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WO2018134974A1 - Film de résine, stratifié, élément optique, matériau formant une barrière aux gaz et substrat de capteur tactile - Google Patents

Film de résine, stratifié, élément optique, matériau formant une barrière aux gaz et substrat de capteur tactile Download PDF

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Publication number
WO2018134974A1
WO2018134974A1 PCT/JP2017/001970 JP2017001970W WO2018134974A1 WO 2018134974 A1 WO2018134974 A1 WO 2018134974A1 JP 2017001970 W JP2017001970 W JP 2017001970W WO 2018134974 A1 WO2018134974 A1 WO 2018134974A1
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WIPO (PCT)
Prior art keywords
resin film
layer
group
laminate
resin
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PCT/JP2017/001970
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English (en)
Japanese (ja)
Inventor
野殿　光紀
桜井　孝至
勝紀 望月
池内　淳一
ボラム 片
宗銘 李
奇明 呂
志成 林
Original Assignee
住友化学株式会社
財團法人工業技術研究院
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Priority to PCT/JP2017/001970 priority Critical patent/WO2018134974A1/fr
Publication of WO2018134974A1 publication Critical patent/WO2018134974A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

Definitions

  • the present invention relates to a resin film, a laminate, an optical member, a gas barrier material, and a touch sensor substrate.
  • glass has been used as a base material for display members, a base material for optical members, and a material for a front plate constituting various display devices such as solar cells or displays.
  • glass has the disadvantage of being easily broken and heavy.
  • the glass substrate or the glass front plate has not had sufficient material properties. Therefore, an acrylic resin and a laminate obtained by imparting scratch resistance to the resin have been studied as a material or a substrate that can replace glass.
  • a composite material of an organic material and an inorganic material such as a hybrid film containing polyimide and silica has also been studied (see, for example, Patent Documents 1 and 2).
  • the resin film that replaces the glass substrate in the base material of the display member, the base material of the optical member, and the front plate constituting the flexible device is a laminate in which an adhesive layer, a resin film, and a hard coat layer are laminated in this order (hereinafter, adhesive layer). / May be referred to as a laminate of resin film / hard coat layer).
  • adhesive layer an adhesive layer, a resin film, and a hard coat layer are laminated in this order
  • adhesive layer / May be referred to as a laminate of resin film / hard coat layer.
  • the hardness of the surface of the hard coat layer tends to be insufficient, and it has become clear that there is room for further improvement in this respect.
  • the present invention provides a resin film that makes it possible to increase the hardness of the surface of the hard coat layer in the laminate of the adhesive layer / resin film / hard coat layer.
  • One aspect of the present invention provides a resin film containing a polyimide polymer.
  • the tensile elastic modulus of the resin film is 4.0 GPa or more and the resin film is repeatedly folded back into a U shape until the distance between the resin films facing each other is 3 mm, until the resin film breaks.
  • the number of times the resin film is folded exceeds 100,000.
  • a resin film containing a polyimide-based polymer satisfies the above requirements with respect to the tensile modulus and bending test, so that in the laminate of adhesive layer / resin film / hard coat layer, The hardness of the surface of the coat layer can be sufficiently increased.
  • the yellowness of the resin film is preferably 5 or less.
  • the resin film may have a thickness of 30 to 100 ⁇ m. According to the resin film having such a thickness, the more remarkable effect of the present invention can be obtained.
  • the resin film can be suitably used as an optical member such as a flexible device, a gas barrier material, or a touch sensor substrate.
  • the hardness of the surface of the hard coat layer in the laminate of the adhesive layer / resin film / hard coat layer can be increased with respect to the resin film containing the polyimide polymer.
  • FIG. 1 is a cross-sectional view showing an embodiment of a resin film.
  • a resin film 10 shown in FIG. 1 contains a polyimide-based polymer and has a pair of opposing main surfaces 10a and 10b.
  • the tensile elastic modulus of the resin film 10 is 4.0 GPa or more.
  • the number of times the resin film 10 is bent until the resin film 10 breaks exceeds 100,000.
  • the number of times the resin film is bent in the bending test may be referred to as “the number of bending”.
  • the hardness of the surface of the hard coat layer is sufficiently obtained in the adhesive layer / resin film / hard coat layer laminate. Can be increased.
  • FIG. 2 is a cross-sectional view showing an embodiment of a laminate comprising an adhesive layer / resin film / hard coat layer laminate.
  • a laminated body 30 shown in FIG. 2 includes a resin film 10, a functional layer 20 laminated on one main surface 10a of the resin film 10, and a functional layer 21 laminated on the other main surface 10b of the resin film 10. It is the laminated body which has.
  • the resin film 10 according to the present embodiment when the functional layer 20 is a hard coat layer and the functional layer 21 is an adhesive layer, the hardness of the surface S of the functional layer (hard coat layer) 20 can be increased. Details of the hard coat layer and the adhesive layer as the functional layers 20 and 21 will be described later.
  • the tensile elastic modulus of the resin film 10 is 4 GPa or more, preferably 5 GPs or more, preferably 10 GPa or less, and more preferably 8 GPa or less. When the tensile elastic modulus is within these numerical ranges, an excellent effect can be obtained in terms of bending recovery in addition to the improvement in the hardness of the surface S.
