JPS6259672A - Coating agent for mold release - Google Patents

Abstract

PURPOSE:To provide the titled coating agent which has excellent durability and adhesion to materials to be coated, gives a coating surface having excellent mold release characteristics and lubricity and is useful as a release agent for release paper and as a parting agent for rubber and plastic molding, consisting of a graft polymer. CONSTITUTION:30-90wt% radical-polymerizable silicone macromonomer (A) having a relatively low MW, mainly composed of a polymer having a number- average MW of 1,000-20,000 and contg. a polymerizable functional group at one terminal is copolymerized with 0.1-30wt% radical-polymerizable monomer (B) (a) contg. a hydrolyzable functional group attached to a Si atom, represented by formula I [wherein R1 is H, CH3; R2, R3 are each CH3, C2H5 phenyl; n is 1-3; m is 0, 1; l is 0-2; X is alkoxy, acetoxy, a group of formula II (wherein R is R1, C2H5; p is 1-5)] or 0.5-40wt% radical-polymerizable monomer (B) (b) contg. an OH group, and 30-90wt% radical-polymerizable monomer (C) (e.g., arom. vinyl compd.) other than components A and B in the presence of a radical polymn. initiator.

Description

Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention relates to a mold release coating agent useful in the rubber/plastic industry, paper/pulp industry, electrical/electronic industry, machinery industry, etc. Specifically, the coating agent is suitable as a release coating agent during rubber/plastic molding, and as a release coating agent that imparts release properties to paper/plastic films such as release paper. It is something. The release coating agent of the present invention is also suitable as a coating agent for forming lubricating films on rubber/plastic parts, glass films, and mechanical parts.

[Conventional technology and its problems]

Conventionally, for applications aiming at lubricity and mold release properties, silicone oil, silicone grease, fluorine compounds such as tetrafluoroethylene oligomers and hexafluoropropylene oxide oligomers, paraffin hydrocarbons such as n-dodecane, etc. A large number of compounds, such as phosphoric acid esters such as (2-ethylhexyl) phosphoric acid ester, have been used as appropriate for their intended use.

In applications where mold releasability is the objective, for example, large amounts of silicone oil and the above-mentioned fluorine compounds have been used as mold release agents from molds during rubber and plastic molding.
Since these conventional mold release agents are still the same homogeneous substance, it is extremely difficult to achieve both mold release properties and adhesion to the object to be coated. When the mold is released from a mold coated with these mold release agents, it transfers to the rubber/plastic surface, and when painting the rubber/plastic, there is no repellent,
Poor adhesion occurs, which is a big problem. Furthermore, if a mold coated with these mold release agents is used repeatedly, the mold release effect will gradually decrease, so after using it several times, the mold must be coated with these mold release agents again, and the rubber・The yield of plastic molded products increases (decreases).

Conventionally, reactive silicone has been used as a release agent for paper with release properties, that is, release paper, but when used at high temperatures, for example, 70°C or higher, the paper and the silicone release agent may Due to the poor adhesion between the two, they will peel off and become unusable.Also, plastic films, sometimes P
Although various silicones have been developed for the purpose of imparting release properties to ET films, they are not practically satisfactory due to poor adhesion, water resistance, and moisture resistance of adhesion.

In addition, coatings such as silicone oil, the above-mentioned fluorine compounds, phosphate esters, etc. are used to impart lubricity to the surfaces of polyethylene terephthalate films (hereinafter referred to as PET films) and metal surfaces, for example.
Considering the recent social situation that demands higher performance,
It's never satisfying. Because these conventional coating agents are made of the same homogeneous substance, it is difficult to achieve both lubricity and adhesion to the object being coated, resulting in poor adhesion, water resistance, and moisture resistance between the coating agent and the object.
Excellent lubricity cannot be maintained for a long period of time,
It is difficult to exhibit excellent lubricity in a harsh environment of high temperature and humidity, and the expression of such performance is temporary. In other words, it can be said that the durability is poor.

In addition, these conventional coating agents have poor coating properties depending on the object to be coated (repelling, etc. may occur, making it difficult to coat uniformly, and furthermore, the strength of the coating agent itself is extremely weak. This tendency is remarkable in physically removed shavings, especially in thin films with a coating thickness of 1 μm or less, resulting in a loss of lubricity.

As mentioned above, it can be used as a mold release agent during rubber and plastic molding, and furthermore as a coating agent that imparts mold release properties to paper and plastic films such as release paper, as well as rubber and plastic parts, plastic films, machine parts, etc. Currently, there is no coating agent for forming a lubricating film that is excellent in coating properties, adhesion, water resistance of adhesion, moisture resistance, strength of the coating agent itself, etc.

(B) Structure of the Invention [Means for Solving the Problems] The present inventors have completed the present invention as a result of intensive studies to solve the above problems.

That is, the present invention comprises <A), a radically polymerizable silicone macromonomer, a radically polymerizable monomer having a hydrolyzable functional group bonded to a silicon atom, or a radically polymerizable monomer having a hydroxyl group, and (C1, the above (5)).
It is a mold release coating agent consisting of a graft polymer (hereinafter referred to as the present graft polymer) obtained by radical copolymerization of radically polymerizable monomers other than (and) above.

