WO2009119445A1

WO2009119445A1 - Release agent

Info

Publication number: WO2009119445A1
Application number: PCT/JP2009/055445
Authority: WO
Inventors: 晃之福田; 尚志三橋
Original assignee: ダイキン工業株式会社
Priority date: 2008-03-24
Filing date: 2009-03-19
Publication date: 2009-10-01

Abstract

Disclosed is a release agent comprising a fluoropolymer that does not cause a poor appearance in a molded product surface, can be held and applied well onto the surface of the molded product and has a satisfactorily high water solubility. The release agent comprises a fluoropolymer that comprises (A) a repeating unit derived from a fluoroacrylate monomer and (B) a repeating unit derived from an amino group-containing monomer and is soluble in water. The amino group-containing monomer (B) is preferably represented by formula: Formula (II) wherein R11, R12, and R21, which may be the same or different, represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; Y11 represents an oxygen atom or NH; Z represents a branched or straight-chain alkylene group having 1 to 10 carbon atoms; and R11 and R12 may combine with each other and, together with an adjacent nitrogen atom, form a ring.

Description

Release agent

The present invention relates to a mold release agent, and more particularly, to a mold release agent used by being applied to a mold for molding a synthetic resin or rubber.

The present invention relates to a release agent (release agent composition), and more particularly to a mold release agent suitable for use in molding a molded body such as a synthetic resin or a synthetic rubber.
Conventional technology When molding synthetic resin moldings such as acrylic resins, epoxy resins, urethane resins, vinyl chloride resins, and vinyl acetate resins, and moldings of synthetic rubber, it is easy to release the molding from the molding die. For this purpose, a release agent is applied to the inner surface of the molding die.
As a mold release agent used in such a case, wax-type mold release agents such as paraffin wax, higher fatty acid ester wax, polyethylene wax and the like are known. These wax-based release agents are widely used since they are available at low cost and the surface state of the resulting molded article is good.

However, since the wax-based mold release agent is inferior in mold release force, it is sufficient to apply it thickly to the mold, especially when molding a molded body using a material having strong adhesive force such as epoxy resin or urethane resin. Therefore, there is a problem that the inside of the molding die is contaminated as the number of molding steps is repeated. This problem also adversely affects the dimensional accuracy of the molded body.
Moreover, since the wax-type mold release agent is also inferior in the adhesive force with respect to a shaping | molding die, it also has the problem that it transfers to a molded object surface easily and is inferior to the sustainability of a mold release effect. This problem leads to the problem that a mold release agent must be formed for each molding process.
Furthermore, since the wax-based mold release agent is transferred to the surface of the molded body in large quantities when the molded body is released from the molding die, the problem that the secondary processability (printing and coating) on the surface of the molded body is inferior. Have

As a solution to these problems, a fluorine-based mold release agent [a copolymer of a polyfluoroalkyl ester of (meth) acrylic acid and a substituted vinyl compound] is known (Japanese Patent Laid-Open No. 59-101319). No. and JP-A-60-255404).
Since these fluorine-based mold release agents are excellent in mold release force, a sufficient mold release effect can be obtained only by forming a thin film. Moreover, since it is excellent also in the adhesive force with respect to a shaping | molding die compared with the said wax-type mold release agent, it is excellent also in the sustainability of a mold release effect.
However, even with the above-mentioned fluorinated mold release agents, it is unavoidable to completely transfer to the surface of the molded body, and if this transfers to the surface of the molded body, secondary workability (printing on the surface of the molded body) , Paint). This is because the fluorine-based mold release agent that has been transferred to the surface of the molded product exhibits mold releasability with respect to ink and paint when printing and painting.

Japanese Patent Publication No. 3-8245 discloses a release agent comprising a copolymer obtained by polymerizing a perfluoroalkyl group-containing vinyl monomer, a phosphoric acid-containing vinyl monomer and a hydrocarbon vinyl monomer. Is disclosed. Patent Nos. 0940355 and 0940356 disclose a mold release agent comprising a perfluoroalkyl group phosphate ester.
However, in these fluorine-based mold release agents, a large amount of phosphoric acid is blended. Therefore, a resin or rubber accompanied by a reaction at the time of molding processing, particularly a urethane resin, inhibits the curing reaction, resulting in a molded article resulting from this. The appearance of the surface is poor. Moreover, the problem of mold contamination arises by reaction with a mold release agent and a molded object.