  • the number of bendings until the resin film 10 is broken exceeds 100,000.
  • “the resin film breaks” means that the resin film is partially or wholly broken, that is, a portion that is divided throughout the thickness direction is generated. If the resin film does not break when the number of times of bending reaches 100,000 times, the number of times of bending until the resin film breaks is considered to exceed 100,000 times. According to the knowledge of the present inventors, the contribution of the resin film to the improvement in the hardness of the surface S can be evaluated based on a bending test up to 100,000 times of bending. Details of the bending test will be described in Examples described later.
  • the yellowness (YI value) of the resin film 10 is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less from the viewpoint of the visibility of the flexible device.
  • the yellowness of the resin film 10 is usually 0.5 or more and may be 1 or more.
  • Resin film 10 contains a polyimide polymer.
  • the polyimide polymer means a polymer containing at least one repeating structural unit represented by formula (PI), formula (a), formula (a ′) and formula (b). .
  • the repeating structural unit represented by a formula (PI) is a main structural unit of a polyimide-type polymer.
  • the repeating structural unit represented by the formula (PI) is preferably 40 mol% or more, more preferably 50 mol% or more, further preferably 70 mol%, based on all repeating structural units of the polyimide-based polymer. More preferably, it is 90 mol% or more, and still more preferably 98 mol%.
  • the organic group of the divalent organic group represented by A includes an acyclic aliphatic group, a cyclic aliphatic group, and an aromatic group.
  • the divalent organic group represented by A is preferably selected from a divalent cycloaliphatic group and a divalent aromatic group.
  • the aromatic group include a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group having two or more aromatic rings and connected to each other directly or by a bonding group. Groups. From the viewpoint of transparency of the resin film and suppression of coloring, it is preferable that a fluorine-based substituent is introduced into the organic group of A.
  • the organic group of A is, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, a heteroalkylaryl.
  • the hetero atom include O, N, or S.
  • Examples of the bonding group include —O—, an alkylene group having 1 to 10 carbon atoms, —SO 2 —, —CO—, or —CO—NR— (R represents methyl Group, an alkyl group having 1 to 3 carbon atoms such as an ethyl group or a propyl group, or a hydrogen atom).
  • the carbon number of the divalent organic group represented by A is usually 2 to 40, preferably 5 to 32, more preferably 12 to 28, and further preferably 24 to 27.
  • A include groups represented by the following formula (30), formula (31), formula (32), formula (33), or formula (34).
  • * In the formula indicates a bond.
  • Z 1 to Z 3 are each independently a single bond, —O—, —CH 2 —, —C (CH 3 ) 2 —, —SO 2 —, —CO— or —CO—NR— (R is Represents a C 1-3 alkyl group such as a methyl group, an ethyl group, or a propyl group, or a hydrogen atom.
  • Z 1 and Z 2 , and Z 2 and Z 3 are each preferably in the meta position or the para position with respect to each ring.
  • Z 1 and the single bond at the terminal, Z 2 and the single bond at the terminal, and Z 3 and the single bond at the terminal are in the meta position or the para position, respectively.
  • Z 1 and Z 3 are —O— and Z 2 is —CH 2 —, —C (CH 3 ) 2 — or —SO 2 —.
  • One or two or more hydrogen atoms of these groups may be substituted with a fluorine-based substituent.
  • G 2 in the formula (a) is a trivalent organic group.
  • This organic group can be selected from the same groups as the organic group of G in formula (PI) except that it is a trivalent group.
  • Examples of G 2 include groups in which any one of the four bonds of the groups represented by formulas (20) to (26) listed as specific examples of G is replaced with a hydrogen atom. Can do.
  • a 2 in formula (a) can be selected from the same groups as A in formula (PI).
  • G 3 in formula (a ′) can be selected from the same groups as G in formula (PI).
  • a 3 in formula (a ′) can be selected from the same groups as A in formula (PI).
  • G 4 in the formula (b) is a divalent organic group.
  • This organic group can be selected from the same groups as the organic group of G in formula (PI) except that it is a divalent group.
  • Examples of G 4 include groups in which any two of the four bonds of the groups represented by formulas (20) to (26) listed as specific examples of G are replaced with hydrogen atoms. Can do.
  • a 4 in formula (b) can be selected from the same groups as A in formula (PI).
  • the repeating structural unit represented by the formula (PI) or the formula (a ′) is usually derived from a diamine and a tetracarboxylic acid compound.
  • the repeating structural unit represented by the formula (a) is usually derived from diamines and tricarboxylic acid compounds.
  • the repeating structural unit represented by the formula (b) is usually derived from diamines and dicarboxylic acid compounds.
  • the tetracarboxylic acid compound is an alicyclic tetracarboxylic compound or an aromatic tetracarboxylic acid compound from the viewpoints of solubility of the polyimide polymer in a solvent and transparency and flexibility when the resin film 10 is formed. It is preferable. From the viewpoint of transparency of the resin film and suppression of coloring, the tetracarboxylic acid compound may be selected from an alicyclic tetracarboxylic acid compound having a fluorine-based substituent and an aromatic tetracarboxylic acid compound having a fluorine-based substituent. Preferably, it is an alicyclic tetracarboxylic acid compound having a fluorine-based substituent.
