JP2020189945A - Resin composition for release paper or release film, release paper, and release film - Google Patents

Abstract

To provide a resin composition for release paper or release film capable of obtaining a cured film excellent in releasability, and repeated durability regardless of whether it is cured at a low temperature and cured in a short time.SOLUTION: The resin composition for a release paper or a release film includes: (A) a hydroxyl group-containing acrylic resin having a hydroxyl value of 140-180 mgKOH/g; (B) a resin selected from the group consisting of a phenyl ether-type methylated melamine resin, a methylol type methylated melamine resin, and multimers of these; and (C) an organopolysiloxane having 2 or more functional groups bondable with one or more resin(s) selected from the constituent (A) and the constituent (B).SELECTED DRAWING: None

Description

The present invention relates to a resin composition for a release paper or a release film, and a release paper or a release film having a cured film obtained by curing the composition on a substrate.

Conventionally, a release agent is applied to the surface of a sheet-like base material such as paper or plastic to form a cured film, thereby imparting release characteristics to an adhesive or adhesive substance.

Release papers and release films have a wide variety of uses, such as labels, stickers, and tapes, which are used for sticky substances, and ceramic layers, urethane resins, and other non-sticky substances. Yes, different performance is required depending on the application.

An example of a process paper used in the molding process of a non-adhesive substance is process paper for producing synthetic leather. In the process of manufacturing synthetic leather, a release agent is cured on a base material to form a process paper, and a urethane resin, a vinyl chloride resin, a polyamide resin, a polyamino acid resin, or the like is applied onto the process paper and dried. Synthetic leather is produced by forming an adhesive layer on the dried resin, adhering a base cloth, and peeling the resin from the process paper.

There are matte (matte) type and enamel (strong luster) type synthetic leather, but in the production of enamel type synthetic leather, the surface condition of the release agent film is reflected on the synthetic leather, so it is expensive for the cured film. Glossiness is required. In addition, in order to increase the productivity of synthetic leather, the process paper is generally used multiple times. Therefore, it is desirable that there is little change in peelability (release property) when used repeatedly.

As a resin composition for making the surface of the process paper for synthetic leather removable, three kinds of polypropylene-based, aminoalkyd resin / aminoacrylic resin-based, and silicone-based are known as typical ones. Polypropylene-based products have excellent peelability and durability when used repeatedly, but there is a limit to their use at relatively high temperatures. In this case, the peeled surface is easily damaged, and enamel type products are used. It has drawbacks such as being unsuitable for synthetic leather. Amino alkyd resins and amino acrylic resins have excellent luster, but poor peelability. Although silicone-based products have excellent peelability, they have poor luster and are not suitable for enamel-type synthetic leather.

To solve the above problems, Patent Document 1 (Japanese Unexamined Patent Publication No. 56-14550) states that 15 to 50 mol% of organic groups bonded to silicon atoms in one molecule are phenyl groups, and the remaining organic groups. A resin composition for process release paper comprising a silicone-modified acrylic resin in which at least one of the groups is modified with an organopolysiloxane which is a hydroxy group-substituted organic group and a polyisocyanate compound is disclosed. Then, it is described that "by using a hydroxy group-substituted organic group, a process release paper having excellent heat resistance, good gloss, and good peelability can be obtained."

Further, in Patent Document 2 (Japanese Unexamined Patent Publication No. 56-1980), 15 to 50 mol% of the organic groups bonded to the silicon atom in one molecule are phenyl groups, and at least one of the remaining organic groups is hydroxy. A resin composition for process release paper comprising a silicone-modified alkyd resin modified with an organopolysiloxane which is a group-substituted organic group and a polyisocyanate compound is disclosed. Then, it is described that "a process release paper using an alkyd resin also has excellent heat resistance, has good gloss, and can obtain a process release paper having good peelability."

In Patent Document 3 (Japanese Unexamined Patent Publication No. 56-14566), 15 to 50 mol% of the organic groups bonded to the silicon atom in one molecule are phenyl groups, and at least one of the remaining organic groups is substituted with a hydroxy group. A resin composition for process release paper comprising a silicone-modified acrylic resin modified with an organic group organopolysiloxane, an alkanol-modified amino resin, and an acidic catalyst is disclosed. Then, it is described that "a process release paper containing both an acrylic resin and an amino resin can be obtained with excellent heat resistance, good gloss, and good peelability by using an acidic catalyst." ing.

In Patent Document 4 (Japanese Unexamined Patent Publication No. 3-263475), a methyl group, a phenyl group and an organic group are bonded to a silicon atom, and at least one of the organic groups is a hydroxy group substituted organic group, which is bonded to a silicon atom. A resin composition for process release paper comprising a silicone-modified alkyd resin in which 15 to 50 mol% of all substituents are modified with an organopolysiloxane which is a phenyl group, an alkanol-modified amino resin, and an acidic catalyst is disclosed. .. Then, it is described that "a process release paper containing both an alkyd resin and an amino resin can be obtained by using an acidic catalyst, which has excellent heat resistance, good gloss, and good peelability." There is.

In Patent Document 5 (Japanese Unexamined Patent Publication No. 2-28242), alkido resin or acrylic resin and 15 to 50 mol% of silicon atom-bonded organic groups in one molecule are phenyl groups, and at least one of the remaining organic groups. One is disclosed a resin composition for process release paper, which comprises an organopolysiloxane which is a hydroxy group-substituted organic group, an alkanol-modified amino resin, and an acidic catalyst. Then, it is described that "the process release paper obtained by this resin composition for process release paper is excellent in peelability, heat resistance, and gloss as compared with the conventional process release paper."

