KR20150079984A - Mold release agent, mold release agent composition, and method for producing mold release agent - Google Patents

Abstract

It is an object of the present invention to provide a mold release agent having excellent releasability. (A) a radical polymerization-reactive monomer containing at least 20% by weight, based on the total amount of monomers, of perfluoroalkyl groups having 1 to 6 carbon atoms and not having a functional group, and (B) a radical polymerization- A release agent comprising a fluorine-containing polymer which can be obtained by copolymerizing monomers is used as a solution means.

Description

TECHNICAL FIELD [0001] The present invention relates to a releasing agent, a releasing agent composition and a method for producing the releasing agent. [0002] MOLD RELEASE AGENT, MOLD RELEASE AGENT COMPOSITION, AND METHOD FOR PRODUCING MOLD RELEASE AGENT [

The present invention relates to a release agent, a release agent composition, and a production method of a release agent.

It has become necessary to apply a releasing agent (external releasing agent) to the inner surface of a forming die (metal mold) in advance to increase releasability when molding synthetic resin, rubber, or the like. This release agent is often provided as a composition (release agent composition) previously dissolved or dispersed in a solvent or a dispersant. The releasing agent composition is usually applied to the inner surface of the mold by spraying, brushing or the like. When the solvent and the dispersant are removed after the application, a coating film of the release agent is formed on the inner surface of the mold. This improves the releasability of the mold.

Conventionally, as a releasing agent, a fluorine-based releasing agent has been used in addition to a wax-based or silicone-based releasing agent. As a conventional fluorine-based releasing agent, phosphoric acid esters containing a perfluoroalkyl group are the mainstream (Patent Document 1). However, perfluoroalkyl group-containing phosphoric esters can not exert sufficient releasability on their own, and many of them are used in combination with surfactants, silicone oils, or fluorine oils as effective ingredients having different releasability. (Meth) acrylic ester, a phosphoric acid group-containing (meth) acrylic acid ester and a (meth) acrylic-modified silicone oil are copolymerized as a releasing agent whose releasability has been increased to such a degree that it is not necessary to be used in combination with such another active ingredient Fluorine-containing polymers and the like have been developed (Patent Document 2). It is considered that the phosphoric acid group in the releasing agent composed of such a fluorine-containing polymer serves to improve the adhesion to the mold of the releasing agent and to improve the releasability finally imparted to the forming mold.

The releasing agent is usually used after being applied to a forming mold of about 100 ° C to 190 ° C. In order to exhibit excellent releasability, it is important that the release agent is uniformly coated on the mold. However, the conventional fluorine-containing polymer-based releasing agent has a high melt viscosity and has a problem that it is difficult to obtain uniformity when it is applied to a molding frame at a normal use temperature.

Japanese Patent Application Laid-Open No. 52-39587 Japanese Patent Application Laid-Open No. 2009-12250

The present inventors have found that, in the case of a releasing agent comprising a conventional fluorine-containing polymer containing a phosphoric acid group, the adhesiveness to the forming mold is improved by the presence of a phosphoric acid group, and further, the releasability imparted to the forming mold is improved , The presence of a phosphoric acid group newly finds that the release agent reacts with the molding material depending on the case, and the releasability may be deteriorated. Therefore, the present invention provides a mold release agent capable of imparting excellent releasability to a mold while it does not include a functional group including a phosphate group, which has conventionally been thought to have an effect of improving releasability imparted to a mold frame . Another object of the present invention is to provide a mold release agent that tends to become uniform when it is applied to a mold with a normal use temperature.

The present inventors have conducted intensive studies to obtain a fluorine-based mold release agent capable of imparting excellent releasability to a mold while there is no conventionally used functional group for improving the adhesion to the mold of the mold release agent. As a result, the present inventors have found that a fluorine-containing polymer obtained by using a monomer containing a perfluoroalkyl group having 1 to 6 carbon atoms in an amount of 20% by weight or more based on the total amount of monomers can solve the above problems. That is, this releasing agent can impart excellent releasability to the forming mold, even though the functional group is absent. The present invention has been completed by repeating more various studies based on this new knowledge, and is to be published next.

Section 1.

(A) at least 20% by weight, based on the total amount of monomers, of a radical polymerization-reactive monomer containing a perfluoroalkyl group having 1 to 6 carbon atoms and not having a functional group, and

(B) a fluorine-containing polymer obtainable by copolymerizing a radical polymerization-inhibiting monomer having no functional group.

Section 2.

The releasing agent according to item 1, wherein the monomer (A) is represented by the following general formula (I).

(Wherein Rf represents a perfluoroalkyl group having 1 to 6 carbon atoms,

R ₁ represents a divalent aliphatic hydrocarbon group which is linear or branched, a divalent aromatic hydrocarbon group or a divalent cyclic aliphatic hydrocarbon group,

R ₂ is a hydrogen atom or a methyl group.)

Section 3.