  • the tricarboxylic acid compound examples include aromatic tricarboxylic acid, alicyclic tricarboxylic acid, acyclic aliphatic tricarboxylic acid and related acid chloride compounds, acid anhydrides and the like.
  • the tricarboxylic acid compound is preferably selected from aromatic tricarboxylic acids, alicyclic tricarboxylic acids, acyclic aliphatic tricarboxylic acids, and related acid chloride compounds. Two or more tricarboxylic acid compounds may be used in combination.
  • the tricarboxylic acid compound is preferably an alicyclic tricarboxylic acid compound or an aromatic tricarboxylic acid compound.
  • the tricarboxylic acid compound is more preferably an alicyclic tricarboxylic acid compound having a fluorine-based substituent or an aromatic tricarboxylic acid compound having a fluorine-based substituent.
  • dicarboxylic acid compound examples include aromatic dicarboxylic acid, alicyclic dicarboxylic acid, acyclic aliphatic dicarboxylic acid and related acid chloride compounds, acid anhydrides and the like.
  • the dicarboxylic acid compound is preferably selected from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids and related acid chloride compounds. Two or more dicarboxylic acid compounds may be used in combination.
  • the dicarboxylic acid compound is preferably an alicyclic dicarboxylic acid compound or an aromatic dicarboxylic acid compound.
  • the dicarboxylic acid compound is more preferably an alicyclic dicarboxylic acid compound having a fluorine-based substituent or an aromatic dicarboxylic acid compound having a fluorine-based substituent.
  • diamines examples include aromatic diamines, alicyclic diamines and aliphatic diamines, and these may be used in combination of two or more. From the viewpoint of the solubility of the polyimide polymer in the solvent, and the transparency and flexibility when the resin film 10 is formed, the diamine is selected from an alicyclic diamine and an aromatic diamine having a fluorine substituent. Is preferred.
  • Such a polyimide polymer has particularly excellent flexibility, high light transmittance (for example, 85% or more, preferably 88% or more with respect to light at 550 nm), low yellowness (YI A resin film having a value of 5 or less, preferably 3 or less, and a low haze (1.5% or less, preferably 1.0% or less) is easily obtained.
  • the polyimide polymer may be a copolymer containing a plurality of different types of repeating structural units.
  • the weight average molecular weight of the polyimide polymer is usually 10,000 to 500,000.
  • the weight average molecular weight of the polyimide polymer is preferably 50,000 to 500,000, more preferably 70,000 to 400,000.
  • the weight average molecular weight is a standard polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC). If the weight average molecular weight of the polyimide polymer is large, high flexibility tends to be obtained, but if the weight average molecular weight of the polyimide polymer is too large, the viscosity of the varnish tends to increase and the workability tends to decrease. is there.
  • the polyimide-based polymer may contain a halogen atom such as a fluorine atom that can be introduced by the above-described fluorine-based substituent.
  • a halogen atom such as a fluorine atom that can be introduced by the above-described fluorine-based substituent.
  • a halogen atom is preferably a fluorine atom.
  • the content of halogen atoms in the polyimide polymer is preferably 1 to 40% by mass, more preferably 1 to 30% by mass based on the mass of the polyimide polymer.
  • the resin film 10 may contain 1 type, or 2 or more types of ultraviolet absorbers.
  • the ultraviolet absorber can be appropriately selected from those usually used as an ultraviolet absorber in the field of resin materials.
  • the ultraviolet absorber may contain a compound that absorbs light having a wavelength of 400 nm or less.
  • Examples of the ultraviolet absorber that can be appropriately combined with the polyimide polymer include at least one compound selected from the group consisting of benzophenone compounds, salicylate compounds, benzotriazole compounds, and triazine compounds.
  • the “system compound” refers to a derivative of the compound to which the “system compound” is attached.
  • a “benzophenone compound” refers to a compound having benzophenone as a host skeleton and a substituent bonded to benzophenone.
  • the content of the ultraviolet absorber is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and usually 10% by mass or less with respect to the total mass of the resin film. Yes, preferably 8% by mass or less, more preferably 6% by mass or less.
  • the resin film 10 may further contain an inorganic material such as inorganic particles.
  • the inorganic material is preferably a silicon material containing a silicon atom.
  • the tensile elastic modulus of the resin film 10 can be easily set to 4.0 GPa or more.
  • the method for controlling the tensile elastic modulus of the resin film 10 is not limited to the blending of inorganic materials.
  • silicon materials containing silicon atoms include silica compounds, quaternary alkoxysilanes such as tetraethyl orthosilicate (TEOS), and silicon compounds such as silsesquioxane derivatives.
  • TEOS tetraethyl orthosilicate
  • silica particles are preferable from the viewpoint of the transparency and flexibility of the resin film 10.
  • the average primary particle diameter of the silica particles in the resin film can be determined by observation with a transmission electron microscope (TEM).
  • the primary particle diameter of the silica particles can be a constant direction diameter measured by a transmission electron microscope (TEM).
  • the average primary particle diameter can be obtained as an average value of ten primary particle diameters measured by TEM observation.
  • the particle distribution of the silica particles before forming the resin film can be determined by a commercially available laser diffraction particle size distribution meter.