According to Patent Document 6 (Japanese Patent No. 5282083), the hydroxyl value is 10 to 150 mgKOH / g, the glass transition temperature is 20 to 100 ° C., and the weight average molecular weight is 20,000 to 100,000. A release agent composition comprising a hydroxy group-containing acrylic resin, an amino resin, and a silicone resin having a functional group capable of chemically binding to at least one of the hydroxy group-containing acrylic resin and the amino resin is disclosed. Has been done. Then, it is described that "it is excellent in peelability at high temperature, gloss, surface condition, and repeatability."

As described above, the aminoalkyd resin / aminoacrylic resin-based release agent has improved gloss, heat resistance, and release property, and has obtained a certain effect. However, the aminoalkyd resin / aminoacrylic resin-based release agent has a drawback of slow curing, and it is necessary to improve the curability.

To solve the above problems, Patent Document 7 (Japanese Unexamined Patent Publication No. 2000-095929) describes a silicone containing an alkyd resin, an amino resin, and a functional group reactive with the alkyd resin and the amino resin. A release agent composition for process release paper, which comprises a resin and the amino resin contains a methylated melamine resin containing at least one methylol group per triazine nucleus as a main component, is disclosed. It has excellent gloss, surface condition, and reusability, and can be cured and dried at low temperatures. "

In recent years, in order to increase the production efficiency of process paper, there is a strong demand for a release agent composition that can be cured at a low temperature or a release agent composition that can be cured in a short time. If it can be cured at a low temperature, the amount of heat required for production can be reduced and production efficiency can be improved. On the other hand, if it can be cured in a short time, the production speed can be increased and the production efficiency can be improved. Therefore, if a release agent composition that can be cured at a low temperature and can be cured even in a short time can be found, it is possible to provide stable quality without being affected by changes in the curing temperature and curing time due to production efficiency. become.

Since the amount of the silicone resin that imparts mold releasability is small in the aminoalkyd resin / aminoacrylic resin-based release agent, it was found by examination that the release characteristics change depending on whether or not the silicone can be immobilized on the surface layer. I came. This leads to a change in peeling characteristics depending on whether the product is cured at a low temperature or in a short time, resulting in unstable quality. However, in the conventional release agent composition, there is no composition capable of achieving both curability at a low temperature and curability in a short time.

Japanese Unexamined Patent Publication No. 56-14550 Japanese Unexamined Patent Publication No. 56-1980 Japanese Unexamined Patent Publication No. 56-14566 Japanese Unexamined Patent Publication No. 3-263475 Japanese Unexamined Patent Publication No. 2-28242 Japanese Patent No. 5282083 Japanese Unexamined Patent Publication No. 2000-0959929

The present invention has been made in view of the above circumstances, and is a release paper capable of forming a release film having good peelability and repeatability in both cases of curing at a low temperature and curing in a short time. Alternatively, it is an object of the present invention to provide a resin composition for a release film, and a release paper or release film having a cured film obtained by curing the composition on a substrate.

As a result of diligent studies to achieve the above object, the present inventor (A) a hydroxy group-containing acrylic resin having a hydroxyl value of 140 to 180 mgKOH / g, (B) a full ether type methylated melamine resin, and methylol. A functional group that can be chemically bonded to a type methylated melamine resin, a resin selected from these multimers, and one or more resins selected from the components (C) (A) and (B) is contained in one molecule. A cured film having good peelability and repeated durability can be obtained in both the case where the resin composition containing two or more organopolysiloxanes is cured at a low temperature and the case where the resin composition is cured in a short time. Alternatively, they have found that they are suitable as a resin composition for a release film, and have come up with the present invention.

Therefore, the present invention provides the following resin composition for release paper or release film, and release paper or release film.
1. 1. (A) A hydroxy group-containing acrylic resin having a hydroxyl value of 140 to 180 mgKOH / g,
(B) Full ether type methylated melamine resin, methylol type methylated melamine resin, resin selected from multimer thereof, and one or more resins selected from (C) (A) component and (B) component. A resin composition for a release paper or a release film containing an organopolysiloxane having two or more functional groups that can be chemically bonded in one molecule.
2. 2. The resin composition for a release paper or a release film according to 1, wherein the component (A) has a weight average molecular weight of 5,000 to 400,000.
3. 3. The resin composition for a release paper or a release film according to 1 or 2, wherein the blending amount of the component (B) is 10 to 120 parts by mass with respect to 100 parts by mass of the component (A).
4. The resin composition for a release paper or a release film according to any one of 1 to 3, wherein the component (B) is a full ether type methylated melamine resin and a resin selected from these multimers.
5. The resin composition for a release paper or a release film according to any one of 1 to 4, wherein the amount of the component (C) blended is 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (A).
6. The resin composition for a release paper or a release film according to any one of 1 to 5, wherein the component (C) contains an organopolysiloxane in which 10 to 60 mol% of an organic group bonded to a silicon atom in one molecule is a phenyl group. ..
7. The resin composition for a release paper or a release film according to any one of 1 to 6, further comprising (D) an acidic catalyst.
A release paper or release film having a cured film formed by applying the release paper or the resin composition for a release film according to any one of 8.1 to 7 to a substrate and then heating the substrate.

The release paper or the resin composition for a release film of the present invention can form a release film having good peelability and repeatability in both cases of curing at a low temperature and curing in a short time. The gloss is equal to or higher than that of the conventional release agent composition.

Hereinafter, the present invention will be described in more detail. Hereinafter, the "resin composition for release paper or release film" may be simply abbreviated as "composition".

[(A) component]
The component (A) of the present invention is a hydroxy group-containing acrylic resin having a hydroxyl value of 140 to 180 mgKOH / g, and can be used alone or in combination of two or more.

The hydroxyl value of the hydroxy group-containing acrylic resin is 140 to 180 mgKOH / g, particularly preferably 141 to 178 mgKOH / g. If the hydroxyl value is less than 140 mgKOH / g, the peelability and repeated durability when cured in a short time will deteriorate. On the other hand, if the hydroxyl value exceeds 180 mgKOH / g, the surface condition of the cured film deteriorates and the gloss decreases. In the present invention, the hydroxyl value of the hydroxy group-containing acrylic resin shall be a value measured in accordance with the neutralization titration method (JIS K0070).

