymer, application in the form of a film has been studied.

However, the fluoropolymer inherently has low adhesive strength as described above, and it is difficult to directly adhere the fluoropolymer in the form of a film to another material (substrate).
For example, even if the bonding is attempted by heat fusion, the bonding strength is insufficient, or even if there is a certain degree of bonding strength, the bonding strength tends to vary depending on the type of the base material, and the reliability of the bonding is insufficient. Was often.

As a method for bonding the fluoropolymer film and the substrate, 1. A method of physically roughening the surface of the substrate by sandblasting or the like; 2. A method of subjecting the fluorine-containing resin film to a chemical treatment such as sodium etching, a surface treatment such as a plasma treatment, or a photochemical treatment; A method of bonding using an adhesive has been mainly studied.
Separate processing steps are required, complicating the steps and reducing productivity. In addition, the type and shape of the substrate are limited. further,
The obtained adhesive strength is also insufficient, and the inherent performance of the fluororesin tends to decrease. Also, the color of the treated film is large,
The transparency of the resulting composite material is reduced. Further, the method using a chemical such as sodium etching has a problem in safety.

Various studies have been made on the above-mentioned adhesive. General hydrocarbon-based (non-fluorine-based) adhesives have insufficient adhesiveness and insufficient heat resistance, and generally require a high-temperature molding or processing of a fluoropolymer film. In bonding processing conditions, it can not stand,
Decomposition causes peeling, coloring, and reduced transparency. The composite using the adhesive also has heat resistance of the adhesive layer, chemical resistance,
Since the water resistance is insufficient, the adhesive strength cannot be maintained due to a temperature change or an environmental change, resulting in a lack of reliability.

On the other hand, studies have been made on adhesion by an adhesive composition using a fluorine-containing polymer having a functional group.

For example, a hydrocarbon monomer having a carboxyl group, a carboxylic anhydride residue, an epoxy group, or a hydrolyzable silyl group represented by maleic anhydride or vinyltrimethoxysilane is grafted onto a fluoropolymer. Reports of using a polymerized fluoropolymer as an adhesive (for example, JP-A-7-18035, JP-A-7-25952)
JP-A-7-25954, JP-A-7-173230
JP-A-7-173446, JP-A-7-17344
No. 7 publications) and adhesion of a fluorine-containing copolymer obtained by copolymerizing a hydrocarbon monomer containing a functional group such as hydroxylalkyl vinyl ether with tetrafluoroethylene or chlorotrifluoroethylene, and an isocyanate-based curing agent There is a report (for example, Japanese Patent Application Laid-Open No. Hei 7-228848) in which a curable composition is cured and used as an adhesive between a vinyl chloride resin and ETFE subjected to corona discharge treatment.

An adhesive composition using a fluororesin obtained by graft-polymerizing or copolymerizing a hydrocarbon-based functional group monomer has insufficient heat resistance, and is processed at a high temperature to form a composite with a fluororesin film. At times or when used at high temperatures, decomposition or foaming may occur, resulting in a decrease in adhesive strength, peeling or coloring, and a decrease in transparency. In the adhesive composition described in JP-A-7-228848, the fluororesin film requires corona discharge treatment.

As described above, there is no light-transmitting composite material that is firmly bonded to a light-transmitting substrate such as glass while maintaining transparency.

[0017]

SUMMARY OF THE INVENTION In view of the above facts, an object of the present invention is to provide a transparent polymer material having excellent adhesion to a substrate without requiring a complicated process. An object of the present invention is to provide a light-transmitting composite material applied to a light-transmitting substrate while maintaining the light-transmitting property.

The translucent composite material of the present invention is further excellent in heat resistance, non-adhesion, antifouling properties, chemical resistance, weather resistance, scattering prevention, slidability and water repellency.

[0019]

SUMMARY OF THE INVENTION The present invention provides (a) a functional group containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylate, a carboxyester group and an epoxy group. 0.05 to 30 at least one kind of fluorine-containing ethylenic monomer
(B) at least one monomer of the above-mentioned fluorine-containing ethylenic monomer having no functional group and 70 to 99.95.
The present invention relates to a light-transmitting composite material that maintains transparency by applying a material comprising a functional group-containing fluorine-containing ethylenic polymer obtained by copolymerizing a polymer with a mole% of the same to a light-transmitting substrate.

In this case, the functional group-containing fluorine-containing ethylenic monomer (a) is represented by the formula (1): CX ₂ CX ¹ -R _f -Y (1) (where Y is -CH ₂ OH) , -COOH, a carboxylate salt, a carboxyester group or an epoxy group, X and X ¹ are the same or different and are a hydrogen atom or a fluorine atom,
R _f is a divalent fluorinated alkylene group having 1 to 40 carbon atoms,
A fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group containing an ether group having 1 to 40 carbon atoms or a fluorine-containing oxyalkylene group containing an ether bond having 1 to 40 carbon atoms) Preferably, it is a fluorine-containing ethylenic monomer containing various functional groups.

The fluorine-containing ethylenic monomer having no functional group (b) is preferably tetrafluoroethylene.

The fluorine-containing ethylenic monomer (b) having no functional group is preferably a tetrafluoroethylene 85-
99.7 mol% and formula (2): CF ₂ ＝ CF—R _f ¹ (2) (where R _f ¹ is CF ₃ or OR _f ² (R _f ² is carbon number 1 to
5 perfluoroalkyl group)
It is preferably a mixed monomer of up to 15 mol%.

Further, the fluorine-containing ethylenic monomer (b) having no functional group is preferably tetrafluoroethylene 40 to
It is preferably a mixed monomer of 80 mol%, 20 to 60 mol% of ethylene, and 0 to 15 mol% or less of other copolymerizable monomers.

The functional group-containing fluorine-containing ethylenic monomer (a) is 0.01 to 30 mol%, and the fluorine-containing ethylenic monomer having no functional group (b) is vinylidene fluoride 70 to 70%. It is preferable to apply a material comprising a functional group-containing fluorine-containing ethylenic polymer obtained by copolymerizing 99.9 mol% to the translucent substrate.

The fluorine-containing ethylenic monomer (b) having no functional group is a mixed monomer of 70 to 99 mol% of vinylidene fluoride and 1 to 30 mol% of tetrafluoroethylene, A mixed monomer of 50-99 mol% of vinylidene, 0-30 mol% of tetrafluoroethylene and 1-20 mol% of chlorotrifluoroethylene, or 60-99 mol% of vinylidene fluoride and 0-tetrafluoroethylene
It is preferably a mixed monomer of ３３33 mol% and 1 フ ル オ ロ 10 mol% of hexafluoropropylene.

It is preferable that the functional group-containing fluorine-containing ethylenic polymer is applied to a transparent substrate in the form of a paint.

It is preferable that the functional group-containing fluorine-containing ethylenic polymer is applied to a transparent substrate in the form of an aqueous dispersion.

Preferably, the functional group-containing fluorine-containing ethylenic polymer is applied to a light-transmitting substrate in the form of a powder coating.

Preferably, the functional group-containing fluorine-containing ethylenic polymer is applied to a transparent substrate in the form of a film.

It is preferable that the light-transmitting substrate is a glass substrate.

It is preferable that the light-transmitting substrate is a transparent resin substrate.

Preferably, the light-transmitting substrate is a polycarbonate.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of repeated studies to achieve the above object, the present inventor has found that the inherent heat resistance of a fluoropolymer,
It has been found that it can be directly bonded to a transparent substrate such as glass without losing weather resistance, antifouling property, non-adhesiveness, and water repellency, and as a result, it is possible to obtain a composite material that maintains transparency. Was.

The light-transmitting composite material of the present invention comprises (a) a functional group containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylate, a carboxylester group and an epoxy group. 0.05 to 30 at least one kind of fluorine-containing ethylenic monomer
(B) at least one monomer of the above-mentioned fluorine-containing ethylenic monomer having no functional group and 70 to 99.95.
In this case, a material comprising a fluorine-containing ethylenic polymer having a functional group obtained by copolymerization with a mole% is applied to a light-transmitting substrate.

The material comprising the functional group-containing fluorine-containing polymer is applied in the form of a paint or a film to a transparent substrate such as glass or transparent resin, using an adhesive, treating the surface of the substrate, and forming a primer layer. It has surprisingly strong adhesion even without forming and further adding an adhesive component to the material.

The functional group-containing fluorine-containing polymer used for obtaining the composite material of the present invention is prepared by using the functional group-containing fluorine-containing ethylenic monomer (a) and containing the functional group-free fluorine-containing monomer. It is important to copolymerize with the fluoroethylenic monomer (b) and to introduce a functional group into the fluoropolymer, whereby various types of light-transmitting groups which have been insufficient or impossible in the past. It can provide excellent adhesion directly to the material surface. That is, even a functional group-containing fluoropolymer has excellent heat resistance as compared with a copolymer obtained by copolymerizing a non-fluorine-based functional group-containing monomer, and is processed at a high temperature (eg, 200 to 400 ° C.). It is possible to form a coating layer on the base material, which minimizes thermal decomposition at the time, can provide a large adhesive strength, and can prevent coloration, transparency deterioration, foaming, pinholes and leveling defects. it can. Also, when using composite materials at high temperatures, maintain adhesiveness and transparency,
Further, defects of the coating layer such as coloring, whitening, foaming, and pinholes are less likely to occur.