  • the blending ratio of the polyimide-based polymer and the inorganic material is preferably 1: 9 to 10: 0 in terms of mass ratio, with the sum of both being 10 and 3: 7 to 10: 0. More preferably, it is more preferably 3: 7 to 8: 2, and still more preferably 3: 7 to 7: 3.
  • the ratio of the inorganic material to the total mass of the polyimide-based polymer and the inorganic material is usually 20% by mass or more, preferably 30% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less. .
  • the compounding ratio of the polyimide polymer and the inorganic material silicon material
  • the transparency and mechanical strength of the resin film tend to be improved.
  • the tensile elasticity modulus of the resin film 10 can be easily made 4.0 GPa or more.
  • the resin film 10 may further contain components other than the polyimide polymer and the inorganic material as long as the transparency and flexibility are not significantly impaired.
  • components other than the polyimide-based polymer and the inorganic material include colorants such as antioxidants, mold release agents, stabilizers, and bluing agents, flame retardants, lubricants, thickeners, and leveling agents.
  • the proportion of components other than the polyimide-based polymer and the inorganic material is preferably more than 0% and not more than 20% by mass, more preferably more than 0% and not more than 10% by mass with respect to the mass of the resin film 10. It is.
  • Si / N which is the atomic ratio of silicon atoms to nitrogen atoms, is 8 or more on at least one main surface 10a.
  • This atomic ratio Si / N is determined by evaluating the composition of the main surface 10a by X-ray photoelectron spectroscopy (XPS) and calculating the amount of silicon atoms and the amount of nitrogen atoms present. This is a calculated value.
  • XPS X-ray photoelectron spectroscopy
  • the thickness of the resin film 10 is appropriately adjusted according to the flexible device to which the laminate 30 is applied, but is usually 10 to 500 ⁇ m, preferably 15 to 200 ⁇ m, more preferably 20 to 100 ⁇ m. Preferably, the thickness is 30 to 100 ⁇ m. The thickness of the resin film 10 is more preferably 50 to 100 ⁇ m, and most preferably 70 to 90 ⁇ m.
  • the resin film 10 having such a configuration has particularly excellent flexibility and practically sufficient strength.
  • an inorganic material is added to a polyimide polymer varnish, and stirred and mixed by a known stirring method to prepare a dispersion in which the silicon material is uniformly dispersed.
  • a UV absorber is blended, the UV absorber can be added to this dispersion.
  • the polyimide-based polymer varnish or the dispersion may contain a metal alkoxide such as alkoxysilane that contributes to the bonding between inorganic particles (silica particles and the like).
  • a metal alkoxide such as alkoxysilane that contributes to the bonding between inorganic particles (silica particles and the like).
  • This compound is preferably an alkoxysilane having an amino group.
  • Such a combination of the compound and the inorganic particles can achieve a high elastic modulus and can contribute to increasing the number of bendings until the resin film is broken in the bending test.
  • the polyimide polymer varnish or dispersion may further contain water.
  • the water content is usually 0.1 to 10% by mass relative to the mass of the polyimide polymer varnish or dispersion.
  • the use of water can also achieve a high elastic modulus and contribute to an increase in the number of bendings until the resin film breaks in the bending test.
  • the polyimide polymer or dispersion may further contain an additive.
  • additives include colorants such as antioxidants, mold release agents, stabilizers, and bluing agents, flame retardants, lubricants, thickeners, and leveling agents.
  • the resin film can be produced by an appropriate known method. The following method is mentioned as an example of a manufacturing method.
  • the polyimide polymer varnish or dispersion is applied to a substrate by, for example, a known roll-to-roll or batch method to form a coating film.
  • the coating is dried to form a film.
  • the resin film 10 is obtained by peeling a film from a base material.
  • the substrate include a polyethylene terephthalate (PET) substrate, a stainless steel (SUS) belt, or a glass substrate.
  • a surface treatment may be applied to at least one main surface of the resin film.
  • the surface treatment is preferably UV ozone treatment.
  • Si / N can be easily increased to 8 or more.
  • the method of setting Si / N to 8 or more is not limited to UV ozone treatment.
  • the main surface 10a and / or 10b of the resin film 10 may be subjected to a surface treatment such as a plasma treatment or a corona discharge treatment in order to improve adhesion with a functional layer described later.
  • UV ozone treatment can be performed using a known ultraviolet light source including a wavelength of 200 nm or less.
  • An example of an ultraviolet light source is a low-pressure mercury lamp.
  • the ultraviolet light source various commercially available devices equipped with an ultraviolet light source may be used. Examples of the commercially available apparatus include an ultraviolet (UV) ozone cleaning apparatus UV-208 manufactured by Technovision.
  • the resin film 10 of the present embodiment thus obtained is excellent in flexibility. Moreover, when at least one principal surface 10a has Si / N, which is the atomic ratio of silicon atoms and nitrogen atoms, of 8 or more, excellent adhesion to the functional layer 20 described later can be obtained.
  • the functional layer 20 may be a layer for further imparting a function (performance) to the laminate 30 when the laminate 30 is used as an optical member of a flexible device or a base material of a display member, or a front plate.
  • the optical member means a sensor unit such as a touch sensor or a signal transmission unit in the display device
  • the display member means an image display unit such as an organic EL device or a liquid crystal display device in the display device.