The mold release coating agent of the present invention can be used as a coating agent for forming a lubricating film, and can be used as a coating agent for forming a lubricating film, including the types and proportions of each of the above-mentioned hexamers, (B) and (C1), the method of radical copolymerization, and the composition of the ingredients. Regarding the type, amount used, crosslinking method of the coating agent, method of use, etc., the same conditions as in the present invention are adopted for the coating agent for forming a lubricating film.

The film obtained from the coating agent has a non-uniform phase separation structure derived from the graft polymer, with a large amount of silicone component on the surface of the film (usually at the air interface of the film) and a small amount of silicone component at the interface of the coated object. Due to the synergistic effect of the formation of a polyurethane resin and the crosslinking and curing action, it has excellent mold releasability and lubricity, as well as excellent adhesion to the object to be coated, water resistance, moisture resistance, and excellent root plate strength of the coating. occur simultaneously.

[(A) Radically polymerizable silicone macromonomer] The radically polymerizable silicone macromonomer in the present invention refers to a polymer having a number average molecular weight of 1.000 to 20.000 and having a polymerizable functional group at one end of the molecular chain. Refers to relatively low molecular weight polymers.

The number average molecular weight in the present invention is a polystyrene equivalent molecular weight measured by gel permeation chromatography (hereinafter referred to as GPC), and the measurement conditions are as follows.

Apparatus: High performance liquid chromatography (for example, manufactured by Toyo Soda Kogyo, part name: HLC-802UR) Column: Polystyrene gel (for example, manufactured by Toyo Soda Kogyo, part name: G4000H)
8 and G3000H8) Bathing solvent: Tetrahydrofuran Outflow rate: 1.0111/,,! .

Column temperature: 40° C. Detector: RI detector The radically polymerizable silicone macromonomer can be obtained by various manufacturing methods as described below, and any of them can be used.

An example of the production method is a method of obtaining a silicone macromonomer by reacting a living polymer obtained by anionically polymerizing a cyclic siloxane represented by the following general formula (al) with a radically polymerizable silicone compound represented by the following general formula (b). (%Kokai No. 59-126478).

R8 is a methyl group, an ethyl group or a phenyl group, and P is 3 or 4.

or C) I2=CH-Q -8i (R,)s -n
C1n is hydrogen or methyl group, m is 0 or 1, R4 is methyl group, ethyl group or phenyl group, n
is an integer from 1 to 6, l is an integer from 0 to 2 when m = Q, and 2 when m = 1.

The anionic polymerization of the cyclic siloxane can be carried out according to a conventional method (it can be easily carried out by a bulk polymerization method or a solution polymerization method using a known anionic polymerization initiator).

Examples of the cyclic siloxane represented by general formula (a) are:
Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaethylcyclotrisiloxane, octaethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, and octaphenylcyclotrisiloxane, among which hexamethylcyclotrisiloxane and octaethylcyclotrisiloxane Methylcyclotetrasiloxane is particularly preferred in terms of cost and ease of anionic polymerization. Examples of the anionic polymerization initiator include known ones such as organolithium compounds, alkali metal hydroxides, alkali metal alkoxides, and alkali metal syralates, and among these, organolithium compounds are particularly preferred.

The molecular weight of the living polymer obtained by anionic polymerization controls the molecular weight of the silicone macromonomer, and is controlled by the molar ratio of cyclic siloxane and initiator, with the molar ratio of initiator/cyclic siloxane being 0.01 to 0.2.
is preferred. If it is less than 0.01, the silicone macromonomer will have an extremely high molecular weight (more than 20,000), and if it is more than 0.2, the silicone macromonomer will have an extremely low molecular weight (more than 20,000).
(less than 1,000). The number average molecular weight of the silicone macromonomer is 1.000 to 20.000, but if the molecular weight is less than 1.000, the effects of silicone, that is, 4z2 water, dual oil properties, and low friction properties will decrease, and the mold release property will decrease. If it exceeds 20,000, the obtained coating resin tends to become oily.〇Silicone macromonomer can be obtained as described above or combined with Ping polymer as shown in general formula (b). It can be obtained by reacting (living polymerization termination reaction) a radically polymerizable silicone compound. The reaction is easily carried out by mixing the two.

The radically polymerizable silicone compound represented by the general formula (b) can be easily obtained by a known method. = c-c-o÷C crane ÷, mo0-C seagull CH=CH.

It can be obtained by a hydrosilylation reaction between an unsaturated (meth)acrylate (F (,,, l, m are the same as above) and H81 (R,), -Cl (R,, n are the same as above) n The amount of the radically polymerizable silicone compound to be used is based on the general formula (5i-
A combination in which C1 is 1 to 5 times equivalent is preferable.

Another example of a method for producing a silicone macromonomer is a silicone represented by the following general formula (a) and an acrylic compound represented by the following general formula (bl) per 1 mole of the silicone represented by the following general formula (a).
This is a method of obtaining a silicone macromonomer by condensation reaction with moles (Japanese Patent Application Laid-open No. 154766/1983).