In Japanese Patent Publication No. 3-8245 and Japanese Patent Publication No. 5-517288, there is also known a release agent obtained by blending a polyfluoroalkyl group-containing copolymer with silicone oil and silicone resin. However, since silicone is blended, stickiness is generated on the surface of the molded body and the secondary processability is poor. Silicone also causes work environment contamination. The silicone-based release agent has a problem that when it is transferred to the surface of the molded body, the surface of the molded body becomes sticky or the secondary workability to the surface of the molded body is inferior.
Further, when these fluorine-based mold release agents are dispersed in water, a large amount of an emulsifier is required. When this emulsifier is transferred to the surface of the molded product, a large amount of the same is obtained as in the case of the wax-type mold release agent and the silicone mold release agent. Therefore, there is a problem that the surface of the molded body is sticky or the secondary workability to the surface of the molded body is inferior.

Next, I will explain the environmental problems of PFOA. From recent research results [EPA report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)] Concerns about the environmental impact of PFOA (perfluorooctanoic acid), a type of fluoroalkyl compound, have become apparent, and on April 14, 2003, EPA (US Environmental Protection Agency) will strengthen scientific research on PFOA Announced.
On the other hand, Federal Register (FR Vol.68, No.73 / April 16, 2003 [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr.pdf) and EPA Environmental News FOR RELEASE : MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) and EPA OPPT FACT SHEET April 14, 2003 (http: // www. epa.gov/opptintr/pfoa/pfoafacts.pdf) publishes that telomers can produce PFOA by degradation or metabolism (telomers mean long chain fluoroalkyl groups). We also announced that telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather. Yes.

If the Rf group carbon number of the fluorine-containing copolymer mentioned above is 8 or more, there is a concern that it may contain PFOA and PFOA analogs that have bioaccumulation potential, and the carbon number is 6 or less as soon as possible. There has been a demand for a fluoropolymer having an improved transition to a short-chain Rf group-containing fluoroacrylate polymer and improved affinity with other materials and skin.
USP4147851 specification JP-A-8-225620 Special Table 2002-524645

An object of the present invention is to provide a mold release agent comprising a fluoropolymer having a sufficiently high water-solubility and having good appearance on the surface of the molded body, good maintainability to the surface of the molded body. .

The present invention comprises (A) a repeating unit derived from a fluorine-containing acrylate monomer, and (B) a fluorine-containing polymer having a repeating unit derived from an amino group-containing monomer, which is water-soluble. A mold release agent containing is provided.

The release agent of the present invention is characterized in that the fluoropolymer has a short-chain fluoroalkyl group having 7 or less carbon atoms, particularly 6 or less, so that sufficient solubility in water can be obtained. . Since the fluoropolymer of the present invention has a sufficiently high water solubility, it does not require a large amount of emulsifier, so there is no appearance defect on the surface of the molded body, and the maintainability to the surface of the molded body is good. It has an excellent releasability. In particular, the surface state of the molded body is good, there are no holes on the surface, and the surface is fine.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the “acrylate monomer” includes not only an acrylate having a hydrogen atom at the α-position but also an acrylate in which the hydrogen atom at the α-position is substituted with a substituent such as a methyl group or a halogen atom. .
In the fluorine-containing polymer, examples of the fluorine-containing acrylate monomer (A) include at least one fluorine-containing group selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group and a fluoroether group (hereinafter referred to as “fluorine-containing group”). And the formula: —O—CO—CX═CH ₂
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, A substituted or unsubstituted phenyl group. ]
It is a monomer which has an unsaturated group represented by these.

Examples of the acrylate monomer having a fluorine-containing group include a formula:

[Wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms (for example, 1 to 6), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group. (Where X ¹ and X ² are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituent Or an unsubstituted benzyl group, a substituted or unsubstituted phenyl group,
Y represents a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms) or a —CH ₂ CH (OY ¹ ) CH ₂ — group ( Y ¹ is a hydrogen atom or an acetyl group.
Rf represents a linear or branched fluoroalkyl group having 1 to 7 carbon atoms, a fluoroalkenyl group having 2 to 7 carbon atoms, or repeating units: —C ₃ F ₆ O—, —C ₂ F ₄ O— and — A fluoroether group having a total number of 1 to 200 of at least one repeating unit selected from the group consisting of CF ₂ O—. ]
Indicated by