  • the functional layer 20 is preferably a layer having at least one function selected from the group consisting of ultraviolet absorption, a function of developing high hardness on the surface, adhesiveness, hue adjustment, and refractive index adjustment.
  • a layer having an ultraviolet absorption function is, for example, a main material selected from an ultraviolet curable transparent resin, an electron beam curable transparent resin, and a thermosetting transparent resin; It is comprised from the ultraviolet absorber disperse
  • the ultraviolet curable, electron beam curable, or thermosetting transparent resin as the main material of the ultraviolet absorbing layer is not particularly limited, and examples thereof include poly (meth) acrylate.
  • the ultraviolet absorber can be selected from the same compounds as those exemplified as the ultraviolet absorber that can be contained in the resin film 10.
  • the ultraviolet absorbing layer may be a layer that absorbs 95% or more of light having a wavelength of 400 nm or less (for example, light having a wavelength of 313 nm).
  • the ultraviolet absorbing layer may be a layer having a transmittance of light having a wavelength of 400 nm or less (for example, light having a wavelength of 313 nm) of less than 5%.
  • the ultraviolet absorbing layer can contain an ultraviolet absorber having a concentration that provides such transmittance. From the viewpoint of suppressing the increase in yellowness of the laminate due to light irradiation, the content ratio of the ultraviolet absorber in the ultraviolet absorbing layer (functional layer 20) is usually 1% by mass or more based on the mass of the ultraviolet absorbing layer. Yes, preferably 3% by mass or more, usually 10% by mass or less, and preferably 8% by mass or less.
  • the layer having an adhesive function (adhesive layer) as the functional layer 20 has a function of bonding the laminate 30 to another member.
  • the material for forming the adhesive layer include a thermosetting resin composition and a photocurable resin composition.
  • the adhesive layer may be composed of a resin composition containing a component having a polymerizable functional group. In this case, strong adhesion can be realized by further polymerizing the resin composition constituting the adhesive layer after the laminate 30 is brought into close contact with another member.
  • the adhesive strength between the resin film 10 and the adhesive layer is preferably 0.1 N / cm or more, and more preferably 0.5 N / cm or more.
  • the adhesive layer may contain a thermosetting resin composition or a photocurable resin composition as a material.
  • the resin composition can be polymerized and cured by supplying energy afterwards.
  • the pressure-sensitive adhesive layer may be a layer called a pressure-sensitive adhesive (Pressure Sensitive Adhesive, PSA) that is stuck to an object by pressing.
  • PSA Pressure Sensitive Adhesive
  • the pressure-sensitive adhesive may be a pressure-sensitive adhesive that is “a substance that is sticky at normal temperature and adheres to an adherend with light pressure” (JIS K6800). And an adhesive that can maintain stability until the coating is broken by appropriate means (pressure, heat, etc.) (JIS K6800).
  • the layer having a function of adjusting the hue (hue adjusting layer) as the functional layer 20 is a layer capable of adjusting the laminate 30 to a target hue.
  • the hue adjustment layer may be a layer containing a resin and a colorant, for example.
  • the colorant include inorganic pigments such as titanium oxide, zinc oxide, dial, titanium oxide-based fired pigment, ultramarine blue, cobalt aluminate, and carbon black; azo-based compounds, quinacridone-based compounds, anthraquinone-based compounds, and perylene-based materials.
  • Organic pigments such as compounds, isoindolinone compounds, phthalocyanine compounds, quinophthalone compounds, selenium compounds and diketopyrrolopyrrole compounds; body pigments such as barium sulfate and calcium carbonate; basic dyes, acid dyes and mordant dyes And the like.
  • the layer having a function of adjusting the refractive index (refractive index adjusting layer) as the functional layer 20 is a layer having a refractive index different from that of the resin film 10 and can impart a predetermined refractive index to the laminate.
  • the refractive index adjusting layer may be, for example, an appropriately selected resin, a resin layer further containing a pigment in some cases, or a metal thin film.
  • Examples of the pigment for adjusting the refractive index include silicon oxide, aluminum oxide, antimony oxide, tin oxide, titanium oxide, zirconium oxide, and tantalum oxide.
  • the average particle diameter of the pigment is preferably 0.1 ⁇ m or less.
  • Examples of the metal used for the refractive index adjustment layer include metals such as titanium oxide, tantalum oxide, zirconium oxide, zinc oxide, tin oxide, silicon oxide, indium oxide, titanium oxynitride, titanium nitride, silicon oxynitride, and silicon nitride. Examples thereof include oxides and metal nitrides.
  • the functional layer 20 appropriately has the above function according to the use of the laminate 30.
  • the functional layer 20 may be a single layer or a plurality of layers. Each layer may have one function or two or more functions.
  • the functional layer 20 preferably has a function of expressing high hardness on the surface and a function of absorbing ultraviolet rays.
  • the functional layer 20 in this case is “a single layer having a function of developing high hardness on the surface and an ultraviolet absorbing function”, “a multilayer including a layer having a function of developing high hardness on the surface and an ultraviolet absorbing function” Or “a multilayer including a single layer having a function of developing high hardness on the surface and a function of absorbing ultraviolet light and a layer of developing high hardness” is preferable.
