TWI862862B - Thermosetting release coating agent, cured product, and thermosetting release film and method of manufacturing the same - Google Patents

Abstract

The present invention provides a heat-curing peeling coating, a cured product, a heat-curing peeling film and a method for producing the same. The present invention provides a heat-curing peeling coating, comprising a polymer (A), a melamine resin (B), and an acid catalyst (C), wherein the polymer (A) comprises 40% to 98% by mass of a structural unit 1 derived from a (meth)acrylate containing an alkyl group having 4 to 11 carbon atoms and 2% to 60% by mass of a structural unit 2 derived from a (meth)acrylic monomer containing a hydroxyl group.

Description

Thermosetting peeling coating agent, cured product, and thermosetting peeling film and method for producing the same

The present invention relates to a thermally curable peeling coating agent, a cured product, a thermally curable peeling film and a method for manufacturing the same.

Release films are used as step films for casting films of urethane resins, acrylic resins, vinyl chloride resins, etc., as protective films for adhesive layers such as adhesive tapes, adhesive sheets, and adhesive films, and as step films for manufacturing electronic parts such as ceramic green sheets or printed circuit boards.

As a peeling coating agent for preparing a peeling film, various peeling coating agents have been proposed. For example, Patent Document 1 describes a peeling treatment agent containing a main agent containing a reaction product of a polymer (A) selected from a vinyl alcohol polymer or polyethyleneimine and a long-chain alkyl isocyanate. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2000-119608

[Problem to be solved by the invention] However, the stripping agent described in the patent document 1 does not undergo crosslinking, so there is a problem of low solvent resistance. In addition, the stripping force of the adhesive layer at room temperature (room temperature stripping force) and the stripping force after heating (heated stripping force) also need to be improved. Furthermore, a high residual adhesion rate after stripping is also required. The problem to be solved by the present invention is to provide a heat-curing stripping coating agent with good solvent resistance, room temperature stripping force, heated stripping force, and residual adhesion rate.

[Technical means to solve the problem] The inventors of the present invention have conducted diligent research and found that the above problem can be solved by using specific ingredients.

According to the present disclosure, the following items are provided. (Item 1) A heat-curing stripping coating agent comprising: a polymer (A), a melamine resin (B), and an acid catalyst (C), wherein the polymer (A) comprises 40% to 98% by mass of structural unit 1 [Chemical 4] (wherein R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is an alkyl group having 4 to 11 carbon atoms) and 2% to 60% by weight of the structural unit 2 [Chemistry 5] (wherein, R ²¹ is a hydrogen atom or a methyl group, R ²² is NHR ^2' or OR ^2' , and R ^2' is an alkyl group containing a hydroxyl group). (Item 2) The thermosetting peeling coating agent according to the item, comprising a polyol (D) (excluding the polymer (A)). (Item 3) The thermosetting peeling coating agent according to the item, wherein the polyol (D) comprises a polyol (D1), and the polyol (D1) comprises a structural unit D1 [Chemistry 6] (wherein, R ^D1 is a hydrogen atom or a methyl group, and R ^D2 is an alkyl group having 12 to 28 carbon atoms). (Item 4) A cured product, which is a cured product of the thermosetting peeling coating described in any of the above items. (Item 5) A thermosetting peeling film, comprising the cured product described in the above items and a plastic film. (Item 6) A method for producing a thermosetting peeling film, comprising: applying the thermosetting peeling coating described in any of the above items to at least one side of a plastic film and heating it.

In the present disclosure, in addition to the explicit combinations, the one or more features may be provided in further combinations.

[Effect of the invention] The heat-curing peeling coating of this embodiment has good solvent resistance, peeling force at room temperature, peeling force after heating, and residual adhesion rate.