In the present invention, by using a hydroxy group-containing acrylic resin having a hydroxyl value of 140 to 180 mgKOH / g as the component (A), it is releasable and repeatable regardless of whether it is cured at a low temperature or in a short time. It has been found that the durability is good. Although not bound by theory, it is considered that the exfoliation property is improved by immobilizing the organopolysiloxane of the component (C) on the surface of the coating film. Therefore, it is presumed that the shorter the curing time, the shorter the time for the organopolysiloxane to migrate to the surface layer, and the organopolysiloxane is immobilized in the film before being transferred to the surface layer, resulting in poor peelability. As the amount of the hydroxyl group of the component (A) increases, the compatibility between the component (A) and the organopolysiloxane of the component (C) becomes worse, and the migration to the surface becomes easier. Therefore, it is considered that a film in which organopolysiloxane is fixed on the surface of the film was obtained even under a short curing condition, and excellent peelability and repeatability were exhibited.

The hydroxy group-containing acrylic resin of the component (A) is not particularly limited as long as it is the above-mentioned hydroxy group-containing acrylic resin having a specific hydroxyl value, but it has one or more hydroxy groups in one molecule and is radically polymerizable. A radically polymerizable monomer (Aa) having one or more groups in one molecule and a radically polymerizable monomer having one or more radically polymerizable groups in one molecule without having a hydroxy group in one molecule (A) It is preferable to use a copolymer with Ab).

Here, the component (Aa) is not particularly limited as long as it is a radically polymerizable monomer having one or more hydroxy groups in one molecule and one or more radically polymerizable groups in one molecule. One type may be used alone, or two or more types may be mixed and used. Examples of the radically polymerizable group include an acrylic group, a methacryl group, a styryl group, a siliceous ester group, a vinyl group, an allyl group and the like.

Specifically, as the component (Aa), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) ) Acrylate, 1,4-cyclohexanedimethanol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and Praxel F series (manufactured by Daicel Co., Ltd.) obtained by modifying these with caprolactone are exemplified.

The component (Ab) is not particularly limited as long as it is a radically polymerizable monomer that does not have a hydroxy group in one molecule and has one or more radically polymerizable groups in one molecule. Or two or more of them can be used in combination as appropriate. Examples of the radically polymerizable group include an acrylic group, a methacryl group, a styryl group, a siliceous ester group, a vinyl group, an allyl group and the like.

Specifically, as the component (Ab), a styrene compound such as styrene, o-methylstyrene, p-methylstyrene, α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl ( Meta) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, trifluoropropyl (meth) acrylate, Estel compounds of (meth) acrylic acid such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epylcyclohexyl Epyl group-containing radically polymerizable monomer such as methyl (meth) acrylate; γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane , Γ-Methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropyltriisopropenoxysilane, γ-acryloxypropyltrimethoxysilane, acryloxymethyltrimethoxysilane, γ-acry Radical polymerizable silane compounds such as loxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, α-methylstyryltrimethoxysilane; polyoxyalkylene group-containing radically polymerizable monomer ; Propyl (meth) acrylate and the like are exemplified.

The polymerization ratio of the component (Aa) and the component (Ab) is adjusted according to the hydroxyl value of the hydroxy group-containing acrylic resin. The hydroxyl value of the hydroxy group-containing acrylic resin obtained by polymerization needs to be 140 to 180 mgKOH / g, and specifically, the polymerization ratio of the component (Aa) and the component (Ab) is (A). The molar ratio of the A-a) component and the (A-b) component is preferably 1: 0.1 to 1:10 ((A-a) :( (A-b))), preferably 1: 0.3 to 1: 10. It is more preferably 1: 5. If the amount of the component (Aa) is too small or too large, synthesis may be difficult.

The copolymerization of the component (Aa) and the component (Ab) is carried out by peroxides such as benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, and tert-butyl 2-ethylperoxyhexaneate. It is carried out in the presence of a usual radical polymerization initiator such as an azo compound such as 2'-azobis (2-methylbutyronitrile), and can be obtained by a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or a massive polymerization method. It is also possible to apply the method of.
The amount of the polymerization initiator used is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, based on 100 parts by mass of the total of the components (Aa) and (Ab). preferable.

In the present invention, among these polymerization methods, the solution polymerization method is preferable because it is easy to adjust the weight average molecular weight of the (A) hydroxy group-containing acrylic resin to the optimum range.
The solvent used in this case includes aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; ethanol. , Isopropanol, n-butanol, monovalent alcohols such as isobutanol, and the like, and one type alone or two or more types can be used in combination as appropriate.
The amount of the solvent used is preferably 10 to 900 parts by mass, more preferably 20 to 800 parts by mass, based on 100 parts by mass of the total of the components (Aa) and (Ab).

When the component (Aa) and the component (Ab) are copolymerized by the solution polymerization method, the polymerization conditions are 50 to 180 ° C., particularly 60 to 120 ° C. for 1 to 15 hours, particularly 2 It is preferably 10 hours.

The weight average molecular weight of the component (A) is preferably 5,000 to 400,000, more preferably 10,000 to 300,000, and even more preferably 20,000 to 200,000. When the weight average molecular weight is within the above range, the coatability and handleability are good. The weight average molecular weight is a polystyrene-equivalent value obtained by gel permeation chromatography (hereinafter abbreviated as “GPC”) using tetrahydrofuran as a developing solvent.

[(B) component]
The component (B) is a resin selected from a full ether type methylated melamine resin, a methylol type methylated melamine resin, and a multimer of these, and can be used alone or in combination of two or more. The component (B) in the present invention contains a structure in which a functional group is bonded around a triazine ring via three nitrogen atoms. The component (B) serves as a cross-linking agent that reacts with the component (A) and / or the component (C).

