TW202112952A - Resin composition for release paper or release film, release paper, and release film - Google Patents

Abstract

The present invention is a resin composition for release paper or a release film, and provides a resin composition for release paper or a release film, the resin composition being capable of obtaininga cured coating film having good releasability and good repeated durability even when cured at a low temperature and cured in a short time. The resin composition for release paper or release film comprises: (A) a hydroxyl group-containing acrylic resin having a hydroxyl group value of 140-180 mgKOH/g; (B) a resin selected from the group consisting of a perether-type methylated melamine resin, a hydroxymethyl-type methylated melamine resin, and polymers thereof; and (C) an organopolysiloxane having, per molecule, two or more functional groups capable of chemically binding to one or more resinsselected from the group consisting of component (A) and component (B).

Description

Resin composition for release paper or release film, release paper and release film

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 formed by curing the composition on a substrate.

In the past, by coating a release agent on the surface of a sheet-like substrate such as paper or plastic to form a cured film, adhesiveness or peeling properties to adhesive substances are imparted.

The use of release paper and release film is diverse. It is used for adhesive materials such as labels, stickers, and tapes, or used in the forming steps of non-adhesive materials such as ceramic layers or urethane resins. Circumstances require different performance depending on the use.

As an example of the forming step used for non-adhesive materials, engineering paper for synthetic leather manufacturing can be cited. The manufacturing process of synthetic leather is to harden the release agent on the substrate to form engineering paper, and coat the engineering paper with urethane resin, vinyl chloride resin, polyamide resin, polyamino acid resin, etc. dry. An adhesive layer is formed on the dried resin, the base cloth is attached, and the resin is peeled off from the engineering paper, thereby manufacturing synthetic leather.

Synthetic leather has matte (matte) type and enamel (strong luster) type. In the manufacture of patent leather type synthetic leather, the surface state of the release agent film will be reflected in the synthetic leather, so the hardened film system requires high The gloss. In addition, in order to improve the productivity of synthetic leather, engineering paper is generally used multiple times. Therefore, there is less change in releasability (releasing properties) when repeated use is expected.

Three types of resin compositions used to impart peelability to the surface of engineering paper for synthetic leather are known as representative ones of polypropylene, amino alkyd resin/amino acrylic resin, and silicone. Polypropylene, although it has excellent peelability and durability when used repeatedly, it has its limits when used at higher temperatures. In this case, it is easy to damage the peeling surface, and it is not suitable for patent leather type synthetic leather. . The amino alkyd resin/amino acrylic resin system has excellent gloss, but lacks releasability. The silicone type has excellent peelability but poor gloss, so it is not suitable for patent leather type synthetic leather.

As a solution to the above-mentioned problems, Patent Document 1 (Japanese Patent Application Laid-Open No. 56-14550) discloses a resin composition for engineering release paper, which is composed of an organic group bonded by silicon atoms in one molecule. 15-50 mol% of it is phenyl, and at least one of the remaining organic groups is a polysiloxane-modified acrylic resin modified by organopolysiloxane with a hydroxyl-substituted organic group, which is composed of polyisocyanate compounds. In addition, it states that "by using an organic group substituted with a hydroxyl group, an engineered release paper with excellent heat resistance, good gloss, and good peelability can be obtained."

In addition, Patent Document 2 (Japanese Patent Application Laid-Open No. 56-11980) discloses a resin composition for engineering release paper, which is composed of 15-50 mol% of organic groups bonded by silicon atoms in one molecule It is a phenyl group, and at least one of the remaining organic groups is a polysiloxane-modified alkyd resin modified by an organic polysiloxane substituted with a hydroxyl group and a polyisocyanate compound. In addition, it states that "even in engineered release paper using alkyd resin, engineered release paper with excellent heat resistance, good gloss, and good peelability can be obtained."

Patent Document 3 (Japanese Patent Laid-Open No. 56-14566) discloses a resin composition for engineered release paper, which is composed of: 15-50 mol% of organic groups bonded by silicon atoms in one molecule are benzene At least one of the remaining organic groups is composed of polysiloxane-modified acrylic resin, alkanol-modified amine-based resin and acid catalyst modified by organopolysiloxane modified by hydroxyl-substituted organic group. . In addition, it is stated that "Even in engineering release paper containing acrylic resin and amino resin together with acid catalyst, engineering release paper with excellent heat resistance, good gloss, and good peelability can be obtained."

Patent Document 4 (Japanese Patent Application Laid-Open No. 3-263475) discloses a resin composition for engineered release paper, which is composed of a silicon atom bonded to a silicon atom via a methyl group, a phenyl group, and an organic group. One is an organic group substituted by a hydroxy group, and 15-50 mol% of all the substituents bonded by the silicon atom are modified by polysiloxane modified alkyd resins and alkyd resins. It is composed of high-quality amine-based resin and acid catalyst. In addition, it is stated that "with an acid catalyst, even in engineered release paper containing alkyd resin and amino resin together, engineered release paper with excellent heat resistance, good gloss, and good peelability can be obtained."