In the formula (I), R ₁ is preferably a linear or branched divalent aliphatic hydrocarbon group of 1 to 30 carbon atoms, a divalent aromatic hydrocarbon group of 6 to 12 carbon atoms, or a divalent cyclic aliphatic hydrocarbon group of 6 to 12 carbon atoms , ≪ / RTI >

Section 4.

In the formula (I), R ₁ represents a linear or branched divalent aliphatic hydrocarbon group of 1 to 10 carbon atoms, a divalent aromatic hydrocarbon group of 6 to 10 carbon atoms, or a divalent cyclic aliphatic hydrocarbon group of 6 to 10 carbon atoms , ≪ / RTI >

Item 5.

The releasing agent according to item 2, wherein in the formula (I), R ₁ is an alkylene group having 1 to 10 carbon atoms.

Section 6.

The releasing agent according to item 2, wherein in the formula (I), R ₁ is an alkylene group having 1 to 6 carbon atoms.

Item 7.

The releasing agent according to item 2, wherein in the formula (I), R ₁ is an alkylene group having 1 to 4 carbon atoms.

Section 8.

The releasing agent according to item 2, wherein in the formula (I), R ₁ is an alkylene group having 1 to 2 carbon atoms.

Section 9.

The releasing agent according to any one of items 1 to 8, wherein the monomer (B) is an alkyl (meth) acrylate ester represented by the following formula (II).

(Wherein R ₃ represents a linear or branched monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group or a monovalent cyclic aliphatic hydrocarbon group,

R ₄ is a hydrogen atom or a methyl group.)

Item 10.

In the formula (II), R ₃ represents a linear or branched monovalent aliphatic hydrocarbon group of 1 to 30 carbon atoms, a monovalent aromatic hydrocarbon group of 6 to 12 carbon atoms, or a monovalent cyclic aliphatic hydrocarbon group of 6 to 12 carbon atoms , And the release agent described in item 9.

Section 11.

The releasing agent according to item 9, wherein in the formula (II), R ₃ is a linear or branched alkyl group having 1 to 22 carbon atoms.

Item 12.

The releasing agent according to any one of items 1 to 11, wherein the releasing agent is composed of 98% by weight or less of the monomer (A) based on the total amount of the monomers, and the fluorine-containing polymer obtainable by copolymerizing the monomer (B).

Item 13.

A release agent composition comprising the release agent according to any one of items 1 to 12.

Item 14.

Lt; RTI ID = 0.0 > 13, < / RTI >

Item 15.

A release agent composition according to item 14, which contains a nonionic emulsifier or an anionic emulsifier.

Item 16.

(A) at least 20% by weight, based on the total amount of monomers, of a radical polymerization-reactive monomer containing a perfluoroalkyl group having 1 to 6 carbon atoms and not having a functional group, and

(B) the use of a fluorine-containing polymer which can be obtained by copolymerizing a radical polymerization-inhibiting monomer having no functional group as a release agent.

Item 17.

A process for producing a mold release agent according to any one of items 1 to 12,

(A) a radical polymerization-reactive monomer containing a perfluoroalkyl group having 1 to 6 carbon atoms and not containing a functional group in an amount of not less than 20% by weight, based on the total amount of the monomers, and

(B) a radical polymerization-inhibiting monomer having no functional group.

Item 18.

(1) A method for forming a releasing agent coating, comprising the step of applying the releasing agent composition according to claim 4 or 5 to the inner surface of a mold to form a releasing agent coating.

Item 19.

In addition to the step (1) described in item 18,

(2) a step of molding a molding material by filling a molding composition having a release agent coating film formed by the step (1) into a molding composition; and

(3) A process for producing a molded molding material, comprising the step of releasing a molding material molded by the process (2) from the molding die.

According to the present invention, a release agent having excellent releasability can be provided.

1. Releasing agent

The release agent of the present invention is a

(A) a radical polymerization-reactive monomer containing a perfluoroalkyl group having 1 to 6 carbon atoms and not containing a functional group in an amount of not less than 20% by weight, based on the total amount of the monomers, and

(B) a fluorine-containing polymer which can be obtained by copolymerizing a radical polymerization-inhibiting monomer having no functional group.

The releasing agent of the present invention is not particularly limited, but has a number average molecular weight (Mn) of, for example, 2,000 to 200,000, preferably 3,000 to 100,000, and more preferably 5,000 to 50,000. The number average molecular weight can be measured by gel permeation chromatography.

1.1 Monomer (A)

The monomer (A) is not particularly limited as long as it contains a perfluoroalkyl group having 1 to 6 carbon atoms and has radical polymerization reactivity not having a functional group.

Due to the fact that the number of carbon atoms of the perfluoroalkyl group of the monomer (A) is in the range of 1 to 6, the release agent of the present invention can exhibit excellent releasability. For example, the release agent of the present invention exhibits remarkably excellent releasability as compared with the case where the perfluoroalkyl group of the monomer (A) is replaced with a conventionally widely used eight carbon atoms.

In addition, the release agent of the present invention has a lower melt viscosity than the conventional ones due to the fact that the number of carbon atoms of the perfluoroalkyl group of the monomer (A) is within the range of 1 to 6, 190 deg. C), it is easy to be uniform.