  • the thickness of the functional layer 20 is appropriately adjusted according to the flexible device to which the laminate 30 is applied, but is preferably 1 ⁇ m to 100 ⁇ m, and more preferably 2 ⁇ m to 80 ⁇ m.
  • the functional layer 20 is typically thinner than the resin film 10.
  • the laminate 30 can be obtained by forming the functional layer 20 on the main surface 10 a of the resin film 10.
  • the functional layer 20 can be formed by a known roll-to-roll or batch method.
  • the pressure-sensitive adhesive layer as the functional layer 20 is formed by, for example, applying a solution containing a pressure-sensitive adhesive that forms the pressure-sensitive adhesive layer to the main surface 10a of the resin film 10 to form a coating film, and drying and curing the coating film. Can be formed.
  • the hue adjustment layer as the functional layer 20 is, for example, applied to the main surface 10a of the resin film 10 with a dispersion liquid containing a pigment or the like that forms the hue adjustment layer and a main material such as a resin in which the pigment or the like is dispersed.
  • the coating film can be formed by drying and curing the coating film.
  • the refractive index adjusting layer as the functional layer 20 is a dispersion containing, for example, inorganic particles that form the refractive index adjusting layer on the main surface 10a of the resin film 10 and a main material such as a resin in which the inorganic particles are dispersed. It can be formed by applying a liquid to form a coating film, and drying and curing the coating film.
  • a multi-layered functional layer including a function that exhibits high hardness on the surface and a layer that has a function of absorbing ultraviolet light can be formed by the following method. Applying a dispersion liquid containing a UV absorber and a main material such as a resin in which the UV absorber is dispersed to the main surface 10a of the resin film 10 to form a coating film, and drying and curing the coating film Thus, an ultraviolet absorbing layer is formed. Then, a hard coat layer may be formed by applying a solution containing a resin for forming a hard coat layer to the ultraviolet absorbing layer to form a coat, and drying and curing the coat. By this method, a multilayer functional layer including a layer having a function of developing high hardness on the surface and a layer having a function of absorbing ultraviolet rays is formed.
  • a multilayer functional layer including a single layer having a function of developing high hardness and a function of absorbing ultraviolet light on the surface and a layer of developing high hardness can be formed by the following method.
  • a coating film is formed on the main surface 10a of the resin film 10 by applying a dispersion containing an ultraviolet absorbent, a main material such as a resin in which the ultraviolet absorbent is dispersed, and a resin that forms a hard coat layer, The coating film is dried and cured to form a single layer having a function of expressing high hardness and an ultraviolet absorption function on the surface, and further, a solution containing a resin that forms a hard coat layer on the single layer.
  • a multilayer functional layer including a layer having a function of developing high hardness on the surface and a function of absorbing ultraviolet light and a layer having a function of developing high hardness on the surface is formed.
  • the laminate 30 of the present embodiment obtained in this way is excellent in flexibility.
  • the laminate 30 has functionality such as transparency, UV resistance, and a function to develop high hardness on the surface, which are required when applied to a base material of an optical member or a display member of a flexible device or a front plate. be able to.
  • the laminated body 30 has Si / N of 8 or more on the main surface 10a of the resin film 10, the adhesiveness between the resin film 10 and the functional layer 20 is also excellent.
  • the functional layer 20 is a layer (hard coat layer) having a function of developing high hardness on the surface, the functional layer 20 can have a high surface hardness.
  • primer agent examples include a UV-curable, thermosetting, or two-component curable epoxy compound primer agent.
  • the primer agent may be a polyamic acid. These primer agents are suitable for enhancing the adhesion between the resin film 10 and the functional layer 20.
  • the primer agent may contain a silane coupling agent.
  • the silane coupling agent may be chemically bonded to the silicon material contained in the resin film 10 by a condensation reaction.
  • the silane coupling agent can be suitably used particularly when the compounding ratio of the silicon material contained in the resin film 10 is high.
  • Examples of the silane coupling agent include compounds having an alkoxysilyl group having a silicon atom and 1 to 3 alkoxy groups covalently bonded to the silicon atom.
  • a compound having a structure in which two or more alkoxy groups are covalently bonded to a silicon atom is preferable, and a compound having a structure in which three alkoxy groups are covalently bonded to a silicon atom is more preferable.
  • the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group. Among these, a methoxy group and an ethoxy group are preferable because reactivity with a silicon material can be increased.
  • the silane coupling agent preferably has a substituent having high affinity with the resin film 10 and the functional layer 20.
  • the substituent of the silane coupling agent is preferably an epoxy group, an amino group, a ureido group or an isocyanate group.
  • the functional layer 20 contains (meth) acrylates
  • the affinity increases when the silane coupling agent used for the primer layer 25 has an epoxy group, a methacryl group, an acrylic group, an amino group, or a styryl group. preferable.
  • a silane coupling agent having a substituent selected from a methacryl group, an acryl group, and an amino group is preferable because it tends to have excellent affinity with the resin film 10 and the functional layer 20.
  • the thickness of the primer layer 25 is appropriately adjusted according to the functional layer 20, but is preferably 0.01 nm to 20 ⁇ m.
  • the thickness of the primer layer 25 is preferably 0.01 ⁇ m to 20 ⁇ m, and more preferably 0.1 ⁇ m to 10 ⁇ m.