In addition, the functional group-containing fluoropolymer includes:
As such, it has not only adhesive properties, but also excellent properties such as heat resistance, weather resistance, antifouling properties, non-adhesion, chemical resistance, and low friction properties of fluoropolymers. While maintaining these superior properties can be provided without degradation.

Next, the functional group-containing fluorine-containing ethylenic copolymer which is a material of the composite material of the present invention will be described.

The functional group of the functional group-containing fluorine-containing ethylenic polymer is at least one selected from a hydroxyl group, a carboxyl group, a carboxylate, a carboxylester group, and an epoxy group. It can give adhesion to the material. The type and combination of the functional groups are appropriately selected depending on the type, purpose and application of the surface of the substrate, but those having a hydroxyl group are most preferable in terms of heat resistance.

The functional group-containing fluorinated ethylenic monomer (a), which is one of the components constituting the functional group-containing fluorinated ethylenic polymer, is represented by the following formula (1): CX ₂ = CX ¹ -R _f -Y (1) (in the formula, Y is -CH ₂ OH, -COOH, carboxylate, carboxylic ester group or epoxy group, X and X ¹ are the same or different hydrogen atom or a fluorine atom,
R _f is a divalent fluorinated alkylene group having 1 to 40 carbon atoms,
A fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group containing an ether group having 1 to 40 carbon atoms, or a fluorine-containing oxyalkylene group containing an ether bond having 1 to 40 carbon atoms) It is preferably a fluorine-containing ethylenic monomer.

Specific examples of the functional group-containing fluorine-containing ethylenic monomer (a) include the following formula (3): CF ₂ ＣＦCF—R _f ³ —Y (3) R _f ³ is the same as Y in 1) and has 1 to 4 carbon atoms.
0 divalent fluorinated alkylene group or OR _f ⁴ (R _f ⁴ is a divalent fluorinated alkylene group having 1 to 40 carbon atoms or a divalent fluorinated alkylene group containing an ether bond having 1 to 40 carbon atoms) ], Formula (4): CF ₂ = CFCF ₂ -OR _f ⁵ -Y (4) [wherein, Y is the same as Y in formula (1), and R _f ⁵ has 1 to 3 carbon atoms.
9 divalent fluorine-containing alkylene groups or 1 to 39 carbon atoms
Represents a divalent fluorine-containing alkylene group containing an ether bond of the formula], formula (5): CH ₂ ＣＦCFCF ₂ —R _f ⁶ —Y (5) wherein Y is the same as Y in the formula (1); R _f ⁶ has 1 to 3 carbon atoms
9, a divalent fluorine-containing alkylene group, or OR _f ⁷ (R _f ⁷
Represents a C1-C39 divalent fluorinated alkylene group or a C1-C39 divalent fluorinated alkylene group containing an ether bond) or a formula (6): CH ₂ ＣＨCH—R _f ⁸ -Y (6) [in the formula, Y is the same as Y in formula (1), R _f ⁸ is 1 to 4 carbon atoms
And a divalent fluorine-containing alkylene group of 0].

The fluorine-containing ethylenic monomer having a functional group of the formulas (3) to (6) has relatively good copolymerizability with the fluorine-containing ethylenic monomer (b) having no functional group. This is preferred because it does not significantly reduce the heat resistance of the copolymer obtained.

Among these, the formulas (3) and (5) are considered from the viewpoints of copolymerizability with the fluorine-containing ethylenic monomer (b) having no functional group and heat resistance of the obtained polymer. The compound of the formula (5) is preferred, and the compound of the formula (5) is particularly preferred.

As the functional group-containing fluorine-containing ethylenic monomer represented by the formula (3),

[0045]

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And the like.

The functional group-containing fluorine-containing monomer represented by the formula (4) includes

[0048]

Embedded image

And the like.

The functional group-containing fluorine-containing monomer represented by the formula (5) includes

[0051]

Embedded image

And the like.

The functional group-containing fluorine-containing monomer represented by the formula (6) includes

[0054]

Embedded image

And the like.

Others

[0057]

Embedded image

And the like.

The fluorine-containing ethylenic monomer (b) which does not contain a functional group and which is copolymerized with the functional group-containing fluorine-containing ethylenic monomer (a) can be appropriately selected from known monomers. Provides polymer with heat resistance, heat resistance, antifouling property, non-adhesion, chemical resistance and low friction.

Specific fluorinated ethylenic monomer (b)
As tetrafluoroethylene, formula (2): CF ₂
ＣＦCF—R _f ¹ [R _f ¹ represents CF ₃ or OR _f ² (R _f ² represents a C 1-5 perfluoroalkyl group)], chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, Hexafluoropropylene, hexafluoroisobutene,

[0061]

Embedded image

(Wherein X ² is selected from a hydrogen atom, a chlorine atom or a fluorine atom, n is an integer of 1 to 5) and the like.

In addition to the fluorine-containing ethylenic monomer having a functional group (a) and the fluorine-containing ethylenic monomer having no functional group (b), weather resistance, heat resistance and antifouling property An ethylenic monomer having no fluorine atom may be copolymerized as long as the non-adhesiveness is not reduced. In this case, the ethylenic monomer having no fluorine atom is preferably selected from ethylenic monomers having 5 or less carbon atoms in order not to lower the weather resistance and heat resistance. , 1-butene, 2-butene and the like.

The content of the functional group-containing fluorinated ethylenic monomer (a) in the functional group-containing fluorinated ethylenic polymer (A) used in the present invention depends on the total amount of the monomers in the polymer. It is 0.05 to 30 mol%. The content of the functional group-containing fluorine-containing ethylenic monomer (a) depends on the type, shape, coating method, film forming method, conditions,
It is appropriately selected depending on the purpose and use, but is preferably 0.05 to 20 mol%, particularly preferably 0.1 to 1 mol%.
0 mol%.

If the content of the functional group-containing fluorine-containing ethylenic monomer (a) is less than 0.05%, it is difficult to obtain sufficient adhesiveness to the surface of the substrate, and it is difficult to obtain a change in temperature and penetration of chemicals. When used for the exterior, peeling or the like is likely to occur due to climate or weather change. On the other hand, if it exceeds 30 mol%, heat resistance, weather resistance, and chemical resistance are reduced, and poor adhesion, coloring, foaming, pinholes, etc. occur at the time of firing at a high temperature or when used at a high temperature. Lower or
It is easy to cause peeling of the coating layer and elution of thermal decomposition products.

Preferred examples of the functional group-containing fluorine-containing ethylenic polymer used in the present invention are as follows.

(I) Polymer (I) comprising 0.05 to 30 mol% of a functional group-containing fluorine-containing ethylenic monomer (a) and 70 to 99.95 mol% of tetrafluoroethylene (reactive P
TFE).

This polymer is most excellent in heat resistance, weather resistance, antifouling property, chemical resistance and non-adhesiveness, and further excellent in slidability (low friction property, wear resistance). .

(II) The functional group-containing fluorine-containing ethylenic monomer (a) is used in an amount of 0.05 to 30 mol% based on the total amount of the monomers.
And 85 to 99.7 mol% of tetrafluoroethylene with respect to the total amount of the monomer excluding the monomer (a) and the formula (2): CF ₂ = CF-R _f ¹ (2) [ R _f ¹ is ^{_{CF 3, OR f 2 (R}} f 2 is a perfluoroalkyl group having 1 to 5 carbon atoms) polymer of monomer 0.3 to 15 mole% represented by] selected from (II) . For example, a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer having a functional group (reactive PFA) or a tetrafluoroethylene-hexafluoropropylene polymer having a functional group (reactive FEP).

This polymer is the same as the reactive PTFE of the above (I).
It has almost the same heat resistance, weather resistance, stain resistance, chemical resistance, non-adhesiveness, and transparency, and can be melt-molded, and becomes transparent by heat even when applied in the form of paint. It is excellent in that the surface can be smoothed.

(III) a monomer containing the functional group-containing fluorine-containing ethylenic monomer (a) in an amount of 0.05 to 30 mol% based on the total amount of the monomer and further excluding the monomer (a) , 40 to 80 mol% of ethylene, 20 to 60 mol% of ethylene, and other copolymerizable monomer 0
To 15 mol% of the polymer (III) (ethylene-tetrafluoroethylene polymer having a functional group (reactive ETF)
E)).

This polymer has excellent heat resistance, antifouling property and weather resistance, is excellent in transparency, has excellent mechanical strength, is hard and tough, and has a melt fluidity. Because it is excellent, it is excellent in that it can be easily formed and combined with other base materials (such as lamination).