Patent Document 5 (Japanese Patent Laid-Open No. 2-28242) discloses a resin composition for engineered release paper, which is composed of: alkyd resin or acrylic resin, 15 of organic groups bonded to silicon atoms in one molecule ~50mol% is a phenyl group, and at least one of the remaining organic groups is an organic polysiloxane substituted by a hydroxyl group, an alkanol-modified amine-based resin, and an acid catalyst. In addition, it states that "the engineered release paper obtained from the resin composition for engineered release paper is superior in peelability, heat resistance, and gloss compared to conventional engineered release paper."

Patent Document 6 (Patent No. 5282083) discloses a release agent composition consisting of a hydroxyl value of 10 to 150 mgKOH/g, a glass transition temperature of 20 to 100°C, and a weight average molecular weight of 20,000 to 100,000. An acrylic resin, an amino resin, and a polysiloxane resin having a functional group that can chemically bond with at least one of the hydroxyl-containing acrylic resin and the amino resin. In addition, it states that "excellent releasability, gloss, surface condition, and repeat durability at high temperatures".

As mentioned above, the amino alkyd resin/amino acrylic resin release agent has improved gloss, heat resistance and releasability, and a certain effect is obtained. However, the amino alkyd resin/amino acrylic resin release agent has the disadvantage of slow curing, and improvement of the curability is necessary.

As a solution to the above-mentioned problems, Patent Document 7 (Japanese Patent Laid-Open No. 2000-095929) discloses a release agent composition for engineered release paper, which is composed of alkyd resin, amino resin, and the aforementioned alkyd resin. The resin and the aforementioned amino resin are composed of a polysiloxane resin with reactive functional groups, and the aforementioned amino resin contains a methylated melamine resin containing more than one methylol group per triazine core as the main component, It states that "excellent releasability, gloss, surface condition, and reusability, and can be cured and dried at low temperatures."

In recent years, in order to improve the production efficiency of engineered paper, there is a strong demand for a release agent composition that can be cured at low temperatures, or a release agent composition that can be cured in a short time. If it can be hardened at a low temperature, the heat necessary 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 in a short time can be found, it will not be affected by changes in the curing temperature and curing time caused by the increase in production efficiency, and stable quality can be provided.

Through research, it is found that amino alkyd resin/amino acrylic resin release agent has a small blending amount of polysiloxane resin that imparts mold release properties, so the peeling characteristics will depend on whether the polysiloxane can be immobilized on the surface layer. Make a difference. This will cause the peeling characteristics to vary depending on the low-temperature hardening condition and the short-time hardening condition, resulting in unstable quality. However, the conventional release agent composition has not yet found a composition that can achieve both curability at low temperature and curability in a short time. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 56-14550 [Patent Document 2] Japanese Patent Application Laid-Open No. 56-11980 [Patent Document 3] Japanese Patent Application Laid-Open No. 56-14566 [Patent Document 4] Japanese Patent Application Laid-Open No. 3-263475 [Patent Document 5] Japanese Patent Application Laid-Open No. 2-28242 [Patent Document 6] Japanese Patent No. 5282083 [Patent Document 7] JP 2000-095929 A

[The problem to be solved by the invention]

The present invention is made in view of the above-mentioned facts, and its object is to provide a release paper or a release film that can form a release film that has good releasability and repetitive durability regardless of whether it is cured at a low temperature or cured in a short time. A resin composition is used, and a release paper or a release film having a cured film formed by curing the composition on a substrate. [Means to solve the problem]

In order to achieve the above-mentioned object, the inventors conducted in-depth studies and found that (A) a hydroxyl group-containing acrylic resin with a hydroxyl value of 140 to 180 mgKOH/g, and (B) a full ether type methylated melamine resin , Methylol type methylated melamine resins, and resins selected from these polymers, and (C) 1 molecule with 2 or more components that can be selected from components (A) and (B) A resin composition of organopolysiloxane with functional groups that are chemically bonded to one or more resins, regardless of whether it is cured at a low temperature or in a short period of time, a cured film with good peelability and repeat durability can be obtained. , Suitable as a resin composition for release paper or release film, and completed 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. A resin composition for release paper or release film, which contains (A) Hydroxyl-containing acrylic resin with a hydroxyl value of 140~180mgKOH/g, (B) Resins selected from full ether type methylated melamine resins, methylol type methylated melamine resins, and these polymers, and (C) Organopolysiloxane having two or more functional groups in one molecule that can be chemically bonded to one or more resins selected from (A) component and (B) component. 2. The resin composition for release paper or release film as in 1, wherein the weight average molecular weight of component (A) is 5,000 to 400,000. 3. The resin composition for release paper or release film according to 1 or 2, wherein the blending amount of component (B) is 10 to 120 parts by mass relative to 100 parts by mass of component (A). 4. The resin composition for release paper or release film as described in any one of 1 to 3, wherein component (B) is a resin selected from perether methylated melamine resins and their polymers. 5. The resin composition for release paper or release film according to any one of 1 to 4, wherein the blending amount of component (C) is 0.5 to 20 parts by mass relative to 100 parts by mass of component (A). 6. The resin composition for release paper or release film according to any one of 1 to 5, wherein the component (C) contains an organic polymer in which 10 to 60 mol% of the organic groups bonded by silicon atoms in 1 molecule are phenyl groups Siloxane. 7. The resin composition for release paper or release film according to any one of 1 to 6, which further contains (D) an acid catalyst. 8. A release paper or release film having a cured film formed by applying the release paper or release film resin composition of any one of 1 to 7 to a base material and then heating. [Effects of Invention]

The resin composition for release paper or release film of the present invention can form a release film with good release properties and repeat durability regardless of whether it is cured at a low temperature or in a short time. The gloss is the same as the conventional release agent composition The same thing or more.