  • the primer layer 25 preferably has a thickness of 0.1 nm to 1 ⁇ m, and more preferably 0.5 nm to 0.1 ⁇ m.
  • the laminate 30 in FIG. 4 forms a coating film by applying a solution in which the primer agent is dissolved to the main surface 10a of the resin film 10 and then drying and curing the formed coating film to form a primer layer. It can manufacture by the method including doing.
  • the method for forming other members is the same as that of the laminate 30 in FIG.
  • the primer layer 25 may be cured simultaneously with the functional layer 20 or may be separately cured before the functional layer 20 is formed.
  • the laminate of the present embodiment has high transparency and can maintain excellent visibility when bent. Moreover, this laminated body can also have the outstanding flexibility. Moreover, when the primer layer is provided between the resin film and the functional layer, the adhesiveness of the resin film and the functional layer becomes high.
  • the laminate can have functionality such as transparency, UV resistance, and surface hardness required when applied to an optical member of a flexible device or a substrate of a display member, or a front plate.
  • the structure of the resin film and the laminate can be modified as appropriate.
  • functional layers can be provided on both sides of the resin film as in the laminate 30 in FIG.
  • a primer layer may be provided between each functional layer and the resin film.
  • FIG. 5 is a cross-sectional view showing an embodiment of a display device.
  • a display device 100 illustrated in FIG. 5 includes an organic EL device 50, a touch sensor 70, and a front plate 90. These are usually housed in a housing.
  • the organic EL device 50 and the touch sensor 70 and the touch sensor 70 and the front plate 90 are bonded with, for example, an optical adhesive (not shown) (Optical Clear Adhesive, OCA).
  • OCA Optical Clear Adhesive
  • the organic EL device 50 is a display member having an organic EL element 51, a first substrate 55, a second substrate 56, and a sealing material 59.
  • the organic EL element 51 has a pair of electrodes (first electrode 52 and second electrode 53) and a light emitting layer 54.
  • the light emitting layer 54 is disposed between the first electrode 52 and the second electrode 53.
  • the first electrode 52 is made of a light-transmitting conductive material.
  • the second electrode 53 may also have optical transparency.
  • a known material can be employed as the first electrode 52 and the second electrode 53.
  • the light emitting layer 54 can be formed of a known light emitting material constituting the organic EL element.
  • the light emitting material may be either a low molecular compound or a high molecular compound.
  • the first substrate 55 is made of a light transmissive material.
  • the second substrate 56 may be light transmissive.
  • substrate 56 are bonded together by the sealing material 59 arrange
  • the first substrate 55, the second substrate 56, and the sealing material 59 form a sealing structure that seals the organic EL element inside.
  • the first substrate 55 and / or the second substrate 56 is often a gas barrier material.
  • the first substrate 55 and the second substrate 56 that can employ the resin film or laminate according to the present embodiment correspond to the base material or gas barrier material of the display member in the present embodiment.
  • the organic EL device 50 including the first substrate 55 and the second substrate 56 employs the laminate according to the present embodiment, and thus has excellent flexibility.
  • the touch sensor 70 is an optical member having a touch sensor base 71 and an element layer 72 having a detection element formed on the touch sensor base 71.
  • the touch sensor substrate 71 is made of a light transmissive material.
  • an inorganic material such as glass or a known transparent resin such as an acrylic resin can be used.
  • the touch sensor substrate 71 the resin film or laminate according to the present embodiment described above can also be employed.
  • the touch sensor substrate 71 that can employ the laminate according to the present embodiment corresponds to the optical member in the present embodiment. Since the touch sensor 70 having such a touch sensor substrate 71 employs the resin film or laminate according to the present embodiment, it has excellent flexibility.
  • the front plate 90 is made of a light transmissive material.
  • the front plate 90 is located on the outermost layer on the display screen side of the display device and functions as a protective member that protects the display device.
  • the front plate may be referred to as a window film.
  • an inorganic material such as glass or a known transparent resin such as an acrylic resin can be used.
  • the front plate 90 the above-described resin film or laminate according to this embodiment can also be employed.
  • the laminated body is usually arranged in such a direction that the functional layer is located outside the display device.
  • the display device 100 can have excellent flexibility as a whole. . That is, the display device 100 can be a flexible device. In addition, the outer surface of the display device 100 can have a high surface hardness.
  • the apparatus (flexible device) to which the resin film or the laminate according to the present embodiment can be applied is not limited to the display device.
  • it is also applicable to a solar cell having a substrate on which a photoelectric conversion element is formed and a front plate provided on the substrate surface.
  • the solar cell can have excellent flexibility as a whole.
  • polyimide polyimide polymer containing a repeating structural unit of the formula (PI) was obtained by purification and drying.
  • Example 2 A mixed solution for changing a polyimide to a polyimide having a glass transition temperature of 300 ° C. (“Neoprim” manufactured by Mitsubishi Gas Chemical Co., Ltd., a polyimide-based polymer containing a repeating structural unit of the formula (PI)) and forming a resin film A resin film having a thickness of 80 ⁇ m was obtained in the same manner as in Example 1 except that the mass ratio of silica particles to polyimide was changed to 30:70. The yellowness (YI value) of the obtained resin film was 1.8.