(IV) 0.05 to 30 mol% of a functional group-containing fluorine-containing ethylenic monomer (a) and vinylidene fluoride 70
（99.9 mol% of polymer (IV) (reactive PVd
F).

The polymer (IV) has particularly excellent mechanical strength, while maintaining excellent weather resistance of the fluorine-containing resin, and is hard and tough, and has excellent melt fluidity. Therefore, it is excellent in that it can be easily formed at a relatively low temperature and can be easily combined with another polymer (such as lamination).

(V) 0.01 to 3 with respect to the total amount of the monomers
0 mol% of a functional group-containing fluorine-containing ethylenic monomer (a)
And a mixed monomer of 70 to 99 mol% of vinylidene fluoride and 1 to 30 mol% of tetrafluoroethylene, based on the total amount of the monomers excluding the monomer (a); A mixed monomer of 50 to 99 mol% of vinylidene fluoride, 0 to 33 mol% of tetrafluoroethylene, and 1 to 20 mol% of chlorotrifluoroethylene, based on the total amount of the monomers excluding, or the monomer (a) Polymer (V) (reaction) with a mixed monomer of 60 to 99 mol% of vinylidene fluoride, 0 to 30 mol% of tetrafluoroethylene, and 1 to 10 mol% of hexafluoropropylene based on the total amount of the monomers excluding VdF copolymer).

Since this polymer (V) has a low melting point while maintaining the excellent weather resistance of the fluorine-containing resin, the polymer (V) has a temperature of room temperature to 100 ° C.
Processing at a temperature as low as possible is possible, and it is particularly preferable in that a film can be formed and formed at a low temperature in the form of a paint. As a result, a composite with a non-fluoropolymer having no heat resistance (such as lamination) is preferable. Also more flexible,
Excellent flexibility and transparency. The reactive group of the fluoropolymer of the present invention is preferable because it can easily crosslink not only with an adhesive function but also with a curing agent and can improve mechanical properties.

The functional group-containing fluorine-containing polymer is prepared by polymerizing the above-mentioned functional group-containing fluorine-containing ethylenic monomer (a) and the fluorine-containing ethylenic monomer having no functional group (b) by a known method. It can be obtained by copolymerizing by a method. Among them, a method based on radical copolymerization is mainly used. That is, the means for initiating the polymerization is not particularly limited as long as it proceeds radically, but is initiated by, for example, an organic or inorganic radical polymerization initiator, heat, light or ionizing radiation. As the type of polymerization, solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, or the like can be used. The molecular weight is controlled by the concentration of the monomer used for the polymerization, the concentration of the polymerization initiator, the concentration of the chain transfer agent, and the temperature. The composition of the resulting copolymer can be controlled by the composition of the charged monomers.

The functional group-containing fluorine-containing ethylenic polymer described above can take various forms as a material to be applied to a substrate. Typically, it is in the form of a paint material or a film material, but may be in the form of a molded product.

In the present invention, the functional group-containing fluorine-containing ethylenic polymer is applied to a light-transmitting substrate in the form of a paint,
A composite material having excellent transparency can be obtained.

In the present invention, when the composition is applied to a substrate in the form of a coating, the composition may be in the form of an aqueous dispersion, an organic solvent dispersion, a powder (including a granulated substance), an organic solvent soluble material, an organosol, or an aqueous emulsion of an organosol. Can be taken. Among these, it is preferable to apply in the form of an aqueous dispersion or a powder (powder coating) from the viewpoint of environment and safety.

The paint may be applied in such a manner that the functional group-containing fluorine-containing ethylenic polymer (A) exhibits a property of being excellent in adhesion to a substrate, and may be a single layer.
Further, the fluoropolymer of the present invention itself may be used as a primer layer.

The aqueous dispersion for a fluorine-containing paint according to the present invention is obtained by dispersing the particles of the functional group-containing fluorine-containing ethylenic polymer in water. By introducing a functional group into the fluorinated polymer, the dispersion stability of the fine particles in the aqueous dispersion is improved, and a paint having good storage stability is obtained. Further, the leveling property and the transparency of the coating film after application are improved. .

The aqueous dispersion is preferably a composition in which fine particles of the polymer of 0.01 to 1.0 μm are dispersed in water. In general, a surfactant for stabilizing the dispersion may be incorporated therein. Pigments, dyes, surfactants, and defoaming agents which are usually used in a range that does not significantly reduce heat resistance, chemical resistance, non-adhesiveness, and low friction in the aqueous dispersion, and furthermore do not significantly reduce transparency. And additives such as a viscosity modifier and a leveling agent.

The aqueous dispersion for a fluorine-containing paint can be produced by various methods. Specifically, for example, a method of finely pulverizing a fluoropolymer powder having a functional group obtained by a suspension polymerization method or the like and uniformly dispersing it in an aqueous dispersion medium with a surfactant, Emulsion polymerization produces a fluorinated aqueous dispersion at the same time as polymerization, and further incorporates surfactants and additives if necessary. A method of directly producing an aqueous dispersion by an emulsion polymerization method from the powder size) is preferred.

The polymer concentration of the aqueous dispersion varies depending on the target film thickness, the concentration of the paint, the viscosity, the coating method, and the like.
Usually, it may be selected within a range of about 5 to 70% by weight.

[0086] The coating method is not particularly limited.
After application by spray method, roll coating method, etc., it is dried according to the type of polymer and fired at a temperature above the melting point of the polymer and below the decomposition temperature to form a film, or at room temperature or below the melting point of the polymer. The film can be formed by heating the film.

The thickness of the coating film may be appropriately selected depending on the application, purpose, base material and the like.
m, preferably 5 to 100 μm.

The powder coating according to the present invention comprises the above functional group-containing fluorine-containing ethylenic polymer powder. As specific examples of the functional group-containing fluorine-containing ethylenic polymer used in the powder coating, the above-mentioned polymers (I) to (V) can be preferably used depending on the use, purpose, base material and the like.

In particular, weather resistance, heat resistance, antifouling property, non-adhesiveness,
Reactive PFA or reactive FEP (II) is preferred from the viewpoint of corrosion resistance, chemical resistance, and transparency, and reactive ETFE (III) is preferred from the viewpoint of weather resistance, antifouling property, processability, and transparency.

The fluorine-containing powder coating material has a particle size of 10 μm to 100 μm.
A powder or granule having a shape of 0 μm and an apparent density of 0.3 to 1.2 g / cc is preferably used.

The fluorine-containing powder coating material has such a range that the performance of the fluororesin such as heat resistance, weather resistance, chemical resistance, non-adhesion and antifouling property is not significantly reduced, and further that the transparency is not significantly reduced. For example, pigments such as carbon powder, titanium oxide and cobalt oxide, powders such as glass fiber and carbon fiber, reinforcing agents such as mica, amine-based antioxidants, organic sulfur-based compounds, organic tin-based antioxidants, and phenol-based Additives such as an antioxidant, a heat stabilizer such as metal soap, a leveling agent, and an antistatic agent can be appropriately compounded.

The above-mentioned additives may be mixed with the fluorine-containing powder coating material in a powder form (dry) or in a slurry form (wet). preferable. As a mixing device, for example, a sand mill, V
Conventional mixers and pulverizers such as a mold blender and a ribbon blender can be used.

The coating of the fluorine-containing powder coating is generally carried out by a method such as electrostatic spraying, immersion in a fluidized bed, or rotary lining. After that, depending on the type of the polymer, the temperature is higher than the melting point of the polymer and lower than the decomposition temperature. Sintering, a good coating film can be formed.

Generally, in the case of electrostatic powder coating, a film thickness of 10 to 10
200 μm, in case of rotary lining, film thickness 200-1
A 000 μm coating is formed.

Further, the functional group-containing fluorine-containing ethylenic polymer used in the above-mentioned material for a fluorine-containing coating material is a fluororesin which does not have a functional group on the surface of a base material such as metal or glass by utilizing its adhesiveness. Can also be used as a primer layer for fluorine-containing paints having good heat resistance when coating.

The primer for fluorine-containing paint comprises the above functional group-containing fluorine-containing ethylenic polymer.

As the primer, those similar to the above-mentioned fluoropolymers can be specifically used, such as the type of the surface of the substrate and the type of the fluoropolymer to be coated via the primer (the type of the top coat). Is selected as appropriate. In general, the primer for a fluorine-containing paint is preferably one having a structure equivalent to the structure of the fluorine-containing polymer coated thereon and containing a functional group.

This combination has good compatibility between the fluorine-containing polymer used for the primer and the fluorine-containing polymer coated thereon, so that not only the adhesion to the surface of the substrate but also the primer layer Interlayer adhesion strength with the top coat layer can also be good. Further, even when used at a high temperature, unlike a case where a primer to which another resin component is added is used, delamination, cracks, pinholes, and the like due to differences in the thermal shrinkage of the polymer are unlikely to occur. Also, since the entire coating film is composed of a fluoropolymer in the first place, it can sufficiently cope with applications having transparency and vivid coloring, and furthermore, a fluoropolymer layer having no functional group on the outermost surface of the coating film. Excellent weather resistance, heat resistance, antifouling property, chemical resistance, non-adhesiveness, and low frictional property for forming the film.