I-tz 10 monovalent aliphatic hydrocarbon group, phenyl group or -valent halogenated hydrocarbon group. n is a positive number of 1 or more. ) (R3 is a hydrogen atom or a methyl group. R4 is a methyl group, an ethyl group, or a phenyl group. As the silicone represented by the general formula (a), various silicones are easily available, and one of them may be used depending on the purpose. is particularly preferable. In the general formula (a), n is a factor that determines the molecular weight of silicone, and this n is preferably 1 to 500, more preferably 10 to 500. If n is less than 1, the effect of silicone, that is, water drop, If n exceeds 500, the resulting silicone-based graft copolymer becomes oily and difficult to purify.

Examples of the acrylic compound represented by the general formula (b) include Eva γ-methacryloxypropylmethyldichlorosilane, r-methacryloxyglovylmethyldiethoxysilane, γ-methacryloxypyrropylphenyldichlorosilane, and γ-methacryloxyglovylmethyldichlorosilane. Examples include bilethyldichlorosilane and γ-acryloxypropylmethyldichlorosilane. These acrylic compounds are known and can be easily obtained by reacting a silicon compound and a compound having an aliphatic multiple bond in the presence of chloroplatinic acid.

The reaction between the silicone represented by the general formula (al) and the acrylic compound represented by the general formula (b) proceeds smoothly by a conventional method to obtain a silicone macromonomer.That is, when X of the acrylic compound is a chlorine atom, dehydrochlorination In the case where X is a methoxy group or an ethoxy group, a dealcoholization condensation reaction proceeds.

The reaction ratio of silicone and acrylic compound is 0.25 to 1 mol of acrylic compound per 1 mol of silicone. If it is less than 0.25 mol, a large amount of unreacted silicone will remain during the production of the paint resin, and if it exceeds 1 mol, gelation will easily occur during the production of the paint resin.

Furthermore, as a method for producing the silicone macromonomer preferably used in the present invention, an acrylic compound represented by the following general formula (b") is used instead of the acrylic compound represented by the general formula (b'), and other This is a method for synthesizing a silicone macromonomer using the same raw materials, reaction conditions, etc. as the method disclosed in JP-A-58-154767S (JP-A-59-20360).

(In the above general formula, n is an integer of 1 or 3, and the other meanings of R3, R4 and X are the same as in the above general formula (b').)
The products produced by silicone macromonomer production proposed in No. 765 or JP-A No. 59-20560 are as follows:
The main component is one in which silicone is introduced into one molecule of an acrylic compound, and the secondary components are unreacted raw material silicone and by-product acrylic polyfunctional silicone (such as one in which two molecules of an acrylic compound are introduced into one molecule of silicone). However, the product can be usefully used as it is as a silicone macromonomer in the present invention.

The proportion of the radically polymerizable silicone macromonomer used is preferably 3 to 603 m weight, more preferably 5 to 50 m weight, based on the total amount of each monomer (A), (B) and (C).

If the amount of silicone macromonomer used is less than 5% by weight, the intended graft polymer with excellent mold release properties cannot be obtained;
If it exceeds 0% by weight, radical polymerizability deteriorates, the mechanical strength of the film decreases, and it becomes expensive, which is not preferable.

[(B) Radical polymerizable monomer having a hydrolyzable functional group bonded to a silicon atom or a radical polymerizable monomer having a hydroxyl group (hereinafter simply referred to as a crosslinkable monomer)]

The crosslinkable monomer in the present invention has a hydrolyzable functional group because of the need to improve the adhesion between the graft polymer and the coated object, the water resistance and moisture resistance of the adhesion, and the strength of the graft polymer itself. A radically polymerizable monomer or a radically polymerizable monomer having a hydroxyl group.

The hydrolyzable functional groups in the present invention include alkoxy groups, acetoxy groups, and groups represented by the general formula (QC, H4) OR (R is H, methyl group and ethyl group, p is an integer of 1 to 5). cormorant.

Examples of radically polymerizable monomers having a hydrolyzable functional group include acrylate silanes and/or methacrylate silanes represented by the general formula, and other examples of radically copolymerizable silanes include ethylene silanes represented by can be given.

One chapter is a hydrogen atom or a methyl group, R,,R.

is a methyl group, ethyl group, or phenyl group, and n is 1 to 6
is an integer. m is O or 1; t is an integer of 0 to 2 in the case of m20; and 2 in the case of nl-1.

X is an alkoxy group, an acetoxy group, a group with the general formula % (R, is a hydrogen atom, a methyl group, an ethyl group, and p
is an integer from 1 to 5).

Specifically, r-(meth)acryloyloxypropyltrimethoxysilane, r-Cmeth)1 acryloyloxyglobylmethyldimethoxysilane, r-(meth)acryloyloxypropyldimethoxysilane, 3-(2-(
meth)acryloyloxyethoxy)propyltrimethoxysilane, 5-(2-(meth)acryloyloxyethoxy)propylmethyldimethoxysilane, 3-(2-
(meth)acryloyloxyethoxy)propyldimethylmethoxysilane, 5-((meth)acryloyloxy)pentyltrimethoxysilane, 5-((meth)acryloyloxy)pentylmethyldimethoxysilane, 5-
((meth)acryloyloxy)pentyldimethylmethoxysilane, P-vinylphenyltrimethoxysilane,
P-vinylphenylmethyldimethoxysilane, P-vinylphenyldimethylmethoxysilane, r-(meth)acryloyloxypropyltri(β-methoxyethoxy)
Examples include silane.