The melamine resin is a synthetic resin obtained by condensing melamine and formaldehyde, and is a condensate composed of a monomer or a multimer of a dimer or more. It has an imino group, a methylol group or an alkoxymethyl group as a functional group in one molecule, and is classified into a fur ether type, a methylol type, an imino type and a methylol / imino type according to the functional group.

Further, melamine resins are classified according to the type of alkoxymethyl group, melamine resins in which all alkoxymethyl groups are methoxymethyl groups are methylated melamine resins, and melamine resins in which all alkoxymethyl groups are n-butoxymethyl groups are n. The melamine resin which is a butylated melamine resin and in which a methoxymethyl group and an n-butoxymethyl group are mixed in the alkoxymethyl group is a methylated / n-butylated melamine resin.

The component (B) in the present invention is used by a full ether type methylated melamine resin, a methylol type methylated melamine resin, and a multimer of these because a cured film having excellent peelability, repeatability, and curability can be obtained. Therefore, a full ether type methylated melamine resin and a multimer thereof are preferable.

The component (B) in the present invention may be a commercially available product, or may be synthesized according to a conventionally known method. Commercially available products include, for example, Cymel 300, Cymel 303LF, Cymel 350, Cymel 370N (all manufactured by Ornex Japan Co., Ltd.), Nicarac MW-30M, Nicarac MW-30 (all manufactured by Nippon Carbide Industry Co., Ltd.) And so on.

The blending amount of the component (B) is preferably 10 to 120 parts by mass, more preferably 15 to 110 parts by mass, and further preferably 20 to 100 parts by mass with respect to 100 parts by mass of the component (A). Within the above range, a cured film having good peelability and curability and excellent repeatability can be obtained.

[Component (C)]
The component (C) of the present invention contains two or more functional groups in one molecule, preferably 2 to 4, which can chemically bond to one or more resins selected from the components (A) and (B). It is an organopolysiloxane having an individual, and one type can be used alone or two or more types can be used in combination as appropriate. A release layer is formed by having two or more functional groups in one molecule in which the component (C) can chemically bond with one or more resins selected from the above components (A) and (B). By adopting a structure in which the components (A) and (B) and the component (C) which is a peeling component are chemically bonded in the peeling layer, the transfer of the component (C) to the pressure-sensitive adhesive layer is suppressed. This makes it possible to prevent heavy peeling during tape storage and deterioration of adhesive strength during use.

Examples of such a functional group include a hydroxy group, an amino group, a carboxyl group, an epoxy group, an isocyanate group and the like, and a hydroxy group and an epoxy group are preferable, and a hydroxy group is more preferable.

（式中、Ｒ¹は独立に炭素数１〜２０の非置換又は置換の一価炭化水素基、又はヒドロキシ基、アミノ基、カルボキシル基、エポキシ基又はイソシアネート基を有する炭素数１〜２０の一価有機基であり、Ｒ¹の少なくとも２個はヒドロキシ基、アミノ基、カルボキシル基、エポキシ基又はイソシアネート基を有する炭素数１〜２０の一価有機基である。ａは２以上の整数、ｂは１以上の整数、ｃは０以上の整数、ｄは０以上の整数であり、４≦ａ＋ｂ＋ｃ＋ｄ≦５００である。） The organopolysiloxane of the component (C) may have either a linear structure or a branched chain structure as long as the effects of the present invention can be exhibited, but the following average composition formula (1) is used. The represented organopolysiloxane is preferred.

(In the formula, R ¹ is ^one of ¹ to 20 carbon atoms having an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, or a hydroxy group, an amino group, a carboxyl group, an epoxy group or an isocyanate group. It is a valent organic group, and at least two of R ¹ are monovalent organic groups having 1 to 20 carbon atoms having a hydroxy group, an amino group, a carboxyl group, an epoxy group or an isocyanate group. A is an integer of 2 or more, b. Is an integer of 1 or more, c is an integer of 0 or more, d is an integer of 0 or more, and 4 ≦ a + b + c + d ≦ 500.)

In the above formula (1), as an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms of R ¹ , specifically, a methyl group, an ethyl group, a propyl group, a butyl group and the like having 1 to 1 carbon atoms. 20, preferably 1 to 6 alkyl groups, cyclohexyl groups and the like having 3 to 20 carbon atoms, preferably 5 to 8 cycloalkyl groups, phenyl groups, trill groups and the like having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Aralkyl groups having 7 to 20, preferably 7 to 10 carbon atoms such as aryl groups and benzyl groups, or some or all of the hydrogen atoms bonded to the carbon atoms of these groups are fluorine, chlorine, bromine, iodine and the like. A halogen-substituted alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, selected from a hydroxypropyl group, a 1-chloropropyl group, a 3,3,3-trifluoropropyl group and the like substituted with a halogen atom or the like. Can be mentioned. Of these, a methyl group and a phenyl group are more preferable from the viewpoint of peelability.