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

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

The hydroxyl value of the hydroxyl-containing acrylic resin is 140~180mgKOH/g, particularly preferably 141~178mgKOH/g. When the hydroxyl value is less than 140 mgKOH/g, the peelability and repeat durability will deteriorate in the case of short-time curing. On the other hand, when the hydroxyl value exceeds 180 mgKOH/g, the surface condition of the cured film deteriorates and the gloss decreases. In addition, in the present invention, the hydroxyl value of the hydroxyl-containing acrylic resin is a value measured according to the neutralization titration method (JIS K0070).

In the present invention, it was found that by using a hydroxyl group-containing acrylic resin with a hydroxyl value of 140 to 180 mgKOH/g as component (A), whether it is cured at a low temperature or cured in a short time, it has releasability and repeated durability. All are good. Although not bound by theory, it is thought that the organopolysiloxane of the component (C) is fixed on the surface of the coating film and the releasability is improved. Therefore, it is estimated that the shorter the curing time, the less time it takes for the organopolysiloxane to move to the surface layer, and it is immobilized in the film before moving to the surface layer, and the releasability deteriorates. The more the amount of the hydroxyl group of the component (A) increases, the worse the compatibility of the organopolysiloxane of the component (A) and the component (C) becomes, and the movement to the surface becomes easier. Therefore, it can be considered that even in a short-time curing condition, a film in which the organopolysiloxane is fixed to the surface of the film can be obtained, showing excellent releasability and repeat durability.

(A) The hydroxyl-containing acrylic resin of the component is not particularly limited as long as it is a hydroxyl-containing acrylic resin having the above-mentioned specific hydroxyl value. It is preferable to use one or more hydroxyl groups per molecule and one or more per molecule The radical polymerizable monomer (Aa) of the radical polymerizable group, and the radical polymerizable monomer (Ab) that does not have a hydroxyl group in one molecule and has one or more radical polymerizable groups in one molecule Copolymer.

Here, the component (Aa) is not particularly limited as long as it is a radically polymerizable monomer having one or more hydroxyl groups in one molecule and one or more radically polymerizable groups in one molecule, and one type may be used alone. It can also be used by mixing two or more kinds. Examples of the radically polymerizable group include an acryl group, a methacryl group, a styryl group, a cinnamate group, a vinyl group, an allyl group, and the like.

(Aa) Component, specifically, exemplified 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and (meth)acrylic acid 2 -Hydroxy-3-phenoxypropyl ester, 1,4-cyclohexanedimethanol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, Placcel F modified with caprolactone Series ((stock) Daicel system) and so on.

In addition, the (Ab) component is not particularly limited as long as it is a radically polymerizable monomer that does not have a hydroxyl group in one molecule and has one or more radically polymerizable groups in one molecule, and one type can be singly or appropriately combined. More than one kind of use. The radical polymerizable group includes an acryl group, a methacryl group, a styryl group, a cinnamate group, a vinyl group, an allyl group, and the like.

(Ab) component, specifically, styrene compounds such as styrene, o-methylstyrene, p-methylstyrene, α-methylstyrene, etc.; methyl (meth)acrylate, (formaldehyde) Base) ethyl acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid Cyclohexyl ester, benzyl (meth)acrylate, isobornyl (meth)acrylate, trifluoropropyl (meth)acrylate, perfluorobutyl ethyl (meth)acrylate, perfluoro(meth)acrylate (Meth) acrylic acid ester compounds such as octyl ethyl ester; glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-ring (meth)acrylate Epoxy group-containing radical polymerizable monomers such as oxycyclohexyl methyl ester; γ-methacryloxy propyl trimethoxysilane, γ-methacryloxy propyl methyl dimethoxy Yl silane, γ-methacryloxy propyl dimethyl methoxy silane, γ-methacryloxy propyl triethoxy silane, γ-methacryloxy propyl methyl bis Ethoxysilane, γ-methacryloxypropyl tributoxysilane, γ-methacryloxypropyl triisopropenoxysilane, γ-acryloxypropyl trimethoxysilane , Acrylic oxymethyl trimethoxysilane, γ-acryloxy propyl triethoxy silane, γ-acryloxy propyl methyl diethoxy silane, styryl trimethoxy silane, Radical polymerizable silane compounds such as styryltriethoxysilane and α-methylstyryltrimethoxysilane; radical polymerizable monomers containing polyoxyalkylene groups; glycerol (meth)acrylate, etc. .