The perfluoroalkyl group may be linear or branched. Preferably, it is a straight-chain perfluoroalkyl group. The perfluoroalkyl group is not particularly limited, but is preferably a perfluoroalkyl group having 2, 4, or 6 carbon atoms in terms of easiness in industrial production. The perfluoroalkyl group is preferably a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 2 to 6 carbon atoms, more preferably a perfluoroalkyl group having 6 carbon atoms More preferred are perfluoroalkyl groups.

The monomer (A) has no functional group. In the present invention, the functional group means a group including a phosphoric acid group which does not show reactivity with a molding material. If the monomer (A) does not contain such a functional group, the reaction between the releasing agent and the molding material during use can be avoided.

The monomer (A) has a site showing radical polymerization reactivity (radical polymerization reactive site). Examples of such sites include an acrylate group, a methacrylate group, a vinyl group, a vinylidene group and an allyl group, although not particularly limited. As the radical polymerization reactive site, an acrylate group and a methacrylate group are preferable.

The structure of the moiety of the monomer (A) other than the perfluoroalkyl group and the radical polymerization reactive site can be selected from a wide range as long as the effect of the present invention is not impaired. In addition to the perfluoroalkyl group and the radical polymerization reactive site, the monomer (A) may further contain at least one substituent including an alkyl group and an alkylene group which is inert with respect to the reaction with the molding material. The monomer (A) may also contain a bond, such as an ester bond, which is inert with respect to the reaction with the molding material, between the substituents, or between the substituent and the perfluoroalkyl group or the radical polymerization reactive site.

The monomer (A) is not particularly limited. For example, a monomer having a perfluoroalkyl group at one end and a radical polymerization reactive site at the other end, and a perfluoroalkyl group, Or may be connected to a radical polymerization reactive site.

Examples of the monomer (A) include a (meth) acrylic acid ester having a perfluoroalkyl group represented by the following general formula (I).

(Wherein Rf represents a perfluoroalkyl group having 1 to 6 carbon atoms,

R ₁ represents a divalent aliphatic hydrocarbon group which is linear or branched, a divalent aromatic hydrocarbon group or a divalent cyclic aliphatic hydrocarbon group,

R ₂ is a hydrogen atom or a methyl group.)

In the above general formula (I), R ₁ is a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group or a divalent cyclic aliphatic hydrocarbon group which is linear or branched. R ₁ is preferably a straight or branched divalent aliphatic hydrocarbon group of 1 to 30 carbon atoms, a divalent aromatic hydrocarbon group of 6 to 12 carbon atoms, or a divalent cyclic aliphatic hydrocarbon group of 6 to 12 carbon atoms. More preferably, R ₁ is a straight or branched divalent aliphatic hydrocarbon group of 1 to 10 carbon atoms, a divalent aromatic hydrocarbon group of 6 to 10 carbon atoms, or a divalent cyclic aliphatic hydrocarbon group of 6 to 10 carbon atoms.

In the above, the straight or branched divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include an alkylene group having 1 to 10 carbon atoms.

Specific examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a 2-methylethylene group, a hexylene group and an octylene group.

Of the alkylene groups of 1 to 10 carbon atoms, alkylene groups of 1 to 6 carbon atoms are preferred, alkylene groups of 1 to 4 carbon atoms are more preferred, and alkylene groups of 1 to 2 carbon atoms are more preferred.

Examples of the divalent aromatic hydrocarbon group having 6 to 10 carbon atoms include, but are not limited to, 1,4-phenylene group, 1,4-bismethylenephenylene group and 1,4-bisethylenephenylene group .

Examples of the divalent cyclic aliphatic hydrocarbon group having 6 to 10 carbon atoms include, but are not limited to, 1,4-cyclohexylene group, 1,4-bismethylenecyclohexylene group and 1,4-bisethylenecyclohexyl And a silylene group.

Specific examples of the perfluoroalkyl group-containing (meth) acrylic acid ester represented by the above general formula (I) include the following.

CH ₂ = CH-COO-CH ₂ - (CF ₂ ) ₄ F

CH ₂ = CH-COO-CH ₂ - (CF ₂ ) ₆ F

CH ₂ ═CH-COO- (CH ₂ ) ₂ - (CF ₂ ) ₃ F

CH ₂ ═CH-COO- (CH ₂ ) ₂ - (CF ₂ ) ₄ F

CH ₂ ═CH-COO- (CH ₂ ) ₂ - (CF ₂ ) ₆ F

CH ₂ ═C (CH ₃ ) -COO-CH ₂ - (CF ₂ ) ₃ F

CH ₂ = C (CH ₃ ) -COO-CH ₂ - (CF ₂ ) ₄ F

CH ₂ ═C (CH ₃ ) -COO-CH ₂ - (CF ₂ ) ₆ F

CH ₂ ═C (CH ₃ ) -COO- (CH ₂ ) ₂ - (CF ₂ ) ₄ F

CH ₂ ═C (CH ₃ ) -COO- (CH ₂ ) ₂ - (CF ₂ ) ₆ F

As specific examples of the perfluoroalkyl group-containing (meth) acrylic acid ester represented by the above general formula (I), the following are preferred.