In the formula (I), when the Rf group is a fluoroalkyl group, it is preferably a perfluoroalkyl group. Examples of Rf groups are -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ). ₂ , -C (CF ₃ ) ₃ ,-(CF ₂ ) ₄ CF ₃ ,-(CF ₂ ) ₂ CF (CF ₃ ) ₂ , -CF ₂ C (CF ₃ ) ₃ , -CF (CF ₃ ) CF ₂ CF ₂ CF ₃ ,-(CF ₂ ) ₅ CF ₃ ,-(CF ₂ ) ₃ CF (CF ₃ ) ₂ ,-(CF ₂ ) ₄ CF (CF ₃ ) ₂ ,-(CF ₂ ) ₂ H, -CF ₂ CFHCF ₃ , — (CF ₂ ) ₄ H, — (CF ₂ ) ₆ H, and the like. When the Rf group is a fluoroalkyl group, the number of carbons in the Rf group should be 1 to 7, for example 2 to 6, especially 4 to 6, especially 6 from the viewpoints of PFOA and functions described above. Is preferred. Rf may be linear.
When the Rf group is a fluoroalkenyl group, examples of the Rf group are -CF = CF (CF ₃ ), -CF = C (CF ₃ ) ₂ , -CF = C (CF ₃ ) (CF ₂ CF ₂ CF ₃ ) , -CF = C (CF ₃ ) (CF (CF ₃ ) ₂ ), -C (CF ₃ ) = CF (CF (CF ₃ ) ₂ ), -C (CF ₂ CF ₃ ) = C (CF ₃ ) ₂ Etc. When the Rf group is a fluoroalkenyl group, the Rf group preferably has 2 to 7 carbon atoms, particularly 3 to 6 carbon atoms, especially 6 carbon atoms.

When the Rf group is a fluoroether group, the fluoroether group is at least one repeating unit selected from the group consisting of —C ₃ F ₆ O—, —C ₂ F ₄ O—, and —CF ₂ O— (oxypar group). Fluoroalkylene group). —C ₃ F ₆ O— is —CF ₂ CF ₂ CF ₂ O— or —CF ₂ C (CF ₃ ) FO—. —C ₂ F ₄ O— is generally —CF ₂ CF ₂ O—. The total number of oxyperfluoroalkylene repeating units is 1 to 200, for example 1 to 100, in particular 5 to 50. The fluoroether group has a terminal group that is directly bonded to the oxyperfluoroalkylene repeat unit. Examples of the terminal group include a hydrogen atom, a halogen atom (for example, a fluorine atom), an alcohol group (for example, HOCH ₂ —), an epoxy group (for example,

),
An amine group (for example, H ₂ N-), a carboxylic acid group (for example, HOOC-), an acid halide group (for example, F (O =) C-), and a chloromethyl group (ClH ₂ C-). The fluoroether group may have a C1-C10 fluoroalkylene group, particularly a perfluoroalkylene group, in addition to the oxyperfluoroalkylene repeating unit and the terminal group. Examples of the fluoroalkylene group having 1 to 10 carbon atoms are —CF ₂ — and —CF ₂ CF ₂ —.

Examples of fluoroether groups (particularly perfluoroether groups) that are examples of Rf groups are as follows.
F- (CF ₂ CF ₂ CF ₂ O) _n -CF ₂ CF _2- (n is 1 to 200)
F- (CF ₂ C (CF ₃ ) FO) _n -CF ₂ CF _2- (n is 1 to 200)
F- (CF ₂ C (CF ₃ ) FO) _n- (CF ₂ O) _m -CF ₂ CF _2- (total of n and m is 1 to 200)
F- (CF ₂ CF ₂ O) _n- (CF ₂ O) _m -CF ₂ CF _2- (total of n and m is 1 to 200)

Y represents a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms) or a —CH ₂ CH (OY ¹ ) CH ₂ — group ( However, Y < ¹ > is a hydrogen atom or an acetyl group.). The aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, such as 1 or 2). The aromatic group and the cycloaliphatic group may be either substituted or unsubstituted.

X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where X ¹ and X ² are hydrogen atoms) Atom, fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted Of the phenyl group. X may be a hydrogen atom or a methyl group, but the α-position may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or the like.

Examples of the fluorine-containing acrylate monomer are as follows.
Rf- (CH ₂ ) ₁₀ OCOCH═CH ₂
_{_{Rf- (CH 2) 10 OCOC (}} CH 3) = CH 2
Rf—CH ₂ OCOCH═CH ₂
_{_{Rf-CH 2 OCOC (CH 3}} ) = CH 2
Rf- (CH ₂ ) ₂ OCOCH═CH ₂
Rf- (CH ₂ ) ₂ OCOC (CH ₃ ) ═CH ₂
_{_{Rf-SO 2 N (CH 3}} ) (CH 2) 2 OCOCH = CH 2
_{_{Rf-SO 2 N (C 2}} H 5) (CH 2) 2 OCOCH = CH 2
_{_{Rf-CH 2 CH (OCOCH 3}} ) CH 2 OCOC (CH 3) = CH 2
_{Rf-CH 2 CH (OH)} CH 2 OCOCH = CH 2

[Wherein Rf is a linear or branched fluoroalkyl group having 1 to 7 carbon atoms, a fluoroalkenyl group having 2 to 7 carbon atoms, or a repeating unit: —C ₃ F ₆ O—, —C ₂ F ₄ A fluoroether group having a total number of 1 to 200 of at least one repeating unit selected from the group consisting of O— and —CF ₂ O—. ]