The polymerization ratio of (A-a) component and (A-b) component is adjusted according to the hydroxyl value of the hydroxyl-containing acrylic resin. The hydroxyl value of the hydroxyl-containing acrylic resin obtained by polymerization must be 140~180mgKOH/g. Specifically, the polymerization ratio of the (Aa) component and the (Ab) component, and the (Aa) component and (Ab) component in moles The ratio ((Aa): (Ab)) is preferably 1:0.1 to 1:10, more preferably 1:0.3 to 1:5. (A-a) Too little or too much component may make it difficult to synthesize.

The copolymerization of (Aa) component and (Ab) component is the peroxide of benzoyl peroxide, dicumyl peroxide, lauryl peroxide, tert-butyl 2-ethylperoxyhexanoate, etc. Class; 2,2'-azobis (2-methylbutyronitrile) and other azo compounds such as the presence of ordinary radical polymerization initiators, can also be applied to solution polymerization, emulsion polymerization, Any method of suspension polymerization method and block polymerization method. Furthermore, 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 relative to 100 parts by mass of the total of the components (A-a) and (A-b).

In the present invention, among these polymerization methods, since the weight average molecular weight of the (A) hydroxyl-containing acrylic resin can be easily adjusted to an optimum range, the solution polymerization method is preferred. The solvent used at this time includes aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl acetate, n-butyl acetate, Esters such as isobutyl acetate; monohydric alcohols such as ethanol, isopropanol, n-butanol, isobutanol, etc., can be used alone or in a suitable combination of two or more. The usage amount of the solvent is preferably 10 to 900 parts by mass, more preferably 20 to 800 parts by mass relative to 100 parts by mass of the total of the components (A-a) and (A-b).

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

(A) The weight average molecular weight of the component is preferably 5,000 to 400,000, more preferably 10,000 to 300,000, and still more preferably 20,000 to 200,000. If the weight average molecular weight is within the above range, the coatability and handleability will be good. In addition, the weight average molecular weight is a value in terms of polystyrene by gel permeation chromatography (hereinafter abbreviated as "GPC") using tetrahydrofuran as a developing solvent.

[(B) Ingredient] The component (B) is a resin selected from perether type methylated melamine resin, methylol type methylated melamine resin, and these polymers, and can be used alone or in a suitable combination of two or more types. The component (B) in the present invention includes a structure in which a functional group is bonded to the periphery of a triazine ring through three nitrogen atoms. The (B) component plays a role as a crosslinking agent that reacts with the (A) component and/or (C) component.

Melamine resin is a synthetic resin obtained by condensing melamine and formaldehyde, which is a condensation product of monomers or dimers 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 full ether type, a methylol type, an imino type, and a methylol/imino type according to the functional group. .

In addition, melamine resins are distinguished by the types of alkoxymethyl groups. The melamine resins in which all alkoxymethyl groups are methoxymethyl are methylated melamine resins, and the alkoxymethyl groups are all n-butoxy groups. Methyl melamine resin is n-butylated melamine resin, alkoxy methyl is mixed with methoxymethyl and n-butoxymethyl melamine resin is methylated/n-butylated melamine resin .

The component (B) in the present invention can provide a cured film with excellent peelability, repeat durability, and curability, so full ether type methylated melamine resin, methylol type methylated melamine resin, and the like can be used. The polymer is preferably a per-ether methylated melamine resin and its polymer.

The component (B) in the present invention can also be commercially available, and can also be synthesized according to a conventionally known method. Commercial products include, for example, Cymel 300, Cymel 303LF, Cymel 350, Cymel 370N (above, manufactured by Allnex Japan Co., Ltd.), Nikalac MW-30M, and Nikalac MW-30 (above, manufactured by Carbide Industry Co., Ltd.).

The blending amount of (B) component is preferably 10 to 120 parts by mass, more preferably 15 to 110 parts by mass, and still more preferably 20 to 100 parts by mass relative to 100 parts by mass of (A) component. If it is in the above range, peelability and curability are good, and a cured film having excellent repeatability durability can be obtained.

[(C) Ingredient] The (C) component of the present invention has two or more, preferably 2 to 4, functional groups in one molecule that can chemically bond with one or more resins selected from the (A) component and (B) component The organopolysiloxane can be used alone or in a suitable combination of two or more. The component (C) has two or more functional groups in one molecule that can be chemically bonded to one or more resins selected from component (A) and component (B), and it is used to form a release layer (A) Component and (B) component, and (C) component of the peeling component, are chemically bonded in the peeling layer, so the movement of (C) component to the adhesive layer can be suppressed, and heavy peeling during tape storage can be prevented Or the adhesive force during use decreases.

Such a functional group includes a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, etc., preferably a hydroxyl group and an epoxy group; more preferably a hydroxyl group.

(式中，R¹ 係獨立地為碳數1~20之非取代或取代之一價烴基，或具有羥基、胺基、羧基、環氧基或異氰酸酯基的碳數1~20之一價有機基，R¹ 之至少2個為具有羥基、胺基、羧基、環氧基或異氰酸酯基的碳數1~20之一價有機基。a為2以上之整數、b為1以上之整數、c為0以上之整數、d為0以上之整數，4≦a+b+c+d≦500)。The organopolysiloxane of the component (C) can be linear or branched within the range in which the effects of the present invention can be exerted. It is preferably represented by the following average composition formula (1) Organopolysiloxane.