The monovalent organic group having 1 to 20 carbon atoms having a hydroxy group, an amino group, a carboxyl group, an epoxy group or an isocyanate group of R ¹ includes a hydroxy group, an amino group, a carboxyl group, an epoxy group or an isocyanate group. It may contain heteroatoms such as an oxygen atom, a nitrogen atom and a fluorine atom, and preferably has a structure in which a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms is bonded. Here, as the divalent hydrocarbon group which may contain a hetero atom, an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group and an octylene group, and a phenylene group. Examples thereof include an arylene group such as, or a combination of two or more of these groups (alkylene-arylene group, etc.), and a group in which an oxygen atom is interposed in these groups.
Specific examples of such monovalent organic groups include 2-hydroxyethyl group, 3-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group and 2-hydroxybutyl group. Group, 2- (hydroxymethyl) propyl group, 2-hydroxypentyl group, 3-hydroxy-2,2-dimethylpropyl group, 3-hydroxypentyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, 2-hydroxy Hexyl group, 7-hydroxyheptyl group, 8-hydroxyoctyl group, 2-hydroxyethoxy group, 3-[(2-hydroxyethyl) oxy] propyl group, 3-[(3-hydroxypropyl) oxy] propyl group, etc. Hydroxyalkyl group, Polyethylene glycol group represented by − (CH ₂ ) ₃ − (OCH ₂ CH ₂ ) _n1 −OH (n1 is an integer of 1 to 8), − (CH ₂ ) ₃ − (OCH ₂ CH ₂ CH) ₂ ) Polypropylene glycol group, 3-aminopropyl group, N-2- (aminoethyl) -3-aminopropyl group, carboxyoctyl group, 3-glycyl represented by _n2- OH (n2 is an integer of 1 to 5). Examples thereof include a sidoxypropyl group, a 2- (3,4-epoxycyclohexyl) ethyl group, and a 3-isocyanuppropyl group. Among these, a hydroxyalkyl group, a polyethylene glycol group, and a polypropylene glycol group are more preferable from the viewpoint of curability.

In R ¹ , the monovalent organic group having 1 to 20 carbon atoms having a hydroxy group, an amino group, a carboxyl group, an epoxy group or an isocyanate group has two or more, preferably 2 to 4 carbon atoms.
Further, in R ¹ , 10 to 60 mol% is preferably an aryl group or an aralkyl group, and more preferably 15 to 50 mol% is an aryl group or an aralkyl group. Within the above range, the peelability becomes better.

In the above formula (1), a is an integer of 2 or more, preferably an integer of 2 to 30, b is an integer of 1 or more, preferably an integer of 1 to 500, and c is 0 or more. An integer of, preferably an integer of 0 to 10, d is an integer of 0 or more, preferably an integer of 0 to 10, 4 ≦ a + b + c + d ≦ 500, and preferably 10 ≦ a + b + c + d ≦ 400.

Specific examples of the component (C) include, but are not limited to, the following. In addition, Me and Ph in the following formula represent a methyl group and a phenyl group, respectively.

（２≦ｅ１≦４５０、０≦ｆ１≦３００、２≦ｅ１＋ｆ１≦４９８）

（２≦ｅ２≦４５０、０≦ｆ２≦３００、２≦ｅ２＋ｆ２≦４９８、０≦ｇ１≦５、０≦ｇ２≦５）

（２≦ｅ３≦４５０、０≦ｆ３≦３００、０≦ｈ１≦２、２≦ｅ３＋ｆ３＋ｈ１≦４９８）

（２≦ｅ４≦４５０、０≦ｆ４≦３００、０≦ｈ２≦２、２≦ｅ４＋ｆ４＋ｈ２≦４９８）

（２≦ｅ５≦４５０、０≦ｆ５≦３００、０≦ｅ６≦３００、０≦ｆ６≦３００、０≦ｅ７≦１０、２≦（ｅ５＋ｆ５＋ｅ６×ｅ７＋ｆ６×ｅ７＋２×ｅ７）≦４９８）

(2 ≦ e1 ≦ 450, 0 ≦ f1 ≦ 300, 2 ≦ e1 + f1 ≦ 498)

(2 ≦ e2 ≦ 450, 0 ≦ f2 ≦ 300, 2 ≦ e2 + f2 ≦ 498, 0 ≦ g1 ≦ 5, 0 ≦ g2 ≦ 5)

(2 ≦ e3 ≦ 450, 0 ≦ f3 ≦ 300, 0 ≦ h1 ≦ 2, 2 ≦ e3 + f3 + h1 ≦ 498)

(2 ≦ e4 ≦ 450, 0 ≦ f4 ≦ 300, 0 ≦ h2 ≦ 2, 2 ≦ e4 + f4 + h2 ≦ 498)

(2 ≦ e5 ≦ 450, 0 ≦ f5 ≦ 300, 0 ≦ e6 ≦ 300, 0 ≦ f6 ≦ 300, 0 ≦ e7 ≦ 10, 2 ≦ (e5 + f5 + e6 × e7 + f6 × e7 + 2 × e7) ≦ 498)

The blending amount of the component (C) is preferably 0.5 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and further 1 to 8 parts by mass with respect to 100 parts by mass of the component (A). preferable. Within the above range, a cured film having excellent peelability can be obtained, and the transfer of the component (C) to the pressure-sensitive adhesive layer can be suppressed.

[(D) component]
In the composition of the present invention, an acidic catalyst (D) can be used from the viewpoint of promoting the cross-linking reaction between the component (A), the component (B) and the component (C). Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and boric acid, carboxylic acids such as acetic acid, monochloroacetic acid, dichloroacetic acid and butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid and p. -Examples include organic acids selected from organic sulfonic acids such as phenol sulfonic acid, methane sulfonic acid, and ethane sulfonic acid. These acidic catalysts can be used alone or in combination of two or more.

When the component (D) is blended, the blending amount may be a catalyst amount that promotes the reaction. For example, 0.1 to 10 parts by mass is preferable with respect to a total of 100 parts by mass of the components (A) to (C). More preferably, 0.5 to 5 parts by mass. Within the above range, the curability is excellent and the durability of the cured film is also good.

[(E) component]
A solvent can be added to the composition of the present invention as the component (E). By diluting with a solvent, practical advantages such as improvement of coating workability, improvement of coating film condition such as thickness of coating film and surface finish condition can be obtained.