The amino group-containing monomer (B) is a compound having an amino group and a carbon-carbon double bond.
Examples of amino group-containing monomers (B) have the formula:

[Wherein R ¹¹ , R ¹² and R ²¹ are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y ¹¹ is an oxygen atom or NH, and Z is 1 to 4 carbon atoms] 21 (for example, 1 to 10) branched or straight chain alkylene groups. R ¹¹ and R ¹² may be bonded to each other to form a ring together with the adjacent nitrogen atom. ]
It is shown by.
Since the copolymer includes an amino group, for example, when a salt is formed with a protonic acid, the copolymer is dissociated when dissolved in water and becomes cationic.

R ¹¹ , R ¹² and R ²¹ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, butyl, etc.). R ²¹ is preferably a hydrogen atom or a methyl group. R ¹¹ and R ¹² are preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms (that is, methyl, ethyl). When R ¹¹ and R ¹² are bonded to each other to form a ring with an adjacent nitrogen atom, R ¹¹ and R ¹² may be bonded through a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom. Examples of the ring formed by combining R ¹¹ and R ¹² together with the adjacent nitrogen atom (for example, a 3- to 8-membered ring, particularly a 6-membered ring) include an aziridine ring, pyrrolidine ring, piperidine ring, piperazine ring, morpholine A ring etc. are mentioned.
Examples of the alkylene group represented by Z include linear or branched C1-C21 such as methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene groups (for example, 1-10, preferably 1-4 C1). In particular, 1 to 3) alkylene groups are mentioned.

Specific examples of the amino group-containing monomer (B) include chemical formulas (II) such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. compound Y ¹¹ is an oxygen atom in; dimethylaminoethyl (meth) acrylamide, Y ¹¹ in dimethylaminopropyl (meth) formula of acrylamide (II) and the like compounds wherein NH. The amino group-containing monomer (B) can be used alone or in combination of two or more.

The monomer constituting the fluoropolymer may contain a hydrophilic non-fluorine monomer (C) in addition to the monomers (A) and (B). The hydrophilic non-fluorine monomer (C) has hydrophilicity and does not contain a fluorine atom.
An example of a hydrophilic group is an oxyalkylene group.

The hydrophilic non-fluorine monomer (C) may be a monomer having a hydrophilic group which is an oxyalkylene group (2 to 6 carbon atoms of an alkylene group) and a carbon-carbon double bond.
The hydrophilic group which is an oxyalkylene group is nonionic. The number of oxyalkylene groups in the hydrophilic non-fluorine monomer (C) may be 2 to 200, for example 3 to 50.
The hydrophilic non-fluorine monomer (C) may be polyalkylene glycol mono (meth) acrylate and / or polyalkylene glycol di (meth) acrylate.
The molecular weight of the hydrophilic non-fluorine monomer (C) may be 100 or more, such as 150 or more, particularly 200 or more, particularly 250 to 3000.

The polyalkylene glycol mono (meth) acrylate has the general formula:
CH ₂ = CX ¹ C (= O) -O- (RO) _n -X ² (III)
[Where:
X ¹ is a hydrogen atom or a methyl group,
X ² is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is an alkylene group having 2 to 6 carbon atoms,
n is an integer of 2 to 90,
It is. ]
It is preferable that it is shown by these. n may in particular be 3 to 30, for example 4 to 20.

R in the general formula (III) is particularly preferably an ethylene group.
R in the general formula (III) may be a combination of two or more alkylene groups. In that case, at least one of R is preferably an ethylene group. Examples of the combination of R include an ethylene group / propylene group combination and an ethylene group / butylene group combination.
The hydrophilic non-fluorine monomer (C) may be a mixture of two or more. In that case, at least one of the hydrophilic non-fluorine monomers (C) preferably has R in the general formula (III) as an ethylene group.

Specific examples of the hydrophilic non-fluorine monomer (C) include, for example, the following, but are not limited thereto.
CH ₂ = CX ¹ COO- (CH ₂ CH ₂ O) _n -H
CH ₂ = CX ^1- (CH ₂ CH ₂ O) _n -CH ₃
CH ₂ = CX ¹ COO- (CH ₂ CH (CH ₃ ) O) _n -H
CH ₂ = CX ¹ COO- (CH ₂ CH (CH ₃ ) O) _n -CH ₃
CH ₂ = CX ¹ COO- (CH ₂ CH ₂ O) _5- (CH ₂ CH (CH ₃ ) O) ₂ -H
CH ₂ = CX ¹ COO- (CH ₂ CH ₂ O) _5- (CH ₂ CH (CH ₃ ) O) ₃ -CH ₃
_{^{CH 2 = CX 1 COO- (CH}} 2 CH 2 O) 8 - (CH 2 CH (CH 3) O) 6 -CH 2 CH (C 2 H 5) C 4 H 9
CH ₂ = CX ¹ COO- (CH ₂ CH ₂ O) ₂₃ -OOC (CH ₃ ) C = CH ₂
_{^{CH 2 = CX 1 COO- (CH}} 2 CH 2 O) 20 - (CH 2 CH (CH 3) O) 5 -CH 2 -CH = CH 2