Fluorine-containing polymers containing no functional group for use in the top coat layer include PTFE, PFA, FEP,
Examples include ETFE, PVdF, and VdF-based copolymers.

As the primer for a fluorine-containing paint, specifically, the above-mentioned functional group-containing fluorine-containing ethylenic polymer can be used. When the base material is coated with PTFE, reactive PTFE (I), Reactive PFA or FEP
It is preferable to use a primer selected from (II) as the primer, and particularly to use a hot-melt reactive PFA or FEP.
It is more preferable to use (II) as a primer because it can be firmly hot-melted and adhered to the surface of the substrate by firing. When the substrate is coated with PFA or FEP, it is preferable to use reactive PFA or FEP (II) as the primer. Further, when the base material is coated with ETFE, the use of reactive ETFE (III) as a primer is particularly preferred.
It is preferable from the viewpoint of adhesiveness and transparency. Further, the base material is further made of a VdF-based copolymer (PVdF, VdF-based copolymer, etc.)
When coated with reactive PVdF (IV) or reactive Vd
It is preferable to use the F copolymer (V) as a primer from the viewpoint of adhesiveness and transparency.

The coating method using the primer layer includes: (first step) a step of applying a primer for a fluorinated paint made of the fluorinated polymer having a functional group to the surface of a base material; (second step) On the primer layer formed in one step,
A step of applying a fluorinated paint made of a fluorinated polymer having no functional group; and (3) a step of firing the laminate obtained in the first and second steps. A fluoropolymer coating method can be preferably used. Furthermore, the primer layer applied in the first step may be touch-dried at 80 to 150 ° C. for about 5 to 30 minutes, and then proceed to the next second step (two coats and one bake), or the primer layer For example, after firing at a high temperature equal to or higher than the melting temperature, the process may proceed to the second step (two coats and two bake).

In the first step, the method of applying the primer is appropriately selected according to the form of the primer. For example, when the fluorine-containing primer is in the form of an aqueous dispersion, spray coating, spin coating, brushing, dipping, etc. A method is used. In the case of a powder coating, a method such as an electrostatic coating method, a fluid immersion method, or a rotary lining method is used.

The thickness of the primer layer may vary depending on the purpose, application, type of substrate surface, and form of coating.
It is 50 μm, preferably 2 to 20 μm. As described above, since the primer generally has a low film thickness, it is preferable to apply the primer in the form of an aqueous dispersion by spray coating or the like.

The method of applying the coating of the fluoropolymer containing no functional group on the primer layer in the second step is appropriately selected depending on the type of the fluoropolymer, the form of the coating, the purpose and the use. In the case of dispersions and organic solvent dispersions, spray coating, brushing, roll coating, spin coating, etc. are generally performed. Painted in the manner described above.

The coating film of the fluoropolymer in this step is completely different depending on the purpose, application and coating method, but is generally 1 to 100 μm, preferably 5 to 100 μm by spray coating or the like.
When the thickness is to be increased using a powder coating, the thickness is about 20 to 2000 μm by the electrostatic coating method.
Coating with a thickness of 0.3 to 10 mm is possible by the rotary lining method.

The firing conditions in the third step are appropriately selected depending on the type (composition, melting point, etc.) of the fluoropolymer of the primer layer and the top layer thereon, but are generally higher than the melting points of both fluoropolymers. Fired at temperature. The sintering time varies depending on the sintering temperature, but is 5 minutes to 3 hours, preferably 10 to
It takes about 30 minutes. For example, PTFE, PFA, FE
When coating with P or the like, it is fired at 320 to 400 ° C., preferably 350 to 400 ° C., when coating with PVdF, 200 to 280 ° C., when coating with a VdF copolymer, copolymerization is performed. Although various selections can be made depending on the composition, the film is generally formed at room temperature to 200 ° C.

Next, a technique for producing a composite material by applying the functional group-containing fluorine-containing ethylenic polymer in the form of a film to a light-transmitting substrate will be described.

The advantages applied in the form of a film are as follows.

A film made of a functional group-containing fluorine-containing ethylenic polymer can be bonded by hot-pressing by sandwiching it on or between substrates without the need for an indispensable applicator for a hot-melt adhesive. Is also advantageous.

Further, since a uniform adhesive layer is formed on the entire surface of the base material, uniform adhesive strength without uneven bonding can be obtained, and it is possible to cope with base materials having no compatibility or poor compatibility.

Further, it can be used by being cut into various shapes, the working loss is small, the working environment is good, and the cost is advantageous.

The fluorine-containing polymer film of the present invention is preferably a fluorine-containing polymer film obtained by molding the above-mentioned functional group-containing fluorine-containing ethylenic polymer, and is subjected to surface treatment and use of a general adhesive. If not, it can be adhered to a translucent substrate, which can impart the excellent properties of the fluoropolymer to the substrate.

From the functional group-containing fluoropolymers, it is possible to produce an adhesive film using various adhesives according to the use and purpose, the film production process, and the adhesion method. Has heat resistance, chemical resistance, mechanical properties, non-adhesiveness, transparency, etc., and is capable of efficient film forming typified by melt molding, etc. It is possible to make it possible, and it is melted by various thermocompression bonding methods,
Being able to adhere while maintaining transparency,
For example, the polymer (II) (reactive PFA or reactive FEP) or the polymer (III) (reactive ET)
FE) is preferred. Further, the polymer (IV) can be processed at a lower temperature and has transparency, weather resistance, antifouling properties, and the like.
(Reactive PVdF), the polymer (V) (reactive VdF)
(Copolymer). As the functional group, a hydroxyl group is particularly preferable from the viewpoint of heat resistance.

The thickness of the fluorine-containing film is selected depending on the purpose and application, and is not particularly limited.
m, preferably 20 to 500 μm, particularly preferably 40 to 300 μm.

A film that is too thin requires a special manufacturing method, is difficult to handle during the bonding operation, and is liable to cause wrinkles, breakage, and poor appearance.
In some cases, the mechanical strength, weather resistance and chemical resistance are also insufficient. Films that are too thick are disadvantageous in terms of transparency, cost, and workability when joining and integrating.

In the present invention, the fluorine-containing polymer film may be used alone, or the above-mentioned fluorine-containing ethylenic polymer film having a functional group (adhesive layer) and the fluorine-containing ethylenic polymer film having no functional group may be used. It can also be applied in the form of a fluoropolymer laminated film obtained by laminating a united film (surface layer).

That is, on one side, a layer made of a functional group-containing fluorine-containing ethylenic polymer gives adhesion to another base material, and on the other side, a layer made of a general fluorine-containing polymer is used. The surface of the functional group-containing fluorine-containing ethylenic polymer is brought into contact with a substrate and adhered by an operation such as thermocompression bonding, thereby providing excellent weather resistance and antifouling properties of the fluorine-containing polymer.
Excellent properties such as non-adhesion, chemical resistance, and low friction can be imparted to a composite material including a light-transmitting substrate.

In the present invention, the thickness of the two-layer fluoropolymer laminated film is selected depending on the purpose and application.
Although not particularly limited, 20 to 5000 μm in total for two layers
m, preferably 40 to 1000 μm, particularly preferably 100 to 500 μm.

The thickness of each layer is 5 to 1000 μm for the adhesive layer,
A fluoropolymer layer (surface layer) having a thickness of about 15 to 4995 μm can be used, preferably an adhesive layer of 10 to 500 μm,
Surface layer 30 to 990 μm, particularly preferably adhesive layer 10
２００200 μm, surface layer 90-490 μm.

After the film for the adhesive layer is adhered to the substrate, the film for the surface layer may be covered.

In the functional group-containing fluoropolymer film,
It is also possible to incorporate appropriate reinforcing agents, fillers, stabilizers, ultraviolet absorbers, pigments and other additives as long as the transparency and the properties of the fluoropolymer itself are not impaired. With such additives, it is also possible to improve thermal stability, surface hardness, abrasion resistance, weather resistance, chargeability, and the like.

The fluorine-containing film of the present invention may be prepared by a hot-melt method, an extrusion method, a cutting method, a solvent casting, a powder, an aqueous or organic solvent dispersion, depending on the type of the polymer used and the shape of the target film. Can be obtained by various production methods such as a method of obtaining a film by applying a continuous film.

For example, a polymer comprising reactive PTFE which is difficult to be melt-molded can be molded by compression molding, extrusion molding (ram extrusion, paste extrusion and rolling, etc.), and reactive PFA, FEP. , ETFE, PVd
For polymers that can be melt-molded, such as F and VdF-based copolymers, compression molding, extrusion molding, and the like are employed. Melt extrusion molding is a preferred method, particularly from the viewpoint of productivity and quality.