The solvent that can be used may be any compound that can be dissolved, and for example, aromatic hydrocarbon compounds such as toluene and xylene; aliphatic hydrocarbon compounds such as hexane, heptane, and isoparaffin; Alcohol compounds such as methanol, ethanol and 1-butanol; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester compounds such as ethyl acetate and butyl acetate; ether compounds such as diisopropyl ether and 1,4-dioxane. Be done. In the present invention, aromatic hydrocarbon compounds such as toluene and xylene; aliphatic hydrocarbon compounds such as hexane, heptane and isoparaffin; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate, butyl acetate and the like. Ester compound: It is more preferable to use a compound selected from ether compounds such as diisopropyl ether and 1,4-dioxane. These can be blended individually by 1 type or in combination of 2 or more types as appropriate.

When the component (E) is blended, the blending amount is preferably 100 to 20,000 parts by mass, more preferably 200 to 10,000 parts by mass with respect to 100 parts by mass of the component (A). Within the above range, the coating workability is improved and the surface condition of the film can be improved.

[Other ingredients]
Antioxidants, antistatic agents, leveling agents, fillers, antifoaming agents, pigments and the like can be further added to and blended with the composition of the present invention as long as the object of the present invention is not impaired.

[Manufacturing method of resin composition for release paper or release film]
The composition of the present invention may be prepared by mixing the components (A) to (C), and if necessary, the components (D), (E) and any component, but when the component (D) is blended, Storage stability is a method in which the component (A), the component (B), the component (C), the component (E) and the optional component are uniformly mixed in advance, and then the component (D) is added immediately before use. It is preferable in terms of sex. The mixing method and the like are not particularly limited, and a known method can be used.

[Resin composition for release paper or release film]
The viscosity of the release paper or the resin composition for a release film of the present invention at 25 ° C. is preferably 0.1 mPa · s to 10 Pa · s, more preferably 0.2 mPa · s to 5 Pa · s from the viewpoint of coating workability. .. The viscosity is measured by a B-type rotational viscometer.

[Release paper or release film (coated material)]
The present invention provides a release paper or release film having a cured film formed by applying the above-mentioned resin composition for release paper or release film to a base material and then heating the substrate.
The above-mentioned resin composition for release paper or release film is used as it is, or is further diluted with the above-mentioned solvent of the component (E) to a viscosity suitable for coating described later, and then a comma coater, a lip coater, and a roll coater. , Die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, wire bar coater, etc., screen coating, immersion coating, cast coating, etc., paper, film, etc. A cured film can be formed on the substrate by applying 0.01 to 100 g / m ² on one or both sides of the sheet-like substrate and then heating at 50 to 200 ° C. for 1 to 200 seconds. ..
The coating amount is preferably from 0.01 to 100 g / m ^2, more preferably 0.03~50g / m ^2, the temperature at the time of drying is preferably from 50 to 200 ° C., more preferably from 70 to 180 ° C.. The time for drying is preferably 1 to 200 seconds, more preferably 5 to 90 seconds. When the release layers are formed on both sides of the base material, it is preferable to perform the operation of forming the cured film on each side of the base material.

Examples of sheet-like base materials include polyethylene laminated paper, glassin paper, high-quality paper, kraft paper, clay-coated paper, various coated papers such as mirror-coated paper, synthetic papers such as YUPO, polyethylene films, and polypropylenes such as CPP and OPP. Examples thereof include polyester films such as films and polyethylene terephthalate films, polyamide films, polyimide films, polylactic acid films, polyphenol films, and polycarbonate films.
In order to improve the adhesion between these base materials and the release layer, the base material surface may be subjected to corona treatment, etching treatment, or plasma treatment.

The release paper or release film resin composition of the present invention was cured at a lower temperature than the conventional release conditions or release film resin composition (for example, 100 to 200 ° C. for 10 to 200 seconds). In both cases (for example, at 50 to 150 ° C. for 40 to 200 seconds) and when cured in a short time (for example, at 150 to 200 ° C. for 1 to 40 seconds), the peelability and repeatability are good. , A release film having a gloss equal to or higher than that of a conventional release agent composition can be formed.

Hereinafter, the present invention will be specifically described with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

<Ingredients used>
(A) Ingredient (A1)
A 50% by mass butyl acetate solution of the hydroxy group-containing acrylic resin obtained in Synthesis Example 1 below [Synthesis Example 1]
39.6 parts by mass of butyl acetate was charged into a glass reaction device equipped with a stirrer, a thermometer, a reflux cooler, and a dropping device, and after heating to 90 to 100 ° C., 19.5 parts by mass of 2-hydroxyethyl methacrylate (19.5 parts by mass). 0.15 mol), 6.0 parts by mass (0.06 mol) of methyl methacrylate, 33.9 parts by mass (0.10 mol) of stearyl methacrylate, 1.1 parts by mass (0.005 mol) of tert-butyl 2-ethylperoxyhexanoate. And 19.8 parts by mass of butyl acetate was added dropwise over 4 hours under nitrogen aeration. Further, after polymerization at 90 to 100 ° C. for 2 hours, 0.2 parts by mass (0.001 mol) of tert-butyl 2-ethylperoxyhexaneate was added, and polymerization was carried out for 2 hours to obtain 50% by mass of butyl acetate of a hydroxy group-containing acrylic resin. A solution was obtained. The hydroxyl value of the obtained hydroxy group-containing acrylic resin was 141 mgKOH / g. The polystyrene-equivalent weight average molecular weight by GPC was 40,000.