The monomer constituting the fluoropolymer may contain another monomer (D) as required in addition to the monomers (A), (B), (C). The other monomer (D) is preferably a non-fluorine monomer. Examples of the other monomer (D) include hydrocarbon group-containing monomers, ethylene, vinyl acetate, vinyl halide (eg, vinyl chloride), vinylidene halide (eg, vinylidene chloride), acrylonitrile, 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, vinyl alkyl ketone, vinyl alkyl Examples include, but are not limited to, ether, isoprene, chloroprene, butadiene and the like.

Another example of the other monomer (D) includes a monomer having a silane group. The monomer having a silane group is preferably a compound having a silane group (particularly a terminal silane group) and a carbon-carbon double bond. The monomer having a silane group may be a terminal silane coupling agent or a monomer having a silane coupling agent in the side chain.
Specific examples of the monomer having a silane group are as follows.
CH ₂ = CHCO ₂ (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
CH ₂ = CHCO ₂ (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ ,
_{_{CH 2 = C (CH 3)}} CO 2 (CH 2) 3 Si (OCH 3) 3
(Γ-methacryloxypropyltrimethoxysilane),
CH ₂ = C (CH ₃ ) CO ₂ (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ ,
_{_{_{CH 2 = CHCO 2 (CH 2}}} ) 3 SiCH 3 (OC 2 H 5) 2,
CH ₂ = C (CH ₃ ) CO ₂ (CH ₂ ) ₃ SiC ₂ H ₅ (OCH ₃ ) ₂ ,
_{_{CH 2 = C (CH 3)}} CO 2 (CH 2) 3 Si (CH 3) 2 (OC 2 H 5),
_{_{CH 2 = C (CH 3)}} CO 2 (CH 2) 3 Si (CH 3) 2 OH,
CH ₂ = CHCO ₂ (CH ₂ ) ₃ SiCH ₃ [ON (CH ₃ ) C ₂ H ₅ ] ₂ ,
CH ₂ = C (CH ₃ ) CO ₂ (CH ₂ ) ₃ SiC ₆ H ₅ [ON (CH ₃ ) C ₂ H ₅ ] ₂ ,
CH ₂ = CHSi (OCH ₃ ) ₃ ,
CH ₂ = CHSi (OC ₂ H ₅ ) ₃ ,
CH ₂ = CHSiCH ₃ (OCH ₃ ) ₂ ,
CH ₂ = CHSi (CH ₃ ) ₂ (OC ₂ H ₅ ),
CH ₂ = CHSi (CH ₃ ) ₂ SiCH ₃ (OCH ₃ ) ₂ ,
CH ₂ = CHSiCH ₃ [ON (CH ₃ ) C ₂ H ₅ ] ₂
Vinyltrichlorosilane,
Vinyltris (2-methoxyethoxy) silane.

The weight average molecular weight of the fluoropolymer may be, for example, from 1,000 to 1,000,000, in particular from 2,000 to 100,000, especially from 4,000 to 20,000. The weight average molecular weight of the fluoropolymer is determined by GPC (gel permeation chromatography) (polystyrene conversion).
The fluoropolymer is soluble in water. The solubility of the fluoropolymer (the amount of the fluoropolymer that can be dissolved in 100 g of water at 25 ° C.) may be 5 g or more, for example, 10 g or more, particularly 20 g or more. The upper limit of solubility may be 500 g, for example 200 g.

The fluorine-containing polymer may be composed of a combination of repeating units derived from the following monomers.
(1) Monomer (A) + Monomer (B)
(2) Monomer (A) + Monomer (B) + Monomer (C)
(3) Monomer (A) + Monomer (B) + Monomer (D)
(4) Monomer (A) + Monomer (B) + Monomer (C) + Monomer (D)

In the fluoropolymer, with respect to 100 parts by weight of the monomer (A),
The amount of monomer (B) is 1 to 500 parts by weight, for example 2 to 100 parts by weight, in particular 3 to 80 parts by weight, especially 5 to 70 parts by weight,
The amount of the monomer (C) is 0 to 10 parts by weight, for example 1 to 5 parts by weight,
The amount of the monomer (D) is 0 to 10 parts by weight, for example 1 to 5 parts by weight,
It may be.