[0124] The bonding and integration of the laminated film are carried out by laminating the respective forming films for the adhesive layer and the surface layer and compressing them, coating one of the forming films on the other, and multi-layer coextrusion. Thus, a method of achieving joining and integration at the same time as film formation can be adopted, and among them, a multilayer coextrusion molding method is preferable in terms of productivity and quality.

The adhesion of the functional group-containing fluoropolymer film to the substrate is achieved by heat activation by heating or the like, and more preferably hot-melt adhesion. Typical bonding methods include a hot roll method and a hot press method. In addition, there are a high frequency heating method, a micro method, a vacuum pressure bonding method (a vacuum press method, etc.), a pneumatic method, and the like. It can be appropriately selected depending on the state and type.

Examples of the light-transmitting substrate to which the functional group-containing fluorine-containing ethylenic polymer can adhere include a glass substrate and a transparent resin substrate.

The composition of the glass substrate is not particularly limited, and examples thereof include quartz glass, lead glass, alkali glass, and alkali-free glass. In addition, crystallized glass, foamed glass, heat ray reflecting glass, heat ray absorbing glass, Composite glass such as double glazing can also be used. Examples of the transparent resin substrate include a polycarbonate resin and an acrylic resin.

The present invention further relates to a weather-resistant composite material obtained by applying the light-transmitting composite material obtained by applying the fluoropolymer of the present invention to a light-transmitting substrate to an application requiring weather resistance.

That is, since the functional group-containing fluoropolymer used in the present invention not only has an adhesive property to a light-transmitting substrate, but also has excellent weather resistance unique to a fluoropolymer, the exterior glass building material It can be effectively used in fields requiring weather resistance such as civil engineering, such as dwelling and soundproof walls, and can provide a weather resistant composite material having excellent transparency.

The present invention further relates to a non-adhesive composite in which the translucent composite obtained by applying the fluoropolymer of the present invention to a translucent substrate is used for applications requiring non-adhesion.

That is, the functional group-containing fluoropolymer used in the present invention not only has an adhesive property to a light-transmitting substrate, but also has an excellent non-adhesive property against oil stains, burns, fingerprints, etc. peculiar to the fluoropolymer. Since it has properties, it can be effectively used in fields requiring non-adhesion, such as cooking appliances and home appliances, and can provide a non-adhesive composite material having excellent transparency.

The present invention further relates to an antifouling composite in which the translucent composite obtained by applying the fluoropolymer of the present invention to a translucent substrate is applied to applications requiring antifouling properties.

That is, the functional group-containing fluoropolymer used in the present invention not only has an adhesive property to a light-transmitting substrate, but also has a characteristic characteristic of a fluoropolymer, such as dust and dirt, and tobacco smoke. It has excellent antifouling properties, so it can be effectively used in fields that require antifouling properties, such as interior and exterior building materials, housing equipment, kitchen housing, and home appliance parts, and has excellent transparency. To provide an antifouling composite.

The present invention further relates to a chemical-resistant composite in which the light-transmitting composite obtained by applying the fluoropolymer of the present invention to a light-transmitting substrate is used for applications requiring chemical resistance.

That is, the functional group-containing fluoropolymer used in the present invention not only has adhesiveness to a light-transmitting substrate, but also has excellent chemical resistance to acids, alkalis and organic solvents peculiar to the fluoropolymer. Therefore, it can be effectively used in fields requiring chemical resistance, such as semiconductor-related equipment, containers, and liquid crystal-related equipment, and can provide a chemical-resistant composite material having excellent transparency.

The present invention further relates to a scattering-preventing composite material in which the light-transmitting composite material obtained by applying the fluoropolymer of the present invention to a light-transmitting substrate is applied to an application requiring the scattering prevention property.

That is, the functional group-containing fluoropolymer used in the present invention not only has an adhesive property to a light-transmitting substrate, but also has excellent heat resistance and flame retardancy unique to a fluoropolymer. It can be effectively used for the purpose of preventing scattering of glass, such as glass, lighting equipment, and glass building materials, and can provide an anti-scattering composite material having excellent transparency.

The present invention further relates to a water-repellent composite in which the light-transmitting composite obtained by applying the fluoropolymer of the present invention to a light-transmitting substrate is used for applications requiring water repellency.

In other words, the functional group-containing fluoropolymer used in the present invention not only has an adhesive property to a light-transmitting substrate, but also has excellent water repellency containing a fluoropolymer. It can be effectively used in fields requiring water repellency, such as interior building materials and housing equipment, and can provide a water repellent composite material having excellent transparency.

The light-transmitting composite material of the present invention, which maintains transparency, can be applied to various uses owing to the above characteristics. Specific applications are classified and illustrated in Table 1, but are not limited to the examples in this table.

[0141]

[Table 1]

[0142]

EXAMPLES Next, the heat-resistant and scattering-preventing composite material of the present invention will be described with reference to production examples and examples, but the present invention is not limited to these examples.

Production Example 1 (Synthesis of hydroxyl group-containing PFA) Stirrer, valve,
1500 ml of pure water was placed in a 6-liter glass-lined autoclave equipped with a pressure gauge and a thermometer, and sufficiently purged with nitrogen gas, and then evacuated to obtain 1,2-dichloro-1,1,2,2-tetrafluoroethane. (R-11
4) 1500 g was charged.

Then, equation (7):

[0145]

Embedded image

The perfluoro- (1,1,9,
5.0 g of 9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol), perfluoro (propyl vinyl ether) (PPVE) 13
0 g and 180 g of methanol were injected using nitrogen gas.
The temperature in the system was kept at 35 ° C.

While stirring, tetrafluoroethylene gas (TFE) was injected so that the internal pressure became 8.0 kgf / cm ² G. Then, 0.5 g of a 50% methanol solution of di-n-propylperoxydicarbonate was injected under pressure using nitrogen to start the reaction.

[0148] Since the pressure lowered with the progress of the polymerization reaction, re-pressurized with tetrafluoroethylene gas at the time when decreased to 7.5 kgf / cm ² G to 8.0 kgf / cm ^2, the step-down was repeated booster .

While the supply of tetrafluoroethylene was continued, tetrafluoroethylene gas was maintained at about 60 from the start of polymerization.
Each time g of the polymer is consumed, 2.5 g of the above-mentioned fluorine-containing ethylenic monomer having a hydroxy group (the compound represented by the formula (7)) is pressed in 9 times in total (22.5 g in total) to carry out polymerization. Continued, and about 6% of tetrafluoroethylene
At the time of the consumption of 00 g, the supply was stopped, the autoclave was cooled, and unreacted monomer and R-114 were released.

The obtained copolymer was washed with water and methanol, and then dried under vacuum to obtain 710 g of a white solid. The composition of the obtained copolymer was 19F-NM.
By R analysis and IR analysis, TFE / PPVE / (formula (7)
= 97.0 / 2.0 / 1.0 mol%). In addition, the infrared spectrum shows -O at 3620 to 3400 cm ^-1 .
H characteristic absorption was observed. Tm = 3 by DSC analysis
05 ° C., 1% thermal decomposition temperature Td = 37 by DTGA analysis
5 ° C. 2m in diameter using a Koka type flow tester
Using a nozzle having a length of 8 mm and a length of 8 mm, the melt flow rate was measured at 372 ° C. for 5 minutes under a load of 7 kgf / cm ² and found to be 32 g / 10 min.

Production Example 2 (Synthesis of hydroxyl group-containing PFA) Stirrer, valve,
1500 ml of pure water was placed in a 6-liter glass-lined autoclave equipped with a pressure gauge and a thermometer, and sufficiently purged with nitrogen gas, and then evacuated to obtain 1,2-dichloro-1,1,2,2-tetrafluoroethane. (R-11
4) 1500 g was charged.

Then, perfluoro- (1,1,9,9
-Tetrahydro-2,5-bistrifluoromethyl-
2.5 g of 3,6-dioxa-8-nonenol) (formula (7)), perfluoro (propyl vinyl ether)
The reaction was started in the same manner as in Production Example 1 except that 132 g of (PPVE) and 230 g of methanol were used.
C.

While stirring, tetrafluoroethylene ethylene gas (TFE) was introduced at an internal pressure of 8.0 kgf / cm.
^It was press-fitted to ² G. Then, a 50% methanol solution of di-n-propylperoxydicarbonate was added.
The reaction was started by injecting 5 g with nitrogen.

[0154] Since the pressure lowered with the progress of the polymerization reaction, re-pressurized with tetrafluoroethylene gas at the time when decreased to 7.5 kgf / cm ² G to 8.0 kgf / cm ^2, the step-down was repeated booster .