(A2)
A 50% by mass butyl acetate solution of the hydroxy group-containing acrylic resin obtained in Synthesis Example 2 below [Synthesis Example 2]
46.1 parts by mass of butyl acetate was charged into a glass reaction device equipped with a stirrer, a thermometer, a reflux cooler, and a dropping device, and after heating to 90 to 100 ° C., 26.0 parts by mass of 2-hydroxyethyl methacrylate (26.0 parts by mass). 0.20 mol), 14.0 parts by mass (0.14 mol) of methyl methacrylate, 29.2 parts by mass (0.28 mol) of styrene, 1.1 parts by mass (0.005 mol) of tert-butyl 2-ethylperoxyhexanoate and A mixture of 23.1 parts by mass of butyl acetate was added dropwise over 4 hours under nitrogen aeration. Further, after polymerization at 90 to 100 ° C. for 2 hours, 0.2 parts by mass (0.001 mol) of tert-butyl 2-ethylperoxyhexanoate was added, and polymerization was carried out for 2 hours to obtain 50% by mass of butyl acetate of a hydroxy group-containing acrylic resin. A solution was obtained. The hydroxyl value of the obtained hydroxy group-containing acrylic resin was 161 mgKOH / g. The polystyrene-equivalent weight average molecular weight by GPC was 36,000.

(A3)
A 50% by mass butyl acetate solution of the hydroxy group-containing acrylic resin obtained in Synthesis Example 3 below [Synthesis Example 3]
33.4 parts by mass of butyl acetate was charged into a glass reaction device equipped with a stirrer, a thermometer, a reflux cooler, and a dropping device, and after heating to 90 to 100 ° C., 20.8 parts by mass of 2-hydroxyethyl methacrylate (20.8 parts by mass). 0.16 mol), 15.0 parts by mass of methyl methacrylate (0.15 mol), 14.2 parts by mass of n-butyl methacrylate (0.10 mol), 1.1 parts by mass of tert-butyl 2-ethylperoxyhexanoate (0. A mixture of 005 mol) and 16.7 parts by mass of butyl acetate was added dropwise over 4 hours under nitrogen aeration. Further, after polymerization at 90 to 100 ° C. for 2 hours, 0.2 parts by mass (0.001 mol) of tert-butyl 2-ethylperoxyhexaneate was added, and polymerization was carried out for 2 hours to obtain 50% by mass of butyl acetate of a hydroxy group-containing acrylic resin. A solution was obtained. The hydroxyl value of the obtained hydroxy group-containing acrylic resin was 178 mgKOH / g. The polystyrene-equivalent weight average molecular weight by GPC was 44,000.

(A4)
A 50% by mass butyl acetate solution of the hydroxy group-containing acrylic resin obtained in Synthesis Example 4 below [Synthesis Example 4]
36.2 parts by mass of butyl acetate was charged into a glass reaction device equipped with a stirrer, a thermometer, a reflux cooler, and a dropping device, and after heating to 90 to 100 ° C., 13.0 parts by mass of 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate). 0.10 mol), 10.0 parts by mass (0.10 mol) of methyl methacrylate, 31.2 parts by mass (0.30 mol) of styrene, 1.1 parts by mass (0.005 mol) of tert-butyl 2-ethylperoxyhexanoate and A mixture of 18.1 parts by mass of butyl acetate was added dropwise over 4 hours under nitrogen aeration. Further, after polymerization at 90 to 100 ° C. for 2 hours, 0.2 parts by mass (0.001 mol) of tert-butyl 2-ethylperoxyhexanoate was added, and polymerization was carried out for 2 hours to obtain 50% by mass of butyl acetate of a hydroxy group-containing acrylic resin. A solution was obtained. The hydroxyl value of the obtained hydroxy group-containing acrylic resin was 104 mgKOH / g. The polystyrene-equivalent weight average molecular weight by GPC was 43,000.

(A5)
A 50% by mass butyl acetate solution of the hydroxy group-containing acrylic resin obtained in Synthesis Example 5 below [Synthesis Example 5]
45.6 parts by mass of butyl acetate was charged into a glass reaction device equipped with a stirrer, a thermometer, a reflux cooler, and a dropping device, and after heating to 90 to 100 ° C., 19.5 parts by mass of 2-hydroxyethyl methacrylate (19.5 parts by mass). 0.15 mol), 15.0 parts by mass of methyl methacrylate (0.15 mol), 33.9 parts by mass of stearyl methacrylate (0.10 mol), 1.1 parts by mass of tert-butyl 2-ethylperoxyhexanoate (0.005 mol) And 22.8 parts by mass of butyl acetate was added dropwise over 4 hours under nitrogen aeration. Further, after polymerization at 90 to 100 ° C. for 2 hours, 0.2 parts by mass (0.001 mol) of tert-butyl 2-ethylperoxyhexanoate was added, and polymerization was carried out for 2 hours to obtain 50% by mass of butyl acetate of a hydroxy group-containing acrylic resin. A solution was obtained. The hydroxyl value of the obtained hydroxy group-containing acrylic resin was 121 mgKOH / g. The polystyrene-equivalent weight average molecular weight by GPC was 36,000.

(A6)
A 50% by mass butyl acetate solution of the hydroxy group-containing acrylic resin obtained in Synthesis Example 6 below [Synthesis Example 6]
37.3 parts by mass of butyl acetate was charged into a glass reaction device equipped with a stirrer, a thermometer, a reflux cooler, and a dropping device, and after heating to 90 to 100 ° C., 26.0 parts by mass of 2-hydroxyethyl methacrylate (26.0 parts by mass). 0.20 mol), 20.0 parts by mass of methyl methacrylate (0.20 mol), 10.0 parts by mass of n-butyl methacrylate (0.07 mol), 1.1 parts by mass of tert-butyl 2-ethylperoxyhexanoate (0. A mixture of 005 mol) and 18.7 parts by mass of butyl acetate was added dropwise over 4 hours under nitrogen aeration. Further, after polymerization at 90 to 100 ° C. for 2 hours, 0.2 parts by mass (0.001 mol) of tert-butyl 2-ethylperoxyhexaneate was added, and polymerization was carried out for 2 hours to obtain 50% by mass of butyl acetate of a hydroxy group-containing acrylic resin. A solution was obtained. The hydroxyl value of the obtained hydroxy group-containing acrylic resin was 198 mgKOH / g. The polystyrene-equivalent weight average molecular weight by GPC was 41,000.