(In the formula, R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group with 1 to 20 carbons, or a monovalent organic with 1 to 20 carbons having a hydroxyl group, an amino group, a carboxyl group, an epoxy group or an isocyanate group Group, ^{at least two of R 1 are} monovalent organic groups with 1 to 20 carbons having a hydroxyl 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 greater than 0, d is an integer greater than 0, 4≦a+b+c+d≦500).

In the above formula (1), R ¹ is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 20 carbons. Specifically, examples include methyl, ethyl, propyl, butyl, etc., with carbon 1 to 20, Preferably it is an alkyl group of 1 to 6; the carbon number of cyclohexyl and the like is 3 to 20, preferably a cycloalkyl group of 5 to 8, and the carbon number of phenyl and tolyl groups is 6 to 20, preferably 6 to 10 The aryl group; benzyl and other aralkyl groups with 7 to 20 carbon atoms, preferably 7 to 10, or part or all of the hydrogen atoms bonded to the carbon atoms of these groups are fluorine, chlorine, bromine , Iodine and other halogen atoms are substituted by hydroxypropyl, 1-chloropropyl, 3,3,3-trifluoropropyl, etc. with carbon numbers of 1 to 20, preferably 1 to 10, substituted by halogen The alkyl group and so on. Among them, from the viewpoint of releasability, methyl group and phenyl group are more preferable.

In addition, the monovalent organic group of 1 to 20 carbons having a hydroxyl group, an amino group, a carboxyl group, an epoxy group, or an isocyanate group of ^{R 1 preferably has a hydroxyl group, an amino group, a carboxyl group, an epoxy group or an isocyanate group,} Those having a structure having a carbon number of 1 to 20, preferably 1 to 10, which may include heteroatoms such as oxygen atoms, nitrogen atoms, and fluorine atoms, are bonded to the divalent hydrocarbon group. Here, a divalent hydrocarbon group that may contain a hetero atom, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, etc.; Arylene groups such as phenylene groups, or a combination of two or more of these groups (alkylene groups, aryl groups, etc.), and further, groups having oxygen atoms in these groups. Specific examples of such monovalent organic groups include 2-hydroxyethyl, 3-hydroxypropyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, and 2-hydroxybutyl , 2-(hydroxymethyl)propyl, 2-hydroxypentyl, 3-hydroxy-2,2-dimethylpropyl, 3-hydroxypentyl, 5-hydroxypentyl, 6-hydroxyhexyl, 2- Hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 2-hydroxyethoxy, 3-[(2-hydroxyethyl)oxy]propyl, 3-[(3-hydroxypropyl)oxy ] Propyl and other hydroxyalkyl groups; -(CH ₂ ) ₃ -(OCH ₂ CH ₂ ) _n1 -OH (n1 is an integer from 1 to 8) represented by polyethylene glycol groups; -(CH ₂ ) ₃ -( OCH ₂ CH ₂ CH ₂ ) _n2- OH (n2 is an integer from 1 to 5) represented by polypropylene glycol group; 3-aminopropyl, N-2-(aminoethyl)-3-aminopropyl, Carboxyoctyl, 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-isocyanate propyl, etc. Among these, in terms of curability, hydroxyalkyl, polyethylene glycol, and polypropylene glycol are particularly preferred.

Furthermore, in the above-mentioned R ¹ , a monovalent organic group having 1 to 20 carbon atoms having a hydroxyl group, an amino group, a carboxyl group, an epoxy group, or an isocyanate group has two or more, preferably 2 to 4. In addition, in the above-mentioned R ¹ , preferably 10-60 mol% are aryl groups and aralkyl groups; more preferably 15-50 mol% are aryl groups and aralkyl groups. If it is in the said range, peelability will become more favorable.

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

(C) Specific examples of the component include the following, but are not limited to these. 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 (C) component is preferably 0.5 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 1 to 8 parts by mass relative to 100 parts by mass of the (A) component. If it is in the above-mentioned range, a cured film with excellent releasability can be obtained, and the movement of the component (C) to the adhesive layer can be suppressed.

[(D) Ingredient] From the viewpoint of promoting the cross-linking reaction of (A) component, (B) component and (C) component, (D) acidic catalyst can be used in the composition of the present invention. Examples of acid catalysts 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, and xylenesulfonic acid , P-phenolsulfonic acid, methanesulfonic acid, ethanesulfonic acid and other organic sulfonic acids selected from organic acids. These acidic catalysts can be used alone or in appropriate combination of two or more.

The blending amount when blending component (D) is the amount of the catalyst that promotes the reaction, for example, it is preferably 0.1-10 parts by mass relative to 100 parts by mass of the total of components (A) to (C) , More preferably, it is 0.5 to 5 parts by mass. If it is in the above range, the curability is excellent, and the durability of the cured film is also good.