Further, the amount of the fluorine-containing ethylenic polymer having a hydroxy group (compound represented by the above formula (7)), which is injected every time about 60 g of tetrafluoroethylene gas is consumed from the start of the polymerization, is set to 1. 680 g of a copolymer white solid was obtained in the same manner as in Production Example 1 except that 23 g was used 9 times in total (11.10 g in total). The composition of the obtained copolymer was determined by ¹⁹ F-NMR analysis and IR analysis.
PPVE / (a fluorine-containing ethylenic monomer having a hydroxy group represented by the formula (7)) = 97.6 / 2.0 / 0.
It was 4 mol%. The infrared spectrum is 3620-
Characteristic absorption of -OH was observed at 3400 cm ^-1 . DS
C analysis revealed that Tm was 310 ° C., and DTGA analysis showed that the decomposition initiation temperature was 368 ° C. and the 1% thermal decomposition temperature Td was 375 ° C. Using a nozzle with a diameter of 2 mm and a length of 8 mm using a Koka type flow tester, preheating at 372 ° C. for 5 minutes and a load of 7
The melt flow rate measured at kgf / cm ² was 42 g / 10 min.

Production Example 3 (Synthesis of hydroxyl group-containing PFA) Stirrer, valve,
1500 ml of pure water was placed in a 6-liter glass-lined autoclave equipped with a pressure gauge and a thermometer, and sufficiently purged with nitrogen gas, and then evacuated to obtain 1,2-dichloro-1,1,2,2-tetrafluoroethane. (R-11
4) 1500 g was charged.

Next, perfluoro- (1,1,9,9
-Tetrahydro-2,5-bistrifluoromethyl-
3,6-dioxa-8-nonenol) (formula (7))
0.2 g, perfluoro (propyl vinyl ether)
130 g of (PPVE) and 180 g of methanol were injected using nitrogen gas, and the temperature in the system was kept at 35 ° C.

While stirring, tetrafluoroethylene gas (TFE) was injected so that the internal pressure became 8.0 kgf / cm ² G. Then, 0.5 g of a 50% methanol solution of di-n-propylperoxydicarbonate was injected under pressure using nitrogen to start the reaction.

[0159] Since the pressure lowered with the progress of the polymerization reaction, re-pressurized with tetrafluoroethylene gas at the time when decreased to 7.5 kgf / cm ² G to 8.0 kgf / cm ^2, the step-down was repeated booster .

While continuing the supply of tetrafluoroethylene, about 60% of tetrafluoroethylene gas was supplied from the start of polymerization.
Every time the g was consumed, 5.14 g of the fluorine-containing ethylenic monomer having a hydroxy group (compound represented by the formula (7)) was injected 9 times in total (46.3 g in total) to carry out polymerization. Continuously, when about 600 g of tetrafluoroethylene was consumed from the start of the polymerization, the supply was stopped, the autoclave was cooled, and the unreacted monomer and R-114 were released.

The obtained polymer was washed with water and methanol, and then dried under vacuum to obtain 721 g of a white solid (powder). The composition of the obtained copolymer was ¹⁹ F-
According to NMR analysis and IR analysis, TFE / PPVE / (formula 7
= 97.6 / 2.0 / 1.8 mol%). In addition, the infrared spectrum shows -O at 3620 to 3400 cm ^-1 .
H characteristic absorption was observed. Tm = 3 by DSC analysis
11 ° C., decomposition start temperature 368 ° C. by DTGA analysis, 1
% Thermal decomposition temperature Td = 362 ° C. The melt flow rate was measured with a nozzle having a diameter of 2 mm and a length of 8 mm using a Koka type flow tester at 372 ° C. for 5 minutes and a load of 7 kgf / cm ² , and the melt flow rate was measured to be 85 g / 10 min.
Met.

Production Example 4 (Synthesis of PFA containing no functional group)
Perfluoro (1,1,9,9-tetrahydro-2,
5-bistrifluoromethyl-3,6-dioxa-8-
Synthesis was performed in the same manner as in Production Example 1 except that nonenol) (the compound represented by the formula (7)) was not used, and that 240 g of methanol was used, to obtain 597 g of PFA containing no functional group.

The obtained PFA was analyzed in the same manner as in Production Example 1. TFE / PPVE = 98.2 / 1.8 mol% Tm = 310 ° C. Td = 469 ° C. (1% weight loss) Melt flow rate = It was 24 g / 10 min.

Production Example 5 (Production of hydroxyl group-containing PFA powder coating) Production Example 1
Hydroxyl group-containing PFA powder (approximate specific gravity: 0.1).
5, a true specific gravity of 2.1, and an average particle diameter of 600 microns) were compressed into a sheet having a width of 60 mm and a thickness of 5 mm using a roller compactor (BCS-25, manufactured by Shinto Kogyo Co., Ltd.). Next, it is crushed by a crusher to a diameter of about 10 mm.
Using Nara Machine Co., Ltd. Cosmomizer N-1)
Milled at 11000 rpm at room temperature. Next, use a classifier (Shin-Tokyo Machinery Co., Ltd. High Boulder 300SD) for 1
Coarse particles having a size of 70 mesh (opening of 88 microns) or more were removed to obtain a PFA powder coating having a hydroxyl group. The apparent density of the powder was 0.7 g / ml and the average particle size was 2
It was 0 μm.

Production Example 6 (Production of PFA Powder Coating Containing No Functional Group) The PFA powder containing no functional group obtained in Production Example 4 was replaced with the PFA powder having a hydroxyl group obtained in Production Example 1 (apparent specific gravity: 0). .
6, a true specific gravity of 2.1, and an average particle size of 400 μm) to prepare a PFA powder coating in the same manner as in Production Example 5. The apparent density of the powder was 0.83 g / ml and the average particle size was 26 μm.

Production Example 7 (Synthesis of Fluoropolymer Using Fluorine-Free Functional Group-Containing Monomer) A 1-liter stainless steel autoclave equipped with a stirrer, a valve, a pressure gauge and a thermometer was prepared.
250 g of butyl acetate, vinyl pivalate (VPi) 3
6.4 g of 4-hydroxybutyl vinyl ether (HB
VE) 32.5 g and isopropoxycarbonyl peroxide 4.0 g were charged, cooled to 0 ° C. with ice, filled with nitrogen gas and replaced, and evacuated to obtain isobutylene (IB).
5 g and tetrafluoroethylene (TFE) 142 g were charged.

The mixture was heated to 40 ° C. with stirring and reacted for 30 hours, and the reaction was stopped when the pressure in the reaction vessel dropped to 2.0 kg / cm ² or less. When the autoclave was cooled and unreacted gas monomers were released, a butyl acetate solution of the fluoropolymer was obtained. The polymer concentration was 45%.

The fluorinated polymer was taken out from the obtained butyl acetate solution of the fluorinated polymer by a reprecipitation method, sufficiently isolated under reduced pressure and dried to be isolated as a white solid. ^{When the} obtained fluoropolymer was analyzed by ¹ H-NMR and ¹⁹ F-NMR elemental analysis, TFE / IB / V
It was a copolymer consisting of Pi / HBVE = 44/34/15/7 mol.

Production Example 8 (Preparation of Hydroxyl Group-Containing PFA Film) 8.0 g of the white solid obtained in Production Example 1 was placed in a 100 mmφ mold, set on a press set at 350 ° C., and preheated for 30 minutes. And compression molding at 70 kg / cm ² for 1 minute to obtain a film having a thickness of 0.5 mm.

Production Example 9 (Preparation of Hydroxyl Group-Containing PFA Film) A film having a thickness of 0.5 mm was obtained in the same manner as in Production Example 8 except that the white solid obtained in Production Example 2 was used.

Production Example 10 (Production of PFA Film Containing No Functional Group) Production Example 4
A film having a thickness of 0.5 mm was obtained in the same manner as in Production Example 8 except that the obtained white solid was used.

Production Example 11 (Preparation of Film by Extrusion of Hydroxyl Group-Containing PFA) From the white solid obtained in Production Example 1 using a twin-screw extruder (Laboplast mill manufactured by Toyo Seiki Co., Ltd.) at 350 to 370 ° C.
And extruded to produce pellets. The pellets were extruded at 360 ° C. to 380 ° C. at a roll temperature of 120 ° C. using a single screw extruder (Laboplast Mill, Toyo Seiki Co., Ltd.) to obtain a film having a width of 10 cm and a thickness of 100 to 150 μm.

Production Example 12 (Preparation of film by extrusion of hydroxyl group-containing PFA) Pellets were produced in the same manner as in Production Example 11, except that the white solid obtained in Production Example 3 was used as the white solid obtained in Production Example 1. Further, by extrusion, the width is 10c in the same manner as in Production Example 11.
m, a film having a thickness of 100 to 150 μm was obtained.

Production Example 13 (Preparation of film by extrusion of PFA containing no functional group) Pellets were produced in the same manner as in Production Example 11 except that the white solid obtained in Production Example 4 was used. 10 cm in width and 100 to 15 in the same manner as 11
A film of 0 μm was obtained.