CH ₂ = CH-COO-CH ₂ - (CF ₂ ) ₆ F

CH ₂ ═CH-COO- (CH ₂ ) ₂ - (CF ₂ ) ₆ F

CH ₂ ═C (CH ₃ ) -COO-CH ₂ - (CF ₂ ) ₆ F

CH ₂ ═C (CH ₃ ) -COO- (CH ₂ ) ₂ - (CF ₂ ) ₆ F

The ratio of the monomer (A) to the total amount of the monomers (A) and (B) may be 20 wt% or more, and is not particularly limited, but is preferably 98 wt% or less. The ratio of the monomer (A) to the total amount of the monomers (A) and (B) is more preferably 25% by weight to 98% by weight, and still more preferably 30% by weight to 95% by weight.

The release agent of the present invention may be a release agent comprising a fluorine-containing polymer that can be obtained by copolymerizing one kind of the monomers (A) with the monomer (B), or may be obtained by copolymerizing two or more species with the monomer (B) Or a release agent comprising a fluorine-containing polymer.

1.2 Monomer (B)

The monomer (B) is a monomer having no functional group. Since the monomer (B) does not contain a functional group, the reaction between the releasing agent and the molding material can be avoided at the time of use.

The monomer (B) is a monomer copolymerizable with the monomer (A).

The monomer (B) has a radical polymerization reactive site. The radical polymerization reactive site is not particularly limited, and examples thereof include an acrylate group, a methacrylate group, a vinyl group, a vinylidene group and an allyl group. As the radical polymerization reactive site, an acrylate group and a methacrylate group are preferable.

The structure of the portion of the monomer (B) other than the radical polymerization reactive site can be selected from a wide range as long as the effect of the present invention is not impaired. The monomer (B) may further contain at least one substituent including an alkyl group which is inert to the reaction with the molding material, in addition to the radical polymerization reactive site. The monomer (B) may also include a bond, such as an ester bond, which is inert with respect to the reaction with the molding material, between the substituents or between the substituent and the radical polymerization reactive site.

Examples of the monomer (B) include a (meth) acrylic acid ester represented by the following general formula (II).

(Wherein R ₃ represents a linear or branched monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group or a monovalent cyclic aliphatic hydrocarbon group,

R ₄ is a hydrogen atom or a methyl group.)

In the general formula (II), R ₃ is a linear or branched monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, or a monovalent cyclic aliphatic hydrocarbon group. R ₃ is preferably a linear or branched monovalent aliphatic hydrocarbon group of 1 to 30 carbon atoms, a monovalent aromatic hydrocarbon group of 6 to 12 carbon atoms, or a monovalent cyclic aliphatic hydrocarbon group of 6 to 12 carbon atoms.

In the above, the linear or branched monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms is not particularly limited and includes, for example, an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 22 carbon atoms .

Specific examples of the alkyl group having 1 to 22 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, , N-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tridecyl group, A tetradecyl group, a cetyl group, a stearyl group and a behenyl group.

Specific examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a 2-ethylphenyl group, an indenyl group, a toluyl group and a benzyl group.

Specific examples of the monovalent cyclic aliphatic hydrocarbon group having 6 to 12 carbon atoms include cyclohexyl group, norbornyl group, norbornylmethyl group, isobornyl group, boronyl group, menthyl group, octahydroindenyl group, adamantyl group and dimethyl And adamantyl group.

Specific examples of the (meth) acrylic acid ester represented by the general formula (II) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i- butyl (meth) acrylate, n-butyl (meth) acrylate, neopentyl (meth) acrylate, t-pentyl , N-hexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (Meth) acrylate, stearyl (meth) acrylate, dodecyl (meth) acrylate, decyl (meth) acrylate, tridecyl (Meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, isobornyl (Meth) acrylate, phenyl (meth) acrylate, phenyl (meth) acrylate, phenyl (meth) acrylate, Ethylphenyl, indenyl (meth) acrylate, tolyl (meth) acrylate and benzyl (meth) acrylate. Stearyl acrylate and behenyl acrylate are particularly preferred.

The releasing agent of the present invention may be a releasing agent comprising a fluorine-containing polymer which can be obtained by copolymerizing one kind of the above-mentioned monomers (B) with the monomer (A), or may be obtained by copolymerizing two or more kinds of them with the monomer (A) Or a release agent comprising a fluorine-containing polymer structure.

2. Manufacturing method of mold release agent

The release agent of the present invention is a

(A) at least 20% by weight, based on the total amount of monomers, of a radical polymerization-reactive monomer containing a perfluoroalkyl group having 1 to 6 carbon atoms and not having a functional group, and

(B) a radical polymerization-inhibiting monomer having no functional group.

The monomers (A) and (B) are as described above for the release agent.

The copolymerization may be emulsion polymerization or solution polymerization.