[(E) Ingredient] In the composition of the present invention, a solvent may be blended as the (E) component. By diluting with a solvent, practical advantages such as improvement of coating workability, improvement of the coating film state such as the thickness of the coating film or the surface finish state, etc. can be obtained.

The solvent that can be used is anything as long as it is a compound that can be dissolved. For example, aromatic hydrocarbon compounds such as toluene and xylene; aliphatic hydrocarbon compounds such as hexane, heptane, and isoalkane; 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; diisopropyl ether , 1,4-dioxane and other ether compounds. In the present invention, it is more preferable to use aromatic hydrocarbon compounds such as toluene and xylene; aliphatic hydrocarbon compounds such as hexane, heptane, and isoalkane; acetone, methyl ethyl ketone, and methyl isobutyl ketone. Selected from among ketone compounds such as ethyl acetate and butyl acetate, and ether compounds such as diisopropyl ether and 1,4-dioxane. These can be blended alone or in a suitable combination of two or more.

The blending amount when blending the (E) component is preferably 100 to 20,000 parts by mass, more preferably 200 to 10,000 parts by mass relative to 100 parts by mass of the (A) component. If it is in the above range, the coating workability becomes good, and the surface condition of the film can be improved.

[Other ingredients] In the composition of the present invention, in a range that does not impair the purpose of the present invention, antioxidants, antistatic agents, leveling agents, fillers, defoamers, pigments, etc. can be further added and blended.

[Method for manufacturing resin composition for release paper or release film] The composition of the present invention can be prepared by mixing components (A) to (C), (D) components, (E) components, and optional components as needed. When the (D) component is blended, it will be stored and stable. In terms of properties, it is preferable to uniformly mix (A) component, (B) component, (C) component, (E) component as needed, and optional components in advance, and then add (D) component just before use. The mixing method is not particularly limited, and a known method can be used.

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

[Release paper or release film (coating)] The present invention provides a release paper or release film having a cured film formed by applying the above-mentioned release paper or release film resin composition to a substrate and heating it. The above-mentioned resin composition for release paper or release film can be directly or further diluted with the solvent of the above-mentioned (E) component to a composition with a viscosity suitable for the coating described below, and then used with a chipped wheel coater and lip coating Coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, wire bar coater Coating methods such as coating, screen coating, dipping coating, casting coating, etc. by cloth ware, etc. Coating 0.01~100g/m on one or both sides of sheet-like substrates such as paper, film, etc. ^{After 2} , heat at 50~200°C for 1~200 seconds to form a hardened film on the substrate. The coating amount is preferably 0.01-100 g/m ² , more preferably 0.03-50 g/m ² , and the drying temperature is preferably 50-200°C, more preferably 70-180°C. The drying time is preferably 1 to 200 seconds, more preferably 5 to 90 seconds. Furthermore, when making the release layer on both sides of the substrate, it is preferable to perform the formation operation of the hardened film on one side of the substrate each time.

Examples of sheet-like substrates include polyethylene laminated paper, cellophane, high-quality paper, kraft paper, clay-coated paper, mirror coated paper and other coated paper, synthetic paper such as YUPO, polyethylene film, CPP or OPP, etc. Polypropylene film, polyethylene terephthalate film and other polyester film, polyamide film, polyimide film, polylactic acid film, polyphenol film, polycarbonate film, etc. In order to improve the adhesion between the substrate and the release layer, it can also be used for corona treatment, etching treatment, or plasma treatment on the substrate surface.

The resin composition for release paper or release film of the present invention is compared with the curing conditions of the conventional resin composition for release paper or release film (for example, 100~200℃, 10~200 seconds), regardless of low temperature Either the case of curing (for example, at 50~150°C, 40~200 seconds) or the case of curing in a short time (for example, at 150~200°C, for 1~40 seconds), it can be peeled and has good repeat durability. And the gloss is equal to or higher than the peeling film of the conventional peeling agent composition. [Example]

The synthesis examples, examples, and comparative examples are shown below to specifically illustrate the present invention, but the present invention is not limited by the following examples.

＜Raw materials used＞ (A) Ingredient (A1) The 50% by mass butyl acetate solution of hydroxyl-containing acrylic resin obtained in the following synthesis example 1 [Synthesis Example 1] Into a glass reaction device equipped with a stirrer, a thermometer, a reflux cooler, and a dropping device, 39.6 parts by mass of butyl acetate were fed, and after heating to 90~100°C, the 2-hydroxy methacrylic acid was dropped over 4 hours under nitrogen aeration. 19.5 parts by mass (0.15 mol) of ethyl ester, 6.0 parts by mass (0.06 mol) of methyl methacrylate, 33.9 parts by mass (0.10 mol) of stearyl methacrylate, tert-butyl 2-ethylperoxyhexanoate 1.1 A mixture of parts by mass (0.005 mol) and 19.8 parts by mass of butyl acetate. After further polymerization at 90~100°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 butyl acetate of hydroxyl-containing acrylic resin Solution. The hydroxyl value of the obtained hydroxyl-containing acrylic resin was 141 mgKOH/g. The weight average molecular weight in terms of polystyrene obtained by GPC is 40,000.