In the entire disclosure, the range of numerical values such as each physical property value and content can be set appropriately (for example, selected from the upper and lower limit values described in each item below). Specifically, regarding the numerical value α, when A4, A3, A2, A1 (assuming A4>A3>A2>A1) and the like are exemplified as the upper and lower limits of the numerical value α, the range of the numerical value α can be exemplified as A4 or less, A3 or less, A2 or less, A1 or more, A2 or more, A3 or more, A1 to A2, A1 to A3, A1 to A4, A2 to A3, A2 to A4, A3 to A4, and the like.

[Thermosetting peeling coating: also referred to as coating] The present disclosure provides a thermosetting peeling coating, the thermosetting peeling coating comprising: a polymer (A), a melamine resin (B), and an acid catalyst (C), wherein the polymer (A) comprises 40% to 98% by mass of a structural unit 1 [Chemical 7] (wherein R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is an alkyl group having 4 to 11 carbon atoms) and 2% to 60% by weight of the structural unit 2 [Chemistry 8] (wherein, R ²¹ is a hydrogen atom or a methyl group, R ²² is NHR ^2' or OR ^2' , and R ^2' is an alkyl group containing a hydroxyl group).

<Polymer (A): also referred to as component (A)> Component (A) may be used alone or in combination of two or more.

(Structural unit 1) Structural unit 1 is obtained by using a (meth)acrylate (a1) containing an alkyl group having 4 to 11 carbon atoms as a monomer. [Chemical 9] (wherein R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is an alkyl group having 4 to 11 carbon atoms) The structural unit contained in the polymer (A). The (meth)acrylate (a1) containing an alkyl group having 4 to 11 carbon atoms may be used alone or in combination of two or more.

Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and a cycloalkyl group.

A linear alkyl group is represented by the general formula -C _n H _2n+1 (n is an integer of 1 or more).

The branched alkyl group is a group having no ring structure in which at least one hydrogen atom of a linear alkyl group is substituted by an alkyl group.

Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a cross-linked cycloalkyl group, a condensed cycloalkyl group, etc. Furthermore, a cycloalkyl group in which at least one hydrogen atom is substituted by an alkyl group is also regarded as a cycloalkyl group.

In the present disclosure, a single ring refers to a ring structure formed by covalent bonds of carbon and having no internal bridge structure. In addition, a fused ring refers to a ring structure in which two or more single rings share two atoms (i.e., they only share (fuse) one side of each ring). A cross-linked ring refers to a ring structure in which two or more single rings share three or more atoms.

The upper and lower limits of the carbon number of the alkyl group of R ¹² can be exemplified by 11, 10, 9, 8, 7, 6, 5, and 4. In one embodiment, the carbon number is preferably 4 to 11.

R ¹² is preferably an alkyl group having 4 to 11 carbon atoms, more preferably an alkyl group having 4 to 8 carbon atoms, further preferably a butyl group or a 2-ethylhexyl group.

Examples of the alkyl group having 4 to 11 carbon atoms include linear alkyl groups, branched alkyl groups, and cycloalkyl groups such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decamethyl group, and undecyl group.

Examples of the (meth)acrylate containing a linear alkyl group having 4 to 11 carbon atoms include butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, and undecyl (meth)acrylate.

Examples of the (meth)acrylate containing a branched alkyl group having 4 to 11 carbon atoms include 2-ethylhexyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isononyl (meth)acrylate, and isodecyl (meth)acrylate.

Examples of the (meth)acrylate containing a cycloalkyl group having 4 to 11 carbon atoms include cyclopentyl (meth)acrylate and cyclohexyl (meth)acrylate.

Relative to the mass of the polymer (A), the upper and lower limits of the content of the structural unit 1 relative to 100% by mass of the polymer (A) can be exemplified by 98% by mass, 97% by mass, 96% by mass, 95% by mass, 90% by mass, 89% by mass, 88.3% by mass, 88% by mass, 85% by mass, 80% by mass, 77% by mass, 76.7% by mass, 76% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 59% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, etc. In one embodiment, the content is preferably 40% by mass to 98% by mass.

The upper and lower limits of the content of the structural unit 1 relative to 100 mol