  • Example 3 A resin film having a thickness of 80 ⁇ m was obtained in the same manner as in Example 1 except that the alkoxysilane having an amino group was not added to the mixed solution for forming the resin film. The resulting resin film had a yellowness (YI value) of 2.5.
  • Glass transition temperature (Tg) As a measuring device, DSC Q200 manufactured by TA Instruments was used. The differential operation calorimetry (DSC) of the resin film was performed under the conditions of a sample amount: 5 mg, a temperature range: room temperature to 400 ° C., and a heating rate: 10 ° C./min. The glass transition temperature was determined from the obtained DSC curve.
  • the resin film of Comparative Example 4 had an elastic modulus of 4.0 GPa or more, it was ruptured with less than 20000 times of bending.
  • the pencil hardness on the surface of the resin film in the glass substrate / resin film laminate no difference was observed between the Examples and Comparative Examples 1, 2, 3, and 4.
  • the pencil hardness of the hard coat layer surface in the laminate of the adhesive layer / resin film / hard coat layer showed a sufficiently high value only in the case of the resin film of the example. From this result, the resin film satisfies both the tensile elastic modulus of 4 GPa or more and the number of bendings exceeding 100,000 times, so that the hardness of the hard coat layer surface in the laminate of the adhesive layer / resin film / hard coat layer is sufficient. It was confirmed that can be imparted.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Theoretical Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un film de résine 10 contenant un polymère de polyimide. Le module d'élasticité en traction du film de résine est d'au moins 4,0 GPa. Dans un test de flexion dans lequel le film de résine 10 a été plié de façon répétée en une forme de U et redressé (une courbure ayant été réalisée jusqu'à ce que la distance entre des parties opposées du film de résine soit de 3 mm), le nombre de fois où le film de résine 10 pouvait être plié avant la rupture du film de résine 10 était supérieur à 100.000 fois.
PCT/JP2017/001970 2017-01-20 2017-01-20 Film de résine, stratifié, élément optique, matériau formant une barrière aux gaz et substrat de capteur tactile WO2018134974A1 (fr)

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CN112225922A (zh) * 2019-06-28 2021-01-15 Skc株式会社 聚合物膜及其制造方法
WO2021020054A1 (fr) * 2019-07-26 2021-02-04 住友化学株式会社 Stratifié optique et son procédé de fabrication
CN113167932A (zh) * 2019-10-28 2021-07-23 住友化学株式会社 光学层叠体和显示装置

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JP2005187768A (ja) * 2003-12-26 2005-07-14 Mitsubishi Gas Chem Co Inc ポリイミド／無機複合材料の製造方法
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WO2016060213A1 (fr) * 2014-10-17 2016-04-21 三菱瓦斯化学株式会社 Composition de résine de polyimide, film de polyimide et stratifié
WO2016063993A1 (fr) * 2014-10-23 2016-04-28 宇部興産株式会社 Film polyimide, précurseur de polyimide, et polyimide
WO2016076243A1 (fr) * 2014-11-10 2016-05-19 住友化学株式会社 Film de résine, film stratifié, élément optique, élément d'affichage, plaque avant, et procédé de production de film stratifié
WO2017014287A1 (fr) * 2015-07-22 2017-01-26 住友化学株式会社 Film de résine, stratifié, élément optique, matériau barrière aux gaz et substrat de capteur tactile

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JP2005068347A (ja) * 2003-08-27 2005-03-17 Mitsui Chemicals Inc ポリイミド組成物およびその製造方法と用途
JP2005187768A (ja) * 2003-12-26 2005-07-14 Mitsubishi Gas Chem Co Inc ポリイミド／無機複合材料の製造方法
JP2008163309A (ja) * 2006-12-29 2008-07-17 Ind Technol Res Inst ハイブリッド組成物およびこれを用いて製造されるフィルム
JP2009215412A (ja) * 2008-03-10 2009-09-24 New Japan Chem Co Ltd ポリイミド樹脂組成物及びその成形体
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WO2016060213A1 (fr) * 2014-10-17 2016-04-21 三菱瓦斯化学株式会社 Composition de résine de polyimide, film de polyimide et stratifié
WO2016063993A1 (fr) * 2014-10-23 2016-04-28 宇部興産株式会社 Film polyimide, précurseur de polyimide, et polyimide
WO2016076243A1 (fr) * 2014-11-10 2016-05-19 住友化学株式会社 Film de résine, film stratifié, élément optique, élément d'affichage, plaque avant, et procédé de production de film stratifié
WO2017014287A1 (fr) * 2015-07-22 2017-01-26 住友化学株式会社 Film de résine, stratifié, élément optique, matériau barrière aux gaz et substrat de capteur tactile

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112225922A (zh) * 2019-06-28 2021-01-15 Skc株式会社 聚合物膜及其制造方法
CN112225922B (zh) * 2019-06-28 2023-09-29 爱思开迈克沃有限公司 聚合物膜及其制造方法
WO2021020054A1 (fr) * 2019-07-26 2021-02-04 住友化学株式会社 Stratifié optique et son procédé de fabrication
CN113167932A (zh) * 2019-10-28 2021-07-23 住友化学株式会社 光学层叠体和显示装置

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