The fluoropolymer in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. In particular, solution polymerization is preferable.

In solution polymerization, a method is adopted in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, for example, is heated and stirred in the range of 50 to 120 ° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, Examples include diisopropyl peroxydicarbonate. The polymerization initiator may be used in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the monomer.

Organic solvents are those that are inert to the monomers and dissolve them, such as pentane, hexane, heptane, octane, isooctane, cyclohexane, benzene, toluene, xylene, petroleum ether, commercial petroleum solvents (ExxonMobil). EXXSOL D40, ISOPER E, etc.), tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, t-butyl acetate, isopropanol, propylene glycol methyl ether acetate, p- Examples include chlorobenzotrifluoride, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like. The organic solvent may be used in the range of 50 to 1000 parts by weight with respect to 100 parts by weight of the total amount of monomers.

After the polymerization reaction, an aqueous solution of the polymer can be obtained by adding water to the reaction mixture and removing the organic solvent (by distillation or the like).

In the present invention, the release agent comprises (1) a fluoropolymer and (2) a liquid medium, that is, water or a mixture of water and a water-soluble organic solvent. Examples of water-soluble organic solvents are alcohols such as methanol, ethanol, n-propanol, isopropanol; ketones such as acetone. The amount of the water-soluble organic solvent may be 50% by weight or less, for example, 1 to 30% by weight with respect to the mixture (the sum of water and the water-soluble organic solvent).
The release agent is in the form of a solution (aqueous solution) of a fluoropolymer.
In the release agent, the amount of the fluorine-containing polymer is not particularly limited and may be appropriately selected from a range in which it can be uniformly dissolved. For example, it may be 0.1 to 50% by weight, for example 0.2 to 20% by weight, in particular 0.5 to 10% by weight, based on the release agent.

The release agent of the present invention may contain (3) an additive in addition to (1) the fluoropolymer and (2) the liquid medium.
Examples of the additive (3) are silicon-containing compounds, waxes, acrylic emulsions and the like.
The silicon-containing compound is preferably a compound having at least one siloxane bond. The silicon-containing compound is a compound excluding a compound having a silane group.

Examples of silicon-containing compounds include alkyl silicates and siliconates.
Examples of alkyl silicates include the following general formula (I):

[Wherein R ¹ⁿ represents an alkyl group having 1 to 18 carbon atoms, and when nn is 2 or more, they may be the same or different. R ²ⁿ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be the same or different when nn is 2 or more. nn represents an integer of 1 to 20. ]
It may be a compound shown by these.

Regarding R ¹ⁿ , the alkyl group having 1 to 18 carbon atoms (that is, a saturated chain aliphatic hydrocarbon group) is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and hexyl. Group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and the like. It may be branched or branched.

Regarding R ²ⁿ , the alkyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and these are linear. Alternatively, it may be branched.
The nn is an integer of 1 to 20, for example, 1 to 10.

More specifically, the alkyl silicate includes, for example, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethyl. Methoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, dodecyltrimethoxysilane, tridecyltrimethoxysilane, tetradecyltrimethoxysilane, pentadecyltrimethoxysilane, hexadecyltrimethoxysilane, heptadecyl Trimethoxysilane, octadecyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrieth Sisilane, pentyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, undecyltriethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetra Examples include decyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane, octadecyltriethoxysilane, and the like. Among them, methyltrimethoxysilane, methyltriethoxysilane, hexyltriethoxy Silane and octyltriethoxysilane are preferred.

In addition, dimers and the like of silicon-containing compounds can also be used as silicon-containing compounds, and examples thereof include those having nn of 2 or 3 in the above general formula (I). Furthermore, nn may be an integer up to 20.

Siliconates (especially alkyl siliconates) are for example represented by the formula:
R ¹ _a Si (OR ² ) _b (OM) _c is a compound represented by _c .
[Wherein, a is an integer of 0 or more (preferably 1), b is an integer of 0 or more (preferably 2), c is an integer of 1 or more (preferably 1), and satisfies a + b + c = 4. R ¹ may be the same or different and represents a hydrocarbon group having 1 to 18 carbon atoms. R ² may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. M may be the same or different and represents an alkali metal. ]

The hydrocarbon group is, for example, an aliphatic hydrocarbon group (for example, an alkyl group), an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group.
Examples of R ¹ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, and n-hexyl. Group, n-heptyl group, n-octyl group, isooctyl group, 2,2,4-trimethylpentyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-octadecyl group, cyclopentyl group, cyclohexyl group , Cycloheptyl group, methylcyclohexyl group, phenyl group, naphthyl group, anthryl group, phenanthryl group, tolyl group, xylyl group, ethylphenyl group, benzyl group, phenylethyl group and the like. Among these, a methyl group, an ethyl group, and a propyl group are preferable, and a methyl group is particularly preferable.
Examples of R ² include a hydrogen atom and the same group as R ¹ . Among these, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen atom is particularly preferable.
Examples of M include Li, Na, K and the like, and Na is particularly preferable.
Specific examples of the alkyl siliconate are sodium methyl siliconate [CH ₃ Si (OH) ₂ (ONa)] and potassium ethyl siliconate [C ₂ H ₅ Si (OH) ₂ (OK)].