Of these, γ-(meta) in terms of ease of acquisition and cost.
Acryloyloxyglobyl trimethoxysila/ is preferred.

Furthermore, as the radically polymerizable monomer having a hydroxyl group, any radically polymerizable monomer having a hydroxyl group can be used, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (
meth)acrylate, hydroxypropyl(meth)
Acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 2
, 6-cyhydroxyglobil (meth)acrylate, and the like.

Among these radically polymerizable monomers, ease of acquisition,
2-hydroxyethyl (meth)acrylate is preferred from the viewpoint of cost.

When the crosslinking monomer is a radically polymerizable silicon compound having a hydrolyzable functional group, the proportion used thereof is preferably 0.1 to 60% by weight based on the total amount of each monomer, (B) and (Q), and 0. .5 to 20% by weight is more preferred.

If the proportion of the crosslinkable monomer used is less than 0.1% by weight, it will not be possible to improve the chemical resistance, heat resistance, or coating strength of the coating due to crosslinking and curing, and if it exceeds 30% by weight, the coating will deteriorate. Chemical resistance, hardness, and heat resistance are not sufficiently improved, and if a crosslinking curing catalyst is also used, the pot life becomes short or it becomes difficult to control the pot life.

When the crosslinking monomer is a radically polymerizable monomer having a hydroxyl group, the proportion of its use is as follows:
), (0.5 to 40 storms during the total of Bl and (C1)
% by weight is preferred, and 1 to 60% by weight is more preferred. The reason is the same as in the case of the radically polymerizable silicon compound having a hydrolyzable functional group.

C (C), (A) and (radical polymerizable monomers other than El) The radically polymerizable monomer (C) used in the present invention is other than the above-mentioned monomers and (B), such as the following: can be given.

Examples of olefinic compounds include low molecular weight unsaturated hydrocarbons such as ethylene and propylene, vinyl halides such as vinyl chloride and vinyl fluoride, vinyl esters of organic acids such as vinyl acetate, styrene, styrene-substituted products, and vinylpyridine. Vinyl aromatic compounds such as vinylnaphthalene, acrylic acid, methacrylic acid, and derivatives of acrylic acid and methacrylic acid, including their esters and amides, N-vinyl compounds such as acrolein, acrylonitrile, N-vinylpyrrolidone, and N-vinylcaprolactam. Compounds such as di-substituted ethylene such as vinylidene fluoride and vinylidene chloride, maleic anhydride, esters of maleic acid and fumaric acid, fluoroalkyl acrylates, fluoroalkyl methacrylates, and the like can be mentioned.

These radically polymerizable monomers can be used alone or in combination of two or more. Among these radically polymerizable monomers, styrene, substituted styrene, esters of acrylic acid and methacrylic acid, fluoroalkyl acrylate, and fluoroalkyl methacrylate are preferred.

In addition, as a radical polymerizable monomer, carbon number 1-4
It is preferable to use methacrylic acid esters having an alkyl group of 281 or more in combination, and it is particularly preferable to use methyl methacrylate and butyl methacrylate in combination. In that case, it is preferable to use a relatively large amount of methyl methacrylate when the adherend is a metal, and to use a relatively large amount of butyl methacrylate when the adherend is a Mylar film.

The usage ratio of radically polymerizable monomers is as follows:
), 30 to 90% by weight of the total weight of (B) and (C)
is preferable, and 50 to 85% by weight is preferable.

If the proportion of the radically polymerizable monomer used is less than 60% by weight, the film forming properties tend to be insufficient, and the strength and flexibility of the obtained coating tend to decrease. In addition, the proportions of the radically polymerizable silicone macromonomer and the crosslinkable monomer tend to be low, resulting in insufficient mold releasability, strength, etc. of the coating.

The amount of radically polymerizable monomer to be used is usually determined by first determining the amount of silicone macromonomer and crosslinking monomer.
It is determined by using the remainder as a radically polymerizable monomer.

This is because it is easy to control the releasability of the film and the chemical resistance, water resistance, heat resistance, and pattern strength by crosslinking and curing.

[Radical copolymerization]

As the radical copolymerization method, conventionally known methods can be used,
For example, a radiation irradiation method, a method using a radical polymerization initiator, etc. can be used, but a method using a radical polymerization initiator is preferable in terms of ease of polymerization operation and ease of controlling the molecular weight. Specifically, a method using a solvent is used. Polymerization method, bulk polymerization method,
Any method such as emulsion polymerization can be used, but each hexamer is uniformly dissolved in a solvent such as toluene or methyl isobutyl ketone (hereinafter referred to as MIBK),
A solution polymerization method that allows uniform polymerization is preferred.
.

The present graft polymer can be easily produced by radical copolymerization of a radically polymerizable silicone macromonomer, a radically polymerizable monomer, and a crosslinkable monomer using various polymerization methods as described above.