The emulsion polymerization is not particularly limited, but can be carried out, for example, as follows. Various monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen replacement, they are copolymerized by stirring at 50 to 80 ° C for 1 to 10 hours.

In emulsion polymerization, the polymerization initiator is not particularly limited, and examples thereof include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, A water-soluble polymerization initiator such as acetyl, azobisisobutylamidine-dibasic acid salt, azobisisobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate, and azobisisobutyronitrile, benzoyl peroxide, t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxy pivalate, diisopropyl peroxydicarbonate, and azobismethyl propionate.

In the emulsion polymerization, the polymerization initiator is usually used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

In order to obtain a copolymer aqueous dispersion having excellent stability in emulsion polymerization in emulsion polymerization, monomers are made into fine particles in water by using an emulsifying device capable of imparting strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer, It is preferable to carry out polymerization using a polymerization initiator.

In the emulsion polymerization, various emulsifiers such as anionic, cationic or nonionic emulsifiers can be used as the emulsifier. The emulsifier is usually used in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. Nonionic emulsifiers or anionic emulsifiers are preferred as emulsifiers.

Examples of nonionic emulsifiers include, but are not limited to, polyoxyethylene alkyl ethers, sorbitan alkylates and sorbitan alkyl esters.

The polyoxyethylene alkyl ether is not particularly limited, and examples thereof include polyoxyethylene lauryl ether and the like.

Examples of the anionic emulsifier include alkylsulfates, alkylsulfonates and alkylphosphates. The alkylsulfuric acid ester is not particularly limited, but sodium alkylsulfate and the like can be mentioned.

Examples of the cationic emulsions include quaternary ammonium salts and alkylamine salts.

The quaternary ammonium salt is not particularly limited, and examples thereof include lauryltrimethyl ammonium chloride and the like.

When the monomers are not completely used in the emulsion polymerization, it is preferable to add a compatibilizing agent sufficiently compatible with these monomers, for example, a water-soluble organic solvent or a low molecular weight monomer. By the addition of the compatibilizing agent, it is possible to improve emulsification and copolymerization.

Examples of the water-soluble organic solvent as the compatibilizing agent include, but are not limited to, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, diethylene glycol diethyl ether, And ethanol. The water-soluble organic solvent is usually used in an amount of 1 to 50 parts by weight based on 100 parts by weight of water. The water-soluble organic solvent is preferably used in a range of 10 to 40 parts by weight, relative to 100 parts by weight of water.

In the emulsion polymerization, a chain transfer agent may be used to adjust the molecular weight of the resulting polymer. Examples of the chain transfer agent include, but are not limited to, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, 2-ethylhexyl thioglycolate and 2,3- -Propanol and the like. The chain transfer agent may be used alone or in combination of two or more thereof, if necessary. The chain transfer agent is usually used in the range of 0.001 to 7.0 parts by weight based on 100 parts by weight of the monomer.

The solution polymerization is not particularly limited, but can be carried out, for example, as follows. In the presence of a polymerization initiator, the monomer is dissolved in an organic solvent, and after nitrogen substitution, the mixture is heated and stirred for 1 to 10 hours at 30 to 120 ° C. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate And the like. The polymerization initiator is usually used in a range of 0.01 to 20 parts by weight based on 100 parts by weight of the monomer. The polymerization initiator is preferably used in a range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

In the solution polymerization, the organic solvent is not particularly limited as long as it is inert to the monomers and dissolves them. Examples of the organic solvent include acetone, chloroform, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, , Methyl isobutyl ketone, ethyl acetate, and butyl acetate. The organic solvent is usually used in the range of 50 to 2000 parts by weight based on 100 parts by weight of the total of the monomers. The organic solvent is preferably used in a range of 50 to 1000 parts by weight per 100 parts by weight of the total of the monomers.

3. Release agent composition

The release agent composition of the present invention is a composition containing the above-described release agent.

The form of the release agent composition can be appropriately selected depending on the purpose of use and is not particularly limited, and examples thereof include a solution, an emulsion or an aerosol. The form is preferably an aqueous emulsion.

The release agent composition is not particularly limited, but preferably contains 0.5% by weight to 50% by weight, more preferably 1.0% by weight to 30% by weight, and still more preferably 1.5% by weight to 20% by weight of the release agent described above .

The releasing agent composition may contain a surfactant for the purpose of improving the wettability with respect to the forming die. The surfactant is not particularly limited, but a fluorine-based or non-fluorine-based surfactant can be used. As the fluorine-based or non-fluorine-based surfactant, an anionic surfactant, a nonionic surfactant, and a cationic surfactant can be used.

Examples of the fluorine-based surfactant include fluorine-containing polyoxyethylene, sulfonate, carboxylate and quaternary ammonium salt.

Examples of the non-fluorine-based anionic surfactant include alkylsulfates, alkylsulfonates and alkylphosphates. The alkylsulfuric acid ester is not particularly limited, but sodium alkylsulfate and the like can be mentioned.