(A7)
Alkydia J-524-A (manufactured by DIC Corporation: coconut oil-modified alkyd resin)

(B) Ingredient (B1)
Cymel 303LF (manufactured by Ornex Japan Co., Ltd .: full ether type methylated melamine resin)

（式中、Ｍｅはメチル基、Ｐｈはフェニル基である。） (C) Component (C1)
Organopolysiloxane represented by the following general formula (2): The bonding order of each siloxane unit is not limited to the following.

(In the formula, Me is a methyl group and Ph is a phenyl group.)

(D) Component (D1)
p-toluenesulfonic acid

(E) Component (E1)
toluene

[Examples 1 to 3 and Comparative Examples 1 to 4]
Using the components (A) to (E) shown above as raw materials, a coating composition was prepared by the following procedure.
The components (A), (B), and (C) are placed in a flask according to the compounding ratios shown in Tables 1 and 2, and the components (E) are taken so that the components (A) to (C) have a solid content of 40% by mass. , Mixed uniformly. To the obtained solution, the component (D) is added so as to add 2% by mass with respect to a total of 100 parts by mass of the components (A) to (C), and the mixture is stirred and mixed to form a coating composition. Got The viscosities of the obtained compositions at 25 ° C. measured by a B-type rotational viscometer are also shown in Tables 1 and 2. Using this composition, a release paper was prepared by the method described later.

[Preparation of release paper]
The obtained coating composition was applied to a mirror-coated paper having a thickness of 165 μm with a bar coater so as to have a coating amount of 7.0 g / m ^2, and in a hot air dryer at 130 ° C. for 60 seconds. And heated in a hot air dryer at 170 ° C. for 30 seconds to form a release agent layer, a release paper was obtained.

[Evaluation]
Using the release paper obtained above, "peeling strength", "surface condition", "glossiness", and "repeated durability" were evaluated by the following methods.

[Peeling strength]
A one-component polyurethane solution [Chrisbon 5516S (manufactured by Dainippon Ink and Chemicals Co., Ltd.)] was applied onto the release agent layer of the release paper obtained above so that the thickness of the coating film was 30 μm, and 130 Heat-treated at ° C for 2 minutes. Next, Nittou 31B tape was attached to this treated surface, pressure-bonded once with a 2 kg roller, aged at 25 ° C for 20 hours, then the sample was cut to a width of 3 cm and used at an angle of 180 ° using a tensile tester. The bonding tape was pulled at a peeling speed of 0.3 m / min, and the force (gf / 30 mm) required for peeling was measured. The peeling force when heated at 130 ° C. for 60 seconds is defined as RA, and the peeling force when heated at 170 ° C. for 30 seconds is defined as RB. The smaller the value of the peeling force, the better the peeling property.

[Surface condition]
The presence or absence of repelling and unevenness of the coating film on the release agent layer of the release paper obtained above were visually evaluated. In both the release agent layer cured at 130 ° C. and the release agent layer cured at 170 ° C., the presence of repellent and unevenness of the coating film cannot be confirmed as "○", and the presence of repellent and unevenness of the coating film is confirmed. What can be done is marked with "x".

[Glossiness]
Using a gloss meter (manufactured by Nippon Denshoku Co., Ltd., gloss meter VG7000), the glossiness of the release paper obtained above was measured at an angle of 60 ° with respect to the release agent layer cured at 170 ° C. The higher the value, the better the gloss.

[Repeat durability]
A one-component polyurethane solution [Chrisbon 5516S (manufactured by DIC Corporation)] was applied onto the release agent layer of the release paper obtained above so that the thickness of the coating film was 30 μm, and the temperature was 130 ° C. for 2 minutes. Heat treated. Next, heat treatment was performed at 180 ° C. for 2 minutes, and Nittou 31B tape was attached to the treated surface and pressure-bonded once with a 2 kg roller, and then peeled off. This operation was repeated until the release agent layer was removed and peeling became impossible, and the number of times of repeated use was determined. The repeatability A indicates the number of times of use when heated at 130 ° C. for 60 seconds, and the repeatability B indicates the number of times of use when heated at 170 ° C. for 30 seconds. The more times it is used, the better the repeatability.

These results are shown in Tables 1 and 2. As for the numerical values in the table, the amount of the component (A) including the solvent and the solution is described, and the pure amount of the component (A) is described in ().

Claims (8)

(A) A hydroxy group-containing acrylic resin having a hydroxyl value of 140 to 180 mgKOH / g,
(B) Full ether type methylated melamine resin, methylol type methylated melamine resin, resin selected from multimer thereof, and one or more resins selected from (C) (A) component and (B) component. A resin composition for a release paper or a release film containing an organopolysiloxane having two or more functional groups that can be chemically bonded in one molecule. The resin composition for a release paper or a release film according to claim 1, wherein the component (A) has a weight average molecular weight of 5,000 to 400,000. The resin composition for a release paper or a release film according to claim 1 or 2, wherein the amount of the component (B) blended is 10 to 120 parts by mass with respect to 100 parts by mass of the component (A). The resin composition for a release paper or a release film according to any one of claims 1 to 3, wherein the component (B) is a full ether type methylated melamine resin and a resin selected from the multimer thereof. The resin composition for a release paper or a release film according to any one of claims 1 to 4, wherein the blending amount of the component (C) is 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (A). .. The release paper or release film according to any one of claims 1 to 5, wherein the component (C) contains an organopolysiloxane in which 10 to 60 mol% of the organic group bonded to the silicon atom in one molecule is a phenyl group. Resin composition for use. The resin composition for a release paper or a release film according to any one of claims 1 to 6, further comprising (D) an acidic catalyst. A release paper or release film having a cured film formed by applying the release paper or the resin composition for a release film according to any one of claims 1 to 7 to a base material and then heating the substrate.