Example 1 (Evaluation of Adhesiveness of Hydroxyl Group-Containing PFA Powder Coating) (1) Preparation of Press Sheet for Adhesion Test About 4 g of the hydroxyl group-containing PFA powder coating obtained in Production Example 5 was applied to a cylinder having a diameter of 60 mm. It was placed in a mold and compression-molded at room temperature under a pressure of 300 kgf / cm ² using a press machine to obtain a disk-shaped cold press sheet (hereinafter, also referred to as “PFA sheet”).

(2) Pretreatment of Substrate A 70 × 70 × 2 (mm) Pyrex glass plate was degreased with acetone.

(3) Preparation of Adhesive Sample The PFA sheet obtained in the above (1) was placed on a glass plate (the above (2)), placed in a hot air drier, and heated at 330 ° C.
Heated and melted for minutes. A sample having a PFA sheet having a thickness of about 450 μm adhered to a glass plate was obtained. Figure 1 shows the PF
FIG. 1 shows a schematic plan view of an adhesive sample including an A sheet 1 and a glass plate 2.

(4) Measurement of Adhesive Strength As shown in FIG. 1, the P of the adhesive sample obtained in the above (3) was measured.
Cut the FA sheet 1 at intervals of width a (10 mm) with a cutter, turn one end of each strip-shaped sheet 1,
A measuring instrument for measuring adhesive strength was obtained. FIG. 3 shows a schematic perspective view of the measurement tool for measuring adhesion obtained in FIG. 2. As shown in FIG.
The sheet 1 was pulled at an angle of 90 ° with respect to the glass plate 2, and the peel strength was measured. When measured with a Tensilon universal tester (manufactured by Orientec Co., Ltd.) at room temperature at a crosshead speed of 50 mm / min, an adhesive strength of 2.5 kgf / cm was shown by an average peeling load by an area method.

Comparative Example 1 (Evaluation of Adhesive Property of PFA Powder Coating Containing No Functional Group) PFA powder containing no functional group obtained in Production Example 6 in place of the PFA powder coating having a hydroxyl group obtained in Production Example 5 Except for using the coating material, a press sheet for an adhesion test was prepared, a pretreatment of the substrate was performed, and an adhesion sample was prepared in the same manner as in Example 1 to measure the adhesion strength.

The adhesive strength of the PFA powder coating having no functional group was 0.2 kgf / cm.

Example 2 (Electrostatic Coating of Hydroxyl Group-Containing PFA Powder Coating) (1) Pretreatment of Substrate After washing a 150 × 70 × 2 (mm) glass plate with acetone, an antistatic agent (Japan) Yegan Co., Ltd. Elegan 264
A) 0.5% methanol solution of A) was applied and air-dried.

(2) Electrostatic coating The PFA powder coating having a hydroxyl group obtained in Production Example 5 was applied to the glass plate obtained in (1) above using an electrostatic powder coating machine (GX3300, manufactured by Iwata Coating Co., Ltd.). Was applied at room temperature with an applied voltage of 40 kV. The coated plate was fired at 330 ° C. for 15 minutes using a hot air drier to obtain a coated film having a thickness of 45 to 50 μm.

The coating film was a transparent and uniform continuous film, and adhered firmly to the glass substrate.

An adhesion test was performed by the following method.

(Cross-cut test) JIS
A grid of 100 squares specified in K5400 1990, 8.5.2 is prepared, a cellophane tape (adhesive tape manufactured by Nichiban Co., Ltd.) is sufficiently adhered to this surface, and immediately peeled off. This peeling is performed 10 times with a new cellophane tape, and the number of cells remaining in 100 cells is evaluated.

As a result, all 100 squares remain (100 squares).
/ 100), indicating that the composition exhibits sufficient adhesion.

Comparative Example 2 A glass plate was prepared in the same manner as in Example 2 except that the PFA powder coating having no functional group obtained in Preparation 6 was used instead of the PFA powder having a hydroxyl group obtained in Preparation 5. Was subjected to an electrostatic coating, and a grid test was performed.

As a result, when the cellophane tape was peeled off, 10
All 0 squares were completely peeled (0/100).

Examples 3 to 4 (Adhesion test between hydroxyl group-containing PFA film and glass) Using a Pyrex glass of 30 × 20 × 5 mm as a glass plate, an adhesion test with PFA having a hydroxyl group was carried out as follows. Was performed as follows.

Further, the laminated body after bonding was also subjected to a warm water resistance test and a methanol immersion test. Table 2 shows the results.

(Preparation of Test Piece for Tensile Shear Test) FIG. 3 is a schematic perspective view of a test piece for tensile shear test. As shown in FIG. 3, the hydroxyl group-containing PFA obtained in Production Examples 8 to 9
A film (length f is 10 m, width g is 20 mm, thickness h is 0.1 mm) is used as an adhesive layer 3 and a Pyrex glass plate 4 (length i is 30 m, width g is 20 mm, thickness j is 5 m)
m), a load of 3 kg was applied, and the specimen was left in an electric furnace at 350 ° C. for 30 minutes to obtain a test piece. The thickness of the adhesive layer 3 was adjusted to 0.1 mm by a spacer.

(Adhesive Strength) FIG. 4 is a schematic explanatory view for explaining a test apparatus used for measuring the adhesive strength by the tensile shearing method. As shown in FIG. 4, a test jig 6 conforming to the shape of the test piece 5 obtained as described above was set on a Tensilon universal testing machine 7 manufactured by Orientec Co., Ltd., and the crosshead speed was 20 mm / min. Was used to conduct a tensile shear test. The measurement is the maximum adhesive strength (kgf / c
m ² ).

(Warm Water Resistance Test) Using the test piece prepared by the method described above, the test piece was immersed in warm water at 50 ° C., the adhesive property was observed after 6 hours, and the adhesive strength after 72 hours (kgf / kgf) was measured. c
m ² ) was measured.

(Methanol Immersion Test) The test pieces prepared by the above-described method were immersed in methanol at room temperature, and the adhesion was observed.

Comparative Example 3 (Adhesion between PFA Film Having No Functional Group and Glass) PFA containing no functional group obtained in Production Example 10 in place of the hydroxyl group-containing PFA film of Production Example 8 or 9
Preparation of test pieces and various tests were performed in the same manner as in Example 3 except that a film was used. Table 2 shows the results.

[0196]

[Table 2]

Example 5 (Lamination of hydroxyl group-containing PFA film on glass and its transparency) (Preparation of laminate with glass) FIG. 5 shows a laminate test plate prepared to obtain a laminate for an adhesion durability test. FIG. As shown in FIG. 5, length 150 mm, width 70 m
m, a hydroxyl group-containing PFA film 8 having a thickness of 100 μm obtained in Production Example 11 cut into a glass plate 11 having a thickness of 2.0 mm and the same size (150 × 70 mm) as the glass plate 8
And a thickness 1 having no functional groups of the same size thereon
00 μm PFA film 9 (film of Production Example 13)
And polyimide film 10 (Dupont Kapton 2)
00-H), an aluminum plate 12 having the same size as the glass plate 11 was further stacked, set in a press set at 350 ° C., preheated (20 minutes), and then heated to about 20 k.
A laminate test plate was obtained by pressing at g / cm ² for 1 minute.
Aluminum plate 12 and polyimide film 1 after cooling
By removing 0, a single-sided laminated plate with glass as shown in FIG. 6 was obtained.

Excluding the glass layer, hydroxyl group-containing PF
A and a layer of PFA with no functional groups are 85
μm.

(Visible light transmittance of glass laminate containing hydroxyl group-containing PFA) The laminate of PFA and glass obtained above was subjected to typical light transmission in the visible region using a Hitachi spectrophotometer V-3410. The rate was measured. Table 3 shows the results.

Comparative Example 4 The same glass plate as used in Example 5 was used.
The light transmittance in a representative visible light region was measured in the same manner as in Example 5. Table 3 shows the results.

[0201]

[Table 3]

As shown in Table 3, PFA / P containing hydroxyl group
It can be seen that the FA / glass laminate shows good transparency.

Example 6 (Durability of Hydroxyl Group-Containing PFA Film and Glass) (Preparation of Laminate for Durability Test) FIG. 5 shows an outline of a laminate test plate prepared to obtain a laminate for adhesion durability test. FIG. As shown in FIG. 5, length 150 mm, width 70
120mm long and 40m wide at the center of the glass plate 11 mm
m and the hydroxyl group-containing PF obtained in Production Example 12
An A film 8 is placed thereon, and a PFA film 9 having no functional group of the same size (the film of Production Example 13) and a polyimide film 10 (the same as in Example 5) are stacked thereon. Aluminum sheets 12 of the same size are stacked, set on a press set at 350 ° C., preheated (20 minutes), and then pressed at about 20 kg / cm ² .
After pressing for 1 minute, a laminate test plate was obtained. After cooling, the aluminum plate 12 and the polyimide film 10 were removed to obtain a durability test laminate. FIG. 7 shows a schematic cross-sectional view of the durability test laminate obtained in FIG. 6.