Examples of the non-fluorine-based nonionic surfactant include, but are not limited to, polyoxyethylene alkyl ethers, sorbitan alkylates and sorbitan alkyl esters. The polyoxyethylene alkyl ether is not particularly limited, and examples thereof include polyoxyethylene lauryl ether and the like.

Examples of the non-fluorine-based cationic surfactant include quaternary ammonium salts and alkylamine salts.

The quaternary ammonium salt is not particularly limited, and examples thereof include lauryltrimethyl ammonium chloride and the like.

When the surfactant is contained for the above purpose, the content of the surfactant in the releasing agent composition is not particularly limited, but is usually 0.01 to 20% by weight, preferably 0.01 to 15% by weight, And preferably 0.01% by weight to 10% by weight.

The releasing agent composition may further contain at least one additive selected from the group consisting of a silicone compound, a wax-based compound and a fluorine-based compound for the purpose of improving releasability and / or finishability.

The silicone compound is not particularly limited, and examples thereof include dimethyl silicone oil, methylphenyl silicone oil, fluorosilicone oil, silicone resin and the like. When the silicone compound is contained for the above purpose, the content of the silicone compound in the releasing agent composition is not particularly limited, but is usually 0.01% by weight to 20% by weight, preferably 0.01% by weight to 15% by weight.

The wax-based compound is not particularly limited, and examples thereof include polyethylene wax, paraffin wax and carnauba wax. When the wax-based compound is contained for the above-mentioned purpose, the content of the wax-based compound in the releasing agent composition is not particularly limited, but is usually 0.01% by weight to 20% by weight, preferably 0.01% by weight to 15% by weight.

Examples of the fluorine-based compound include, but are not limited to, polytetrafluoroethylene, fluoropolyether, and fluorochloropolyether. When the fluorine-containing compound is contained for the above-mentioned purpose, the content of the fluorine-containing compound in the release agent composition is not particularly limited, but is usually 0.01% by weight to 20% by weight, preferably 0.01% by weight to 15% by weight.

The release agent composition is not particularly limited when it is an aqueous emulsion, but it contains at least one emulsifier selected from the group consisting of a nonionic emulsifier, an anionic emulsifier and a cationic emulsifier as an emulsifier. As the emulsifier, at least one emulsifier selected from the group consisting of a nonionic emulsifier and an anionic emulsifier is preferable.

The nonionic emulsifier is not particularly limited as long as the emulsion of the present invention can be emulsified and dispersed in the aqueous emulsion. Examples of the nonionic emulsifier include polyoxyethylene alkyl ethers, sorbitan alkylates and sorbitan alkyl esters have. The polyoxyethylene alkyl ether is not particularly limited, and examples thereof include polyoxyethylene lauryl ether and the like.

Examples of the anionic emulsifier include alkylsulfates, alkylsulfonates and alkylphosphates. The alkylsulfuric acid ester is not particularly limited, but sodium alkylsulfate and the like can be mentioned.

Examples of the cationic emulsifier include quaternary ammonium salts and alkylamine salts.

The quaternary ammonium salt is not particularly limited, and examples thereof include lauryltrimethyl ammonium chloride and the like.

When the emulsifier is contained, the content of the emulsifier in the releasing agent composition is not particularly limited, but is usually 0.5 to 25% by weight, preferably 1.0 to 20% by weight, based on 100 parts by weight of the monomer By weight, more preferably 2.0% by weight to 15% by weight.

The releasing agent composition is not particularly limited when it is an aqueous emulsion, but may further contain additives described in the above description of emulsion polymerization, that is, a compatibilizing agent and / or a chain transfer agent.

The release agent composition is not particularly limited in the case of a solution, but may further contain an organic solvent described in the description of the solution polymerization.

In the case of an aerosol, the release agent composition can be filled into an aerosol can using a jetting agent. The jetting agent is not particularly limited, and examples thereof include LPG, dimethyl ether, carbon dioxide and the like. The amount of the jetting agent is usually from 10 to 95% by weight, preferably from 20 to 90% by weight, more preferably from 30 to 90% by weight, based on the total amount of the release agent composition and the jetting agent. When the amount of the jetting agent is 10% by weight or more, jetting can be performed more favorably, and a more uniform film tends to be obtained. When the amount of the jetting agent is 95% by weight or less, the coating film is not too thin, and the releasability tends not to deteriorate too much.

The release agent composition is not particularly limited, but is usually used in the following manner. A mold release agent composition is applied to the inner surface of a mold, the mold release agent coating is formed on the mold after the solvent and the dispersant are dried and removed, the molding composition is filled in the mold to mold the molding material, Release.

Examples of the mold used for the mold release composition include molds made of aluminum, stainless steel, iron, epoxy resin and wood, nickel electroformed or chrome-plated molds, and the like .