[Mold release coating agent]

The M-type coating agent of the present invention is made of the graft polymer described above, and is preferably obtained by crosslinking and curing by the following method. The crosslinking and curing type is a crosslinking and curing type using a hydrolyzable functional group of a radically polymerizable silicon compound having a hydrolyzable functional group.
(referred to as silane cross-linking curing type) and a type in which hydroxyl groups derived from radically polymerizable monomers having hydroxyl groups are cross-linked and curing using a polyvalent incyanate or melamine curing agent (hereinafter referred to as hydroxyl group cross-linking curing type)
From the viewpoint of adhesion of the present graft polymer to various coated objects, water resistance of the adhesion, and moisture resistance, the present graft polymer is particularly preferably a hydroxyl group crosslinked and cured type.

In addition, the mold release coating agent of the present invention may contain other fats other than the present graft polymer, such as acrylic resins, epoxy resins, etc., as long as the properties as a mold release coating agent provided by the present graft polymer are not impaired. Curable compositions comprising unsaturated polyester resins, radically polymerizable components as polymer precursors such as (meth)acrylates, and polyester poly(meth)acrylates disclosed in JP-A-49-120889. It is possible to combine

The allowable blending amount of these resins is not constant depending on the type of resin to be blended, but in order to simultaneously achieve excellent mold release properties, excellent adhesion to the substrate, etc., it is necessary to combine this graft polymer with these resins. In total, it is desirable to have 50 weights or less.

Regarding the silane cross-linked curing type, the submerged solution obtained by the bath liquid polymerization method is used as it is, or is further diluted with a diluting solution such as toluene, and a commonly used silane coupling agent curing catalyst - for example, When a small amount of digtyltin dilaurate, dibutyltin maleate, etc. is added, the coating is applied to one object, and dried, a crosslinked cured film with crushed mold releasability is obtained. The crosslinking of the film is achieved by crosslinking the hydrolyzable functional groups due to moisture in the air.The film thus obtained becomes a seed to various solvents, has significantly improved solvent resistance, and has excellent adhesion to various substrates. The surface hardness of the coating and the mechanical strength of the coating and pattern are also significantly improved.

Examples of usable catalysts for accelerating crosslinking include organic tin compounds such as the aforementioned dibutyltin dilaurate and dibutyltin maleate, dispersible compounds such as phosphoric acid and p-toluenesulfonic acid, and known amine sequential compounds such as ethylenediamine and triethylenetetramine. The amount used is 0.001 to 10% by weight, preferably 0.00% by weight based on the paint resin.
It is a 1 to 8-fold firefly.

Next, regarding the hydroxyl group cross-linked curing type, the hydroxyl group-containing polymer solution obtained by solution polymerization can be used as is or further diluted with a solvent such as toluene, MIBK, methyl ethyl ketone (hereinafter referred to as MEK), By adding a nerat, applying it to the object to be coated, and drying it, a crosslinked cured film with excellent female molding properties can be obtained. Excellent adhesion to
Not only does it have excellent adhesion and moisture resistance, but it also has significantly improved solvent resistance, heat resistance, hardness, and mechanical strength.

Examples of polyvalent isocyanates include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, inphorone diisocyanate, methylene bis(4-7 chlorohexyl isocyanate), and those represented by the following formula % formula %] These can be used alone or in combination of two or more.

When curing at room temperature using isocyanates,
It is also possible to accelerate curing by adding known catalysts such as dibutyltin dilaurate. The amount of polyvalent incyanate used as a curing agent is determined in accordance with the hydroxyl group fL (per OH) based on the above-mentioned hydroxyl group-containing radically polymerizable monomer in the graft polymer of the present invention.

The amount of polyvalent incyanate to be used is determined so that the normal incyanate ff1 (NCO equivalent) is approximately equal to the OH child.

In addition, the hydroxyl group crosslinked curable graft polymer can be cured using a melamine curing agent, a urea resin curing agent, a polybasic acid curing agent, etc., which are used in ordinary heat-curing acrylic paints.
An excellent mold release coating agent that has excellent physical properties (adhesion, adhesion water resistance, moisture resistance, solvent resistance, heat resistance, strength, etc.) that are equivalent to those of the polyvalent incyanate cure by heating and curing. is obtained. Examples of the melamine curing agent include butylated melamine, methylated melamine, epoxy-modified melamine, etc., and those with various degrees of modification can be used depending on the purpose, and the degree of self-condensation can also be selected as appropriate.

Examples of the urea resin include methylated urea and butylated urea. Further, as the polybasic acid curing agent, long-chain aliphatic dicarboxylic acids, aromatic polycarboxylic acids, or anhydrides thereof, etc. are useful.

When using melamine or urea hardeners, curing can be accelerated by adding an acidic catalyst.

Heat curing conditions are usually 80 to 200°C for 5 to 6 minutes.
The heating time is 0 minutes.

As the curing agent, a melamine curing agent is preferred from the viewpoint of ease of controlling coating hardness and thermal crosslinking.

The amount of melamine curing agent used is the same as for normal heat-curing acrylic paints. That is, the amount of melamine is determined depending on the amount of hydroxyl groups in the graft polymer, but the melamine curing agent itself may be condensed, and the amount of melamine varies depending on the application (although it is common to use hydroxyl group-containing polymers and melamine). The amount of melamine hardener in the total amount of hardener is 10-50% by weight.

[Fillers, pigments, stabilizers]

Various fillers, pigments, etc. can be added to the mold release coating agent of the present invention. Examples of these include various silicas, various clays, calcium carbonate, magnesium carbonate, pregelatinized titanium, iron oxide, glass fiber, dispersion stabilizers,
You can use UV absorbers, etc.