The amount of the additive (3) may be 0 to 200 parts by weight, for example 0 to 50 parts by weight, for example, 0.1 to 50 parts by weight with respect to 100 parts by weight of the fluoropolymer (1). .

Furthermore, in addition to the above components (1) to (3), the treating agent may contain other water repellents, other oil repellents, drying rate adjusting agents, cross-linking agents, film-forming aids, compatibilizing agents, Surfactant, antifreezing agent, viscosity modifier, UV absorber, antioxidant, pH adjuster, antifoam agent, slipperiness adjuster, antistatic agent, hydrophilizing agent, antibacterial agent, antiseptic, insecticide, You may contain a fragrance | flavor, a flame retardant, etc.

In this invention, a mold release agent is apply | coated to a metal mold | die and a mold release property is provided to a metal mold | die. The releasable composition of the present invention can be applied to the surface of a mold by a method such as brush coating, roll coating, spray coating, knife coating or dip coating. It may be applied to the surface of the unvulcanized rubber, transferred to the surface of the mold and cured.
The mold may be made of metal (for example, steel, aluminum).

The releasable composition of the present invention is useful for releasing a rubber (for example, an elastomer) and a resin (for example, a thermosetting resin or a thermoplastic resin). Examples of the material to be molded include polyurethane (soft polyurethane, semi-rigid polyurethane and rigid polyurethane), fluoropolymer (for example, fluororubber), silicone (for example, silicone rubber), and synthetic rubber.

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this is only a specific example of this invention, and this invention is not limited to it. In the following, “%” means “% by weight” unless otherwise specified.

Example 1 (Preparation of aqueous solution of “Rf (C6) -DM” polymer)
CF ₃ CF _2- (CF ₂ CF ₂ ) ₂ -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ [Rf (C6) methacrylate] 73.30 g, dimethylaminoethyl methacrylate (DM) 26.70 g, isopropanol (IPA) 150.00 After stirring and dissolving g in a four-necked flask and maintaining at 60 ° C. while purging with nitrogen, 2 g of t-butyl peroxypivalate was added and reacted at 60 ° C. for 6 hours to obtain a polymer solution. The completion of the polymerization reaction was confirmed by gas chromatography to have a monomer conversion rate of 99% or more. Further, while this polymer solution was stirred at 60 ° C., a mixed solution of 10.20 g of CH ₃ COOH (acetic acid) and 300 g of ion-exchanged water was added dropwise. Thereafter, the IPA is removed under reduced pressure, and the solid content of this solution is obtained from the evaporation residue after heating at 130 ° C. for 1 hour, diluted with ion-exchanged water so that the solid content becomes 25 mass%, and is a transparent and stable polymer. An aqueous solution was obtained. Furthermore, the obtained polymer aqueous solution was diluted with ion-exchanged water so that the solid content would be 1 mass%.

Comparative Example 1
Instead of the polymer compound, a fluorine-based mold release agent, Die Free ME-810 (manufactured by Daikin Industries, Ltd.) was used and diluted with ion-exchanged water so that the solid content was 1 mass%.

Test Example 1 and Comparative Test Example 1
About each release agent shown by the said Example and comparative example, according to the following test method, the mold release property, the frequency | count of mold release, and the molding surface were evaluated. The results are shown in Tables 1 to 4 below.

Test Method The mold release agent composition was uniformly applied by spraying only on one surface of a mold having a length of 20 cm, a width of 5 cm, and a depth of 3 cm. Next, the molded product was blended and molded under the conditions shown below, and the release property was evaluated.
Evaluation of releasability is based on the following criteria.
◎: Release with a light force, ○: Release with a little force, △: Release when a strong force is applied, ×: Do not release.

The number of times of mold release was such that after the release agent was applied once, the mold release properties deteriorated without further application. That is, it indicates the number of times that the molded product can be taken out completely.
Moreover, the surface state after shaping | molding was evaluated visually. The evaluation of the surface condition is based on the following criteria. ○: No pinhole or stickiness. Δ: There is no pinhole but there is a sticky feeling. X: Both pinholes and stickiness occur.

The following molded products 1 to 4 were used as molded products.