Examples of the molding material to be released by using the release agent composition include urethane rubber, H-NBR, NBR, silicone rubber, EPDM, CR, NR, fluororubber, SBR, BR, IIR and IR Rubber, urethane foam, epoxy resin, phenol resin, and thermosetting resin such as FRP.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1

45 g of perfluoroalkyl methacrylate (C ₆ F ₁₃ -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ ) and 5 g of stearyl acrylate were thoroughly dissolved and then polyoxyethylene (n = 20) lauryl ether (Nonionic emulsifier), 0.2 g of laurylmercaptan, 7 g of dipropylene glycol monomethyl ether and 95 g of ion-exchanged water were added and emulsified with a high-pressure homogenizer. The obtained emulsion was placed in a 300 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, and maintained at 60 DEG C for about 1 hour under a nitrogen stream. 0.3 g of ammonium persulfate as an initiator dissolved in 5 g of water was added to initiate polymerization. The mixture was heated and stirred at 60 占 폚 for 3 hours to prepare an aqueous copolymer emulsion. The obtained aqueous emulsion was adjusted to a solid concentration of 0.3 mass% by ion-exchange water.

Example 2

After sufficiently dissolving 35 g of perfluoroalkyl acrylate (C ₆ F ₁₃ -CH ₂ CH ₂ OCOCH = CH ₂ ) and 15 g of stearyl acrylate, an aqueous copolymer emulsion was prepared in the same manner as in Example 1, And adjusted so as to have a solid content concentration of 0.3 wt% as replacement water.

Example 3

After sufficiently dissolving 47.5 g of perfluoroalkyl methacrylate (C ₆ F ₁₃ -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ ) and 2.5 g of isobornyl methacrylate, the same procedure as in Example 1 was carried out Aqueous copolymer emulsion was prepared and adjusted to a solid content concentration of 0.3 wt% with ion-exchanged water.

Example 4

25 g of perfluoroalkyl methacrylate (C ₆ F ₁₃ -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ ) and 25 g of stearyl methacrylate were sufficiently dissolved. Thereafter, an aqueous copolymer And adjusted to have a solid concentration of 0.3 mass% with ion-exchanged water.

Example 5

An aqueous copolymer emulsion was prepared in the same manner as in Example 4, and adjusted to have a solid concentration of 0.15 mass% by ion-exchange water.

Example 6

After 15 g of perfluoroalkyl methacrylate (C ₆ F ₁₃ -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ ) and 35 g of lauryl acrylate were sufficiently dissolved, an aqueous copolymer emulsion And adjusted to have a solid content concentration of 0.3 mass% with ion-exchanged water.

Example 7

An aqueous copolymer emulsion was prepared in the same manner as in Example 6, and adjusted to a solid content concentration of 0.15 mass% with ion-exchanged water.

Example 8

An aqueous copolymer emulsion was prepared in the same manner as in Example 1 except that behenyl acrylate was used in place of stearyl acrylate, and adjusted to have a solid content concentration of 0.3 mass% with ion-exchanged water.

Comparative Example 1

50 g of perfluoroalkyl methacrylate (C ₆ F ₁₃ -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ ), 4 g of polyoxyethylene (n = 20) lauryl ether (nonionic emulsifier) , 7 g of dipropylene glycol monomethyl ether and 95 g of ion-exchanged water, and emulsified with a high-pressure homogenizer. The obtained emulsion was placed in a 300 ml four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, and maintained at 60 DEG C for about 1 hour under a nitrogen stream. 0.3 g of ammonium persulfate as an initiator dissolved in 5 g of water was added to initiate polymerization. The mixture was heated and stirred at 60 占 폚 for 3 hours to prepare an aqueous copolymer emulsion. The obtained aqueous emulsion was adjusted to a solid concentration of 0.3 mass% by ion-exchange water.

Comparative Example 2

After 35 g of perfluoroalkyl acrylate (C _n F _{n +1} -CH ₂ CH ₂ OCOCH = CH ₂ (mixture of n = 8-14)) and 15 g of stearyl acrylate were sufficiently dissolved, To prepare an aqueous copolymer emulsion, and adjusted to have a solid content concentration of 0.3 mass% with ion-exchanged water.

Comparative Example 3

An aqueous copolymer emulsion was prepared in the same manner as in Comparative Example 2, and adjusted to a solid content concentration of 0.6 wt% with ion-exchanged water.

Comparative Example 4

47.5 g of perfluoroalkyl methacrylate (C _n F _{n +1} -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (mixture of n = 8-14)) and 2.5 g of isobornyl methacrylate After the dissolution, an aqueous copolymer emulsion was prepared in the same manner as in Example 1, and adjusted to have a solid content concentration of 0.3 mass% by ion exchange water.

Comparative Example 5

25 g of perfluoroalkyl methacrylate (C _n F _{n +1} -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (mixture of n = 8-14)) and 25 g of stearyl methacrylate were sufficiently dissolved , An aqueous copolymer emulsion was prepared in the same manner as in Example 1, and adjusted to a solid content concentration of 0.3 wt% with ion-exchanged water.