[Subject to be coated]

The objects to be coated with the discrete coating agent of the present invention include rubber, plastic parts, plastic films, molds, metal plates, ceramics, glass, and wood.
Any material such as paper may be used.

[For production]

The release coating agent of the present invention exhibits extremely excellent adhesion, adhesion water resistance, and moisture resistance to various objects to be coated. This is thought to be due to the synergistic effect of the formation of a non-uniform phase separation structure derived from the graft polymer, in which there is a large amount of silicone component on the surface of the film and a small amount of silicone component at the interface of the coated object, and the crosslinking and curing effect. It will be done.

Furthermore, in the mold release coating agent of the present invention, since the bond between the silicone component of the silicone macromonomer and the radically polymerizable 7-mer (q component) is not connected by a Si-〇-C bond, This is thought to be because it has excellent hydrolyzability and also has the effect of the embankment effect of silicone.

The fact that the film itself exhibits excellent mechanical strength, heat resistance, and chemical resistance is thought to be due to crosslinking and hardening of the film.

Based on such effects, it is possible to make the surface of the coating exhibit excellent mold releasability, which is of practical value, and it is also possible to exhibit excellent lubricity associated therewith.

[Reference Examples, Examples and Comparative Examples]

The present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples below.

The physical properties of the film on each side were evaluated using the following method. Also, parts and parts represent parts by weight and parts by weight, respectively.

0 Release property 2 A coated object coated with the coating agent of the present invention was used as a sample, KOKUYO sellotape (24u width) was pressed onto the coating surface, and the sellotape was tensile tested using a tensile tester at a speed of 200 fl/51 m x 2 s°C x 60 Chi RH
It is expressed as the tensile strength (?) when peeled at 180° under the conditions of .

0 Adhesion (1): Cut a 2m square grid pattern with a knife on the object coated with the coating agent of the present invention, peel off the grid pattern with cellophane tape, and check the remaining percentage of the grid pattern. expressed.

0 Adhesion (2): Form a coating film as shown in Figure 1, remove the Teflon sheet 3, use it as a sample, hold part A of the film with a bottle set, and pull it in the direction of the arrow to compare the film and the coating. The adhesion of objects was observed. When part A of the film was destroyed, it was marked with a circle (good adhesion), and when part B of the film had peeled off, it was marked with an x (poor adhesion).

Water resistance of 0 adhesion 2 After immersing the sample obtained by the test method of adhesion (2) above in boiling water for a predetermined time, take out the side slope from the boiling water, cool it, and then test the adhesion (2) above. ) The water resistance of the adhesion was evaluated according to the evaluation method.

Heat resistance of 0 film 2. The object coated with the coating agent of the present invention was placed in a dryer at 150°C for 1 hour.
The presence or absence of tackiness on the surface of the film at °C was evaluated for heat resistance.

The tack is the tack used when pressing the gauze against the surface of the film and releasing it, and if there is no tank, it is indicated by a circle indicating that it is heat resistant)
Solvent resistance of 0 film: Teflon sheet was coated with the coating agent of the present invention, and the resulting film was immersed in a specified solvent at room temperature for one week. The solvent resistance of the coating was observed. If the film maintains the same shape7 as before dipping, it is marked with ○ (good solvent resistance), and when it becomes a swollen film, it is marked with Δ (poor solvent resistance), and the film dissolves and loses its shape ( When this occurred, it was marked with an x (extremely poor solvent resistance).

0 Surface Hardness of Film 2 The coating agent of the present invention was coated on a glass plate and evaluated according to JIS K5400 (General Test Methods for Coatings, 6-14 Pencil Scratch Test). A weight of 1 ky was used to measure the pencil hardness when scratches were observed and the pencil hardness when tears in the coating were observed.

0 Lubricity The coefficient of kinetic friction (μk ). In addition, the average value of the measurement time of 10 minutes was taken as μ.

Contact: Sapphire with 0flfL Load cage: 15y (★Load applied to the coating surface through the contact) Peripheral speed: 93.2cN/sec Time: 10 minutes (friction measurement time) Temperature: 25℃ Humidity: 6D Chi RH Reference Example 1 0.5 g of potassium metal (0,0128 (mo
t) and about 54 g of n-hexane were added, and 10 d of methanol was added dropwise over 30 minutes in a water bath under a stream of dry nitrogen. After stirring for an additional 30 minutes, excess methanol and n-hexane were distilled off under reduced pressure.

Subsequently, octamethylcyclotetrasiloxane 401
40 g of tetrahydrofuran, which had been thoroughly dehydrated with a sieve, was added and heated under reflux for 4 hours.

Octamethylcyclotetrasiloxane (molar ratio).

After the temperature of the reaction solution fell to room temperature, 31 g of a 10-titetrahydrofuran solution of γ-methacryloxyglobildimethylchlorosilane (0.0141 mob of r-methacrylogysibropyldimethylchlorosilane) was gradually added dropwise, and after the completion of the dropwise addition, Even at room temperature! Stirred for 10 minutes.