Molded item 1: Urethane resin
(a) Composition
Liquid A polyol Sumifene 3900 90 parts [Sumitomo Bayer Urethane Co., Ltd.]
Water (foaming agent) 1.6 parts Triethanolamine 3 parts Triethylamine 0.5 parts Kaorizer 0.5 part [manufactured by Kao Corporation]
B liquid isocyanate Sumijoule 44V20 41.3 parts [Sumitomo Bayer Urethane Co., Ltd.]

(b) Curing conditions Urethane foam A liquid and B liquid are mixed at 1500 rpm, poured into the mold, and cured at room temperature.

Molding 2: Fluoro rubber
(a) Compound composition Daiel G740 100 parts [Daikin Industries, Ltd.]
Kyowamag 150 3 parts [Kyowa Chemical Industry Co., Ltd.]
Caldic 2000 6th part [Omi Chemical Industry Co., Ltd.]
20 parts of MT carbon black [manufactured by RTVanderblit Co Inc]

(b) Vulcanization conditions The above compound is sufficiently mixed with a rubber roll and vulcanized under the following conditions.
Vulcanization pressure 150Kg / cm ²
Vulcanization temperature 170 ° C
Vulcanization time 10 minutes

Molding 3: Silicone rubber
(a) Composition
KE-551-U 100 parts [Shin-Etsu Chemical Co., Ltd.]
C-8B 1st [Shin-Etsu Chemical Co., Ltd.]

(b) Vulcanization conditions The above compound is sufficiently mixed with a rubber roll and vulcanized under the following conditions.
Vulcanization pressure 150Kg / cm ²
Vulcanization temperature 160 ° C
Vulcanization time 10 minutes

Molding 4: Synthetic rubber
(a) Composition
IR 2000 55 parts [manufactured by JSR Corporation]
SBR TUFDENE2003 30 parts [Asahi Kasei Corporation]
BR 150 15 parts [Ube Industries, Ltd.]
55 parts of White Carbon Toxeal 255G [manufactured by Lianji Chemical Industry]

(b) Vulcanization conditions The above compound is sufficiently mixed with a rubber roll and vulcanized under the following conditions.
Vulcanization pressure 150Kg / cm ²
Vulcanization temperature 150 ° C
Vulcanization time 10 minutes

The release agent of the present invention has sufficiently high water solubility, is excellent in releasability, and gives a good surface state to a molded article of a polymer substance.

Claims

(A) having a repeating unit derived from a fluorine-containing acrylate monomer, and (B) a repeating unit derived from an amino group-containing monomer,
The fluorine-containing acrylate monomer (A) has the formula:
CH 2 = C (-X) -C (= O) -OY-Rf (I)
[Wherein, X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (where X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, A substituted or unsubstituted phenyl group,
Y represents a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 is an alkyl group having 1 to 4 carbon atoms) or a —CH 2 CH (OY 1 ) CH 2 — group ( Y 1 is a hydrogen atom or an acetyl group.
Rf represents a linear or branched fluoroalkyl group having 1 to 7 carbon atoms, a fluoroalkenyl group having 2 to 7 carbon atoms, or a repeating unit: —C 3 F 6 O—, —C 2 F 4 O— and A fluoroether group having a total number of 1 to 200 of at least one repeating unit selected from the group consisting of —CF 2 O—. ]
The mold release agent containing the fluoropolymer which is shown by these.
The mold release agent according to claim 1, wherein Rf of the fluorine-containing acrylate monomer (A) is a fluoroalkyl group having 2 to 6 carbon atoms or a fluoroalkenyl group having 3 to 6 carbon atoms.
The amino group-containing monomer (B) has the formula:

[Wherein R 11 , R 12 and R 21 are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y 11 is an oxygen atom or NH, and Z is 1 to 4 carbon atoms] 21 branched or straight chain alkylene groups. R 11 and R 12 may be bonded to each other to form a ring together with the adjacent nitrogen atom. ]
The mold release agent according to claim 1 or 2, which is represented by:
The mold release agent according to any one of claims 1 to 3, which comprises a fluoropolymer (1) and a liquid medium (2) and is in the form of a solution.
The mold release agent according to claim 4, wherein the liquid medium (2) is (i) water or (ii) a mixture of water and a water-soluble organic solvent.
The mold release agent according to claim 4 or 5, comprising a fluoropolymer (1), a liquid medium (2), and an additive (3).
The mold release agent according to any one of claims 1 to 6, which releases a molded product made of rubber or resin.
The mold release agent according to claim 7, wherein the molded product is made of polyurethane, fluoropolymer, silicone, synthetic rubber, or synthetic resin.
A mold release method comprising releasing a molded product using the mold release agent according to any one of claims 1 to 8.
A molded product released by the method of claim 9.