(A2) The 50% by mass butyl acetate solution of hydroxyl-containing acrylic resin obtained in Synthesis Example 2 below [Synthesis Example 2] 46.1 parts by mass of butyl acetate was fed into a glass reaction device equipped with a stirrer, thermometer, reflux cooler, and dropping device. After heating to 90~100°C, the 2-hydroxy methacrylic acid was dropped over 4 hours under nitrogen aeration. 26.0 parts by mass (0.20 mol) of ethyl methacrylate, 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 of tert-butyl 2-ethylperoxyhexanoate (0.005) mol) and 23.1 parts by mass of butyl acetate. After further polymerization at 90~100°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 butyl acetate of hydroxyl-containing acrylic resin Solution. The hydroxyl value of the obtained hydroxyl-containing acrylic resin was 161 mgKOH/g. The weight average molecular weight in terms of polystyrene obtained by GPC is 36,000.

(A3) A 50% by mass butyl acetate solution of hydroxyl-containing acrylic resin obtained in Synthesis Example 3 below [Synthesis Example 3] In a glass reaction device equipped with a stirrer, a thermometer, a reflux cooler, and a dropping device, 33.4 parts by mass of butyl acetate was fed, and after heating to 90~100°C, the 2-hydroxy methacrylic acid was dropped over 4 hours under nitrogen aeration. 20.8 parts by mass (0.16 mol) of ethyl ester, 15.0 parts by mass (0.15 mol) of methyl methacrylate, 14.2 parts by mass (0.10 mol) of n-butyl methacrylate, tert-butyl 2-ethylperoxyhexanoate A mixture of 1.1 parts by mass (0.005 mol) and 16.7 parts by mass of butyl acetate. After further polymerization at 90~100°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 butyl acetate of hydroxyl-containing acrylic resin Solution. The hydroxyl value of the obtained hydroxyl-containing acrylic resin was 178 mgKOH/g. The weight average molecular weight in terms of polystyrene obtained by GPC is 44,000.

(A4) A 50% by mass butyl acetate solution of hydroxyl-containing acrylic resin obtained in Synthesis Example 4 below [Synthesis Example 4] In a glass reactor equipped with a stirrer, a thermometer, a reflux cooler, and a dropping device, 36.2 parts by mass of butyl acetate was fed, and after heating to 90~100°C, the 2-hydroxy methacrylic acid was dropped over 4 hours under nitrogen aeration. 13.0 parts by mass (0.10 mol) of ethyl ester, 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 of tert-butyl 2-ethylperoxyhexanoate (0.005) mol) and 18.1 parts by mass of butyl acetate. After further polymerization at 90~100°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 butyl acetate of hydroxyl-containing acrylic resin Solution. The hydroxyl value of the obtained hydroxyl-containing acrylic resin was 104 mgKOH/g. The weight average molecular weight in terms of polystyrene obtained by GPC is 43,000.

(A5) A 50% by mass butyl acetate solution of hydroxyl-containing acrylic resin obtained in Synthesis Example 5 below [Synthesis Example 5] In a glass reaction device equipped with a stirrer, a thermometer, a reflux cooler, and a dropping device, 45.6 parts by mass of butyl acetate were fed, and after heating to 90~100°C, the 2-hydroxy methacrylic acid was dropped over 4 hours under nitrogen aeration. 19.5 parts by mass (0.15 mol) of ethyl ester, 15.0 parts by mass (0.15 mol) of methyl methacrylate, 33.9 parts by mass (0.10 mol) of stearyl methacrylate, tert-butyl 2-ethylperoxyhexanoate 1.1 A mixture of parts by mass (0.005 mol) and 22.8 parts by mass of butyl acetate. After further polymerization at 90~100°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 butyl acetate of hydroxyl-containing acrylic resin Solution. The hydroxyl value of the obtained hydroxyl-containing acrylic resin was 121 mgKOH/g. The weight average molecular weight in terms of polystyrene obtained by GPC is 36,000.

(A6) The 50% by mass butyl acetate solution of the hydroxyl-containing acrylic resin obtained in the following synthesis example 6 [Synthesis Example 6] In a glass reactor equipped with a stirrer, a thermometer, a reflux cooler, and a dropping device, 37.3 parts by mass of butyl acetate was fed, and after heating to 90~100°C, the 2-hydroxy methacrylic acid was dropped over 4 hours under nitrogen aeration. 26.0 parts by mass (0.20 mol) of ethyl ester, 20.0 parts by mass (0.20 mol) of methyl methacrylate, 10.0 parts by mass (0.07 mol) of n-butyl methacrylate, tert-butyl 2-ethylperoxyhexanoate A mixture of 1.1 parts by mass (0.005 mol) and 18.7 parts by mass of butyl acetate. After further polymerization at 90~100°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 butyl acetate of hydroxyl-containing acrylic resin Solution. The hydroxyl value of the obtained hydroxyl-containing acrylic resin was 198 mgKOH/g. The weight average molecular weight in terms of polystyrene obtained by GPC is 41,000.