The 5i-CL potassium salt of r-methacrylic acid I ciprovir dimethylchloride 7y = i, 10 (total ratio). After filtering off the generated potassium chloride precipitate, the filtrate was poured into 16 methanol to precipitate the xylicone macromonomer. After decantation and drying, a colorless transparent oil-like silicone macromonomer is obtained.26.0.1? Obtained.

The silicone macromonomer had a polystine equivalent number average molecular weight of 8,900 by GPC.

Next, 10 parts of the obtained silicone macromonomer, 42 parts of methyl methacrylate (hereinafter abbreviated as MMA), 42 parts of butyl methacrylate (hereinafter abbreviated as BMA), 2 to 6 hydroxyethyl methacrylate (hereinafter abbreviated as HEMA)
Part methyl isobutyl ketone (hereinafter abbreviated as MI BK) 1
50 parts, azobis inbutyronitrile (hereinafter referred to as AIBN)
) was placed in a flask equipped with a condenser, a stirrer, and a thermometer, and polymerized for 5 hours at a temperature of 75°C under N2, after which 5 parts of AIBNo was added and 5 parts of AIBNo was added at a temperature of 75°C. Polymerized for hours. In this way, a 40% MIBK solution of the present hydroxyl group crosslinked curable kraft polymer was obtained.

Reference example 2 4 equipped with a stirrer, thermometer, condenser, N, and introduction pipe
α,ω-dihydroxypolydimethylsiloxane CM in a Tulo flask.

CH.

(0.15 mol), 12.4 g (0.05 mol) of γ-methacryloxypropyltrimethoxysilane, and 6.5 g of potassium acetate were charged and reacted under N at a temperature of 150° C. for 20 hours. After cooling, the reaction mixture was poured into 1360 g of toluene to precipitate potassium acetate, which was then removed by filtration.

50 parts of silicone macromonomer 20 titolene solution obtained by oxidation, 42 parts of MMA, 42 parts of BMA, HEM
Polymerization was carried out in the same manner as in Reference Example 1 using 6 parts of A, 110 parts of MIBK, and 5 parts of AIB No. 40 to obtain a 40% solution of the hydroxyl group-crosslinked and curable graft polymer.

Reference example 6 α,ω-DihydroxydimeCH as silicone.

CH.

So(7)2201 (0,1 mo/I/
) and 9.49 g (0.12 mol) of pyridine dissolved in 400 g diethyl ether were added 22.06 g (0.12 mol) of r-methacryloxyglobildimethylchlorosilane.
A 1 mol) solution of 10 thidiethyl ether was gradually added dropwise at room temperature over 20 minutes.

The reaction proceeded immediately and white crystals of pyridine hydrochloride were precipitated. After the addition was completed, the mixture was further stirred at room temperature for 1 hour, and the pyridine hydrochloride crystals were removed by filtration.

Next, put this filtrate into a separatory funnel and add *SOO hemp (shake 5 and wash with water. After washing with water, leave the separatory funnel still and separate the upper layer of ether and the lower aqueous layer. was separated, and anhydrous sodium sulfate was added to the resulting ether layer, and the mixture was left overnight at room temperature to dehydrate.Then, the anhydrous sodium sulfate was removed by p-filtration, and the resulting p solution was distilled under reduced pressure to remove the ether, resulting in a colorless and transparent layer. The silicone macromonomer 2 o s y ca wttt.

Silicone macro 7) -? -10 copies,
34 parts of MMA, 52 parts of HMA, 4 parts of γ-methacryloxypropyltrimethoxysilane, 0.
Polymerization was carried out in the same manner as in Reference Example 1 using 150 parts of 5g of silane cross-linked and curable graft polymer to obtain a 40% toluene solution of the silane crosslinked curable graft polymer.

Reference Example 4 10 parts of the Noricone macromonomer obtained in Reference Example 6,
45 parts of MMA, ethyl acrylate (hereinafter abbreviated as EA)
30 copies, HEMA 15 copies, MIBK 150 copies, AIB
Polymerization was carried out in the same manner as in Reference Example 1 using 5 parts of hydroxyl group crosslinked curable graft polymer.
A solution was obtained.

Reference Example 5 15 parts of the silicone macro 7mer obtained in Reference Example 1,
50 parts of styrene, 29 parts of butyl acrylate, HEMA
(Using 5 copies, 150 copies of MIBK, and 5 copies of AIBNo.
Thereafter, polymerization was carried out in the same manner as in Reference Example 1 to obtain a 40% solution of the hydroxyl group crosslinked curable graft polymer.

Example 1 Reference Example 10 25 parts of 40% MI BK solution of graft polymer, Coronate EH1 manufactured by Nippon Polyurethane Industry ■,
1 part of dibutyltin dilaurate and 0.005 part of dibutyltin dilaurate were mixed together and further diluted with MEK to obtain a solution with a solid content of 20 parts. The solution was applied to a PET film having a thickness of 50 μm using a bar coater, air-dried, and then dried at a temperature of 70° C. for 0.5 hours.

The film is extremely smooth, colorless and transparent with no repellents.
The thickness was 0 μm.

The PET film surface coated product thus obtained was evaluated for each item according to the method for evaluating the physical properties of the film described above. The results are shown in Table 1 as Example 1. Further, the solvent resistance of the coating and the surface hardness of the coating were evaluated by coating in the same manner as above according to the method for evaluating the physical properties of the coating. In this case too, the coating thickness was 20 μm. The results are also shown in Table 1 as Example 1.