Comparative Example 6

Alkyl phosphate ester perfluoroalkyl _{(C 6 F 13 (CH 2} CH 2 O) m PO (OH) 3-m (m is 1, 2, and 3, the compound (molar ratio of 2 (m = 1): 7 (m = 2 ): 1 (m = 3)) was dissolved in 10 g of isopropyl alcohol (IPA). To the solution was added 10 g of water and stirred well, then the solution was neutralized with a small amount of ammonia water, To obtain an aqueous solution of a < RTI ID = 0.0 > luoroalkyl < / RTI >

3 g of polyoxyethylene (n = 20) lauryl ether (nonionic emulsifier) was added to the obtained aqueous solution of perfluoroalkyl phosphate ester and stirred well to obtain an emulsion of perfluoroalkyl phosphate ester. Thereafter, it was diluted with ion-exchanged water so that the solid content concentration became 0.3 mass%.

For each of the compositions containing the fluorine-containing polymer obtained in each of the above Examples and Comparative Examples, the releasability was tested as follows.

The molding process was performed under the following conditions.

(1) 100 parts by weight of a peroxide vulcanization type silicone rubber KE-941U (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.6 parts by weight of C-8A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a vulcanizing agent were kneaded by a refining roll for rubber, Sulfur rubber was obtained.

(2) The fluorine-containing polymer compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 6 were applied to 100 O-ring molds kept at 180 占 폚 under the same conditions using a spray gun, ) Was press-molded at 180 占 폚 for 10 minutes to obtain an O-ring sheet.

(3) The fluorine-containing polymer composition was again coated in the same manner as in the above (2), and the molding was repeated.

Furthermore, the releasability was evaluated as follows. In the above molding process, if the fluorine-containing polymer composition is excellent in releasability, 100 O-rings are integrated into one sheet and released from the mold. On the other hand, if the releasability is poor, the O-ring portion remains in the mold, and the O-ring portion is released into the sheet with the hole opened. This tendency was used to evaluate the releasability. More specifically, when releasing from a single sheet, it was evaluated that the greater the number of O-rings that were formed integrally with the sheet, the better the releasability.

Various fluorine-containing polymers obtained by copolymerizing a monomer containing a perfluoroalkyl group with a monomer having no functional group were evaluated as described above. The results are shown in Tables 1 to 3. From these results, it has become clear that fluorine-containing polymers having excellent releasability can be obtained by using a monomer having 1 to 6 carbon atoms as a monomer containing a perfluoroalkyl group at a specific ratio, despite the absence of a functional group.

In the tables, the respective abbreviations indicate the following compounds.

&Quot; 13FMA ": C ₆ F ₁₃ -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂

&Quot; 13FA ": C ₆ F ₁₃ -CH ₂ CH ₂ OCOCH = CH ₂

&Quot; 17FA ": C _n F _{n +1} -CH ₂ CH ₂ OCOCH = CH ₂ (mixture of n = 8-14)

&Quot; STA ": stearyl acrylate

&Quot; STMA ": stearyl methacrylate

&Quot; LA ": lauryl acrylate

"IBM": isobornyl methacrylate

&Quot; BeA ": Behenyl acrylate

[Table 1]

[Table 2]

[Table 3]

Claims (9)

(A) at least 20% by weight, based on the total amount of monomers, of a radical polymerization-reactive monomer containing a perfluoroalkyl group having 1 to 6 carbon atoms and not having a functional group, and
(B) a fluorine-containing polymer obtainable by copolymerizing a radical polymerization-inhibiting monomer having no functional group. The method according to claim 1,
Wherein the monomer (A) is represented by the following general formula (I).

(Wherein Rf represents a perfluoroalkyl group having 1 to 6 carbon atoms,
R ₁ represents a divalent aliphatic hydrocarbon group which is linear or branched, a divalent aromatic hydrocarbon group or a divalent cyclic aliphatic hydrocarbon group,
R ₂ is a hydrogen atom or a methyl group.) The method according to claim 1 or 2,
Wherein the monomer (B) is an alkyl (meth) acrylate ester represented by the following general formula (II).

(Wherein R ₃ represents a linear or branched monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group or a monovalent cyclic aliphatic hydrocarbon group,
R ₄ is a hydrogen atom or a methyl group.) A release agent composition comprising the release agent according to any one of claims 1 to 3. The method of claim 4,
An aqueous emulsion. The method of claim 5,
A release agent composition comprising a non-ionic emulsifier or an anionic emulsifier. A method of producing a mold release agent according to any one of claims 1 to 3,
(A) at least 20% by weight, based on the total amount of monomers, of a radical polymerization-reactive monomer containing a perfluoroalkyl group having 1 to 6 carbon atoms and not having a functional group, and
(B) a radical polymerization-inhibiting monomer having no functional group. (1) A method for forming a releasing agent coating, comprising the step of applying the releasing agent composition according to any one of claims 4 to 6 to the inner surface of a molding die to form a release agent coating. In addition to the step (1) of claim 8,
(2) a step of molding a molding material by filling a molding composition having a release agent coating film formed by the step (1) into a molding composition; and
(3) A process for producing a molded molding material, comprising the step of releasing a molding material molded by the process (2) from the molding die.