(A7) Alukidir J-524-A (manufactured by DIC Co., Ltd.: coconut oil modified alkyd resin)

(B) Ingredients (B1) Cymel 303LF (manufactured by Allnex Japan: fully ether methylated melamine resin)

(式中，Me為甲基、Ph為苯基)。(C) Component (C1) Organopolysiloxane represented by the following general formula (2): The bonding sequence 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) Ingredients (D1) p-toluenesulfonic acid

(E) Ingredients (E1) Toluene

[Examples 1 to 3, Comparative Examples 1 to 4] Using the components (A) to (E) shown above as raw materials, the coating composition was prepared in the following order. Take the components (A), (B), and (C) into the flask according to the blending ratios in Tables 1 and 2, take the (E) component so that the (A) ~ (C) components become 40% by mass, and mix them uniformly . The (D) component was added to the obtained solution so that the added amount was 2% by mass relative to 100 parts by mass of the total of the (A) to (C) components, and the coating composition was obtained by stirring and mixing. Tables 1 and 2 also record the viscosity of the obtained composition at 25°C measured with a B-type rotary viscometer. Using this composition, a release paper was produced by the method described later.

[Preparation of release paper] On mirror coated paper with a thickness of 165μm, the coating composition obtained was coated by a bar coater to a coating amount of 7.0g/m ² , and heated in a hot air dryer at 130°C 60 seconds, and heated in a 170°C hot air dryer for 30 seconds to form a release agent layer to obtain a release paper.

[Assessment] Using the release paper obtained above, the "peel strength", "surface condition", "gloss", and "repetitive durability" were evaluated by the following methods.

[Peel strength] On the release agent layer of the release paper obtained above, apply a one-liquid polyurethane solution [Crisvon 5516S (manufactured by Dainippon Ink Chemical Co., Ltd.)] so that the thickness of the coating film becomes 30 μm, at 130°C Heat treatment for 2 minutes. Next, stick Nitto 31B tape on the treated surface with a 2kg roll crimping once back and forth. After aging at 25°C for 20 hours, cut the sample into a width of 3cm, and use a tensile testing machine at an angle of 180° with a peeling speed. Stretch the adhesive tape at 0.3m/min, and measure the force required for peeling (gf/30mm). Furthermore, the peeling force when heated at 130°C for 60 seconds is referred to as RA; the peeling force when heated at 170°C for 30 seconds is referred to as RB. The smaller the value of the peeling force, the better the peelability.

[surface condition] The coating film on the release agent layer of the release paper obtained above was visually evaluated for the presence or absence of dents and unevenness. For both the release agent layer cured at 130°C and the release agent layer cured at 170°C, if the coating film collapse and unevenness can not be confirmed, it is "〇", and the coating film collapse and unevenness can be confirmed. Is "×".

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

[Repeat durability] On the release agent layer of the release paper obtained above, apply a one-liquid polyurethane solution [Crisvon 5516S (manufactured by DIC)] to make the thickness of the coating film 30μm, and heat-treat it at 130°C 2 minute. Next, heat treatment was performed at 180°C for 2 minutes, and Nitto 31B tape was attached to the treated surface, and then peeled back and forth by pressing with a 2 kg roller. This operation was repeated until the release agent layer was stuck and could not be peeled off as the number of repeated uses. In addition, the repeat durability A represents the number of uses when heated at 130°C for 60 seconds, and the repeat durability B represents the number of uses heated at 170°C for 30 seconds. The more times of use, the better the repeat durability.

These results are shown in Tables 1 and 2. In addition, the values in the table refer to the blending amount of component (A) to record the amount of solvent or solution contained, and the content of () to record the pure component amount of component (A).

Claims (8)

A resin composition for release paper or release film, which contains (A) Hydroxyl-containing acrylic resin with a hydroxyl value of 140~180mgKOH/g; (B) Resins selected from full ether type methylated melamine resins, methylol type methylated melamine resins, and these polymers; and (C) Organopolysiloxane having two or more functional groups in one molecule that can be chemically bonded to one or more resins selected from (A) component and (B) component. Such as the resin composition for release paper or release film of claim 1, wherein the weight average molecular weight of component (A) is 5,000 to 400,000. The resin composition for release paper or release film of claim 1 or 2, wherein the blending amount of component (B) is 10 to 120 parts by mass relative to 100 parts by mass of component (A). The resin composition for release paper or release film according to claim 1 or 2, wherein component (B) is a resin selected from perether methylated melamine resins and their polymers. The resin composition for release paper or release film of claim 1 or 2, wherein the blending amount of component (C) is 0.5 to 20 parts by mass relative to 100 parts by mass of component (A). The resin composition for release paper or release film of claim 1 or 2, wherein the component (C) contains an organopolysiloxane in which 10 to 60 mol% of organic groups bonded by silicon atoms in a molecule are phenyl groups. The resin composition for release paper or release film of claim 1 or 2, which further contains (D) an acid catalyst. A release paper or release film, which has a cured film formed by applying the release paper or release film resin composition according to any one of claims 1 to 7 to a substrate and heating it.