Example 2 Reference Example 20 Using a 40% solution of the present graft polymer, a PET film surface coating was obtained in the same manner as in Example 1, and the physical properties of the film were evaluated in the same manner as in Example 1.

The results are shown in Table 1 as Example 2.

Example 6 Reference Example 40 Per 100 parts of a 40% solution of the graft polymer, 15 parts of Cyme Pressure 266J (trade name manufactured by Mitsui Tozai Chemical ■) as a melamine curing agent, 1)
- Add and mix 0.5 parts of toluenesulfonic acid, and further M
It was diluted with EK to make a solution with a solids content of 20%. The solution is A
Using a bar coater on the T-board (painted and air-dried for 200 minutes)
C. Heated for 30 minutes.

The film is extremely smooth, colorless and transparent with no repellency.
The thickness was 0 μm.

The physical properties of the thus obtained At plate surface coated product were evaluated in the same manner as in Example 1. The results are shown in Table 1 as Example 6.

Example 1 + Tj 4 40φ bath solution 1 of the present graft polymer obtained in Reference Example 6
Per 00 parts, dibutyltin dilaure) 0.004
of the solution was added and further diluted with MgK to obtain a solution with a solid content of 20%. Coat the solution on a glass plate using bar caulk,
After drying the lice, it was dried at 70°C for 60 minutes.

The coating is smooth, colorless and transparent with no repellency.
The thickness was 0 μm. The physical properties of the resulting glass plate surface coating were evaluated in the same manner as in Example 1. For the evaluation of lubricity, the above solid content of 20% was applied to the At plate.
The solution was coded in the same manner as above.

The evaluation results are shown in Table 1 as Example 4.

Example 5 Reference Example 50 Using a 40% solution of the graft polymer, the same procedure as in Example 1 was carried out to obtain a PET film surface coating, and the physical properties of the film were evaluated in the same manner as in Example 1. The results are shown in Table 1 as Example 5.

Example 6 10 parts of silicone macromonomer obtained in Reference Example 6,
MMA 42 Division, BMA 42 Division, Anal Kite 6 Division, MIBKl
Polymerization was carried out in the same manner as in Example 1 using 50 parts of AIB No. and 5 parts of AIB No. to obtain a 40% solution of the hydroxyl group crosslinked curable graft polymer.

25 parts of the obtained solution, 1.1 part of Coronate EH manufactured by Nippon Polyurethane Industry ■, dibutyltin dilaure) 0.00
5 parts were mixed and further diluted with MFJK to form a solution with a solid content of 5%. The solution was coated on a PET film with a thickness of ``吃ゝ''+2μrrH7) using a bar coater, air-dried, and then dried at a temperature of 70°C for 0.5 hours.The film was extremely smooth, free from repelling, and transparent and colorless. The thickness was .7 μm.

The physical properties of the PET film surface coated product thus obtained were evaluated in the same manner as in Example 1. The results are shown in Table 1 as Example 6. In this case, since the coating thickness was as thin as 0.7 μm, the evaluation of the adhesion (2) was not performed. The adhesion water resistance was determined by immersing the PET film surface coating obtained above in boiling water for a predetermined time, taking it out, removing the adhering water with paper, and then evaluating the adhesion water resistance according to the adhesion evaluation method (1) above. The gender was evaluated.

Comparative Example 1 Reference Example 10 Silicone macromonomer 10 in polymerization
Polymerization was carried out in the same manner as in Reference Example 1 using 45 parts of MMA, 45 parts of HMA, 5 parts of MIBI (150 parts), and 5 parts of AIB No. to obtain a 40% solution of a graft polymer containing no crosslinkable monomer. Diluted with MEK to make a solution with a solid content of 20%, and then operated as t in the same manner as in Example 1 to prepare P.
An ET film surface coated product was obtained, and the physical properties of the film were evaluated in the same manner as in Example 1. The results are shown in Table 1 as Comparative Example 1.

(No.J Effect of the Invention The mold release coating agent of the present invention has a mold releasability l on the coating surface.
It has excellent adhesion to the coated object, and is also excellent in durability, so it is used as a release agent in release paper.
It is industrially useful as a mold release agent for molds used in rubber plastic molding.

In addition, the coating agent of the present invention has excellent lubricity on the coating surface and excellent adhesion to the coated object, so it can be used as a coating for forming lubricating coatings on rubber/glass parts, plastic films, mechanical parts, etc. It is also useful as an agent.

[Brief explanation of drawings]

Figure 1 is a schematic diagram showing the measurement situation of adhesion (2). Teflon sheet 4, .... Direction A in which the film is pulled ... Part B of the film on the top of the Teflon sheet ... Part of the film that is in direct contact with the object to be coated part

Claims (1)

[Claims] 1, (A), a radically polymerizable silicone macromonomer, (B), a radically polymerizable monomer having a hydrolyzable functional group bonded to a silicon atom or a radically polymerizable monomer having a hydroxyl group, and (C), the above (A) ) and (B) A mold release coating agent comprising a graft polymer obtained by radical copolymerization of radically polymerizable monomers other than (B).