(Weather Resistance Test) The above-mentioned hydroxyl group-containing PFA film 8 was used as an adhesive layer to form a PF having no functional group.
The laminate obtained by laminating the A film 9 on the glass plate 11 was put into an eye super UV tester (manufactured by Iwasaki Electric Co., Ltd.), and an accelerated weather resistance test was performed. A sample having no change in appearance was marked with “○”.

(Heat Resistance Test) The laminate was left in an atmosphere at 200 ° C. for 12 hours. ○ those that have no change in appearance
And

(Temperature / humidity cycle) -40 ° C./1 hour, 8
5 ° C / 85% RH / 4 hours temperature / humidity cycle test
Cycled. A sample having no change in appearance was marked with “○”.

Table 4 shows the results of the various tests described above.

Comparative Example 5 (Durability of PFA Film Having No Functional Group and Glass) A PFA film having no functional group obtained in Production Example 13 was used in place of the hydroxyl group-containing PFA film. A test laminate was prepared and subjected to a durability test in the same manner as in Example 6. Table 4 shows the results.

Comparative Example 6 (Durability of surface-treated FEP / EVA film / glass laminate) EV instead of hydroxyl group-containing PFA film
A film (manufactured by Sumitomo Chemical Co., Ltd., Bond First 7B, thickness: 200 μm) is used as an adhesive layer. Film NF-0100B1) was laminated in the same manner as in Example 6 except that the surface-treated surface was overlapped with the EVA film layer in contact with the surface-treated surface, and pressed and bonded at a temperature of 180 ° C.
An EVA / glass laminate was obtained. Using this, the same durability test as in Example 6 was performed. Table 4 shows the results.

Comparative Example 7 (Heat Resistance and Durability of Fluoropolymer Using Fluorine-Free Functional Group-Containing Monomer) The thermal decomposition temperature of the fluorinated copolymer obtained in Production Example 7 was determined by TGA It was 220 ° C. at a 1% thermal decomposition temperature as determined by analysis. It was found that the fluorinated copolymer using a functional group-containing monomer having no fluorine as obtained in Production Example 7 had low heat resistance. Further, the fluoropolymer obtained in Production Example 7 was dissolved in butyl acetate to a concentration of 10% by weight.

The same glass plate as that used in Example 5 was coated with the butyl acetate solution of the fluoropolymer of Production Example 7 by air spray so as to have a thickness of about 10 μm.
Infrared dried for 0 minutes. Example 6 about the obtained coated plate
The same durability test as described above was performed. Table 4 shows the results.

[0212]

[Table 4]

[0213]

According to the present invention, by applying the material comprising the functional group-containing fluoropolymer of the present invention having excellent adhesiveness to a light-transmitting substrate, it is possible to obtain a transparent material having excellent transparency without requiring complicated steps. An optical composite can be obtained.

Further, according to the present invention, a weather-resistant composite material, a non-tacky composite material, an antifouling composite material having excellent adhesive processability and transparency,
A chemical resistant composite, a shatterproof composite, and a water repellent composite can be obtained, and can be effectively used in various application fields such as building materials, cooking equipment, housing equipment, automobiles, semiconductors, and home appliances.

[Brief description of the drawings]

FIG. 1 is a schematic plan view of an adhesive sample prepared for measuring adhesive strength in Example 1 of the present invention.

FIG. 2 is a schematic perspective view of a measuring tool used for measuring an adhesive strength in Example 1 of the present invention.

FIG. 3 is a schematic perspective view of a test piece to be subjected to an adhesion test (tensile shear test) in the present invention.

FIG. 4 is a schematic explanatory view of a test device used for an adhesion test (tensile shear test) in the present invention.

FIG. 5 is a schematic cross-sectional view of a laminate test plate manufactured to obtain a laminate in Example 5 of the present invention.

FIG. 6 is a schematic sectional view of a laminate obtained in Example 5 of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 PFA sheet 2, 11 Glass plate 3 Adhesive layer 4 Pyrex glass plate 5 Test piece 6 Test jig 7 Testing machine 8 Hydroxyl group-containing PFA film 9 PFA film without functional group 10 Polyimide film 12 Aluminum plate

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masahiro Kumegawa 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Noritoshi Oka 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Inside Yodogawa Seisakusho Co., Ltd. (72) Inventor Hisato Masamitsu 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industrial Co., Ltd. (72) Tetsuo Shimizu 1-1-1, Nishiichitsuya Settsu-shi, Osaka, Daikin Inside Yodogawa Manufacturing Co., Ltd.

Claims (14)

[Claims] 1. A method for producing a functional group-containing fluorine-containing ethylenic monomer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylate, a carboxyester group and an epoxy group. 0.05 to 30 mol% of at least one monomer and 70 to 99.95 mol% of at least one monomer of the fluorine-containing ethylenic monomer having no functional group (b) A translucent composite material which maintains transparency by applying a material comprising a functional group-containing fluorine-containing ethylenic polymer obtained by copolymerization to a translucent substrate. 2. The functional group-containing fluorine-containing ethylenic monomer (a) is represented by the formula (1): CX ₂ ＣCX ¹ -R _f -Y (1) (where Y is -CH ₂ OH,- COOH, carboxylate, carboxyester group or epoxy group, X and X ¹ are the same or different, and are a hydrogen atom or a fluorine atom,
R _f is a divalent fluorinated alkylene group having 1 to 40 carbon atoms,
A fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group containing an ether group having 1 to 40 carbon atoms or a fluorine-containing oxyalkylene group containing an ether bond having 1 to 40 carbon atoms) The translucent composite material according to claim 1, wherein a functional group-containing fluorine-containing ethylenic polymer, which is a kind of a functional group-containing fluorine-containing ethylenic monomer, is applied to the light-transmitting substrate. 3. The method according to claim 1, wherein the fluorine-containing ethylenic monomer (b) having no functional group is obtained by applying a functional group-containing fluorine-containing ethylenic polymer, which is tetrafluoroethylene, to a transparent substrate. Item 3. A translucent composite material having maintained transparency according to item 1 or 2. 4. The method according to claim 1, wherein the fluorine-containing ethylenic monomer (b) having no functional group is tetrafluoroethylene 85-9.
9.7 mol% and the formula (2): CF ₂ ＣＦCF—R _f ¹ (2) (where R _f ¹ is CF ₃ or OR _f ² (R _f ² is carbon number 1 to
5 perfluoroalkyl group)
A functional group-containing fluorine-containing ethylenic polymer which is a mixed monomer of from 1 to 15 mol% is applied to a light-transmitting substrate.
Or a translucent composite material maintaining the transparency described in 2. 5. The fluorinated ethylenic monomer having no functional group (b) is a tetrafluoroethylene 40-80.
The translucent composite material according to claim 1 or 2, which is a mixed monomer of 0 mol% to 15 mol% of ethylene and 20 to 60 mol% of ethylene and another copolymerizable monomer. 6. The functional group-containing fluorinated ethylenic monomer (a) in an amount of 0.01 to 30 mol% and the fluorinated ethylenic monomer having no functional group (b) having a vinylidene fluoride content of 70 to 50%. 3. The translucent transparent material according to claim 1, wherein a material comprising a functional group-containing fluorine-containing ethylenic polymer copolymerized with 99.9 mol% is applied to the translucent substrate. Composite materials. 7. The fluorine-containing ethylenic monomer (b) having no functional group is contained in an amount of 70 to 99 mol% of vinylidene fluoride.
A mixed monomer of 1 to 30 mol% of tetrafluoroethylene, a mixed monomer of 50 to 99 mol% of vinylidene fluoride, 0 to 30 mol% of tetrafluoroethylene and 1 to 20 mol% of chlorotrifluoroethylene, Or 60 to 99 mol% of vinylidene fluoride and 0 to 3 of tetrafluoroethylene
The translucent composite material according to claim 1 or 2, which is a mixed monomer of 3 mol% and 1 to 10 mol% of hexafluoropropylene. 8. A translucent composite having a transparency, wherein the functional group-containing fluorine-containing ethylenic polymer according to any one of claims 1 to 7 is applied to a translucent substrate in the form of a paint. Wood. 9. A translucent translucent material comprising the functional group-containing fluorine-containing ethylenic polymer according to claim 1 applied to a translucent substrate in the form of an aqueous dispersion. Composite. 10. A translucent translucent material, wherein the functional group-containing fluorine-containing ethylenic polymer according to any one of claims 1 to 7 is applied to a translucent substrate in the form of a powder coating. Composite. 11. A translucent composite, wherein transparency is maintained, wherein the functional group-containing fluorine-containing ethylenic polymer according to any one of claims 1 to 7 is applied to a translucent substrate in the form of a film. Wood. 12. The translucent composite material according to claim 1, wherein the translucent substrate is a glass substrate. 13. The translucent composite material according to claim 1, wherein the translucent substrate is a transparent resin substrate. 14. The translucent composite material according to claim 13, wherein the translucent substrate is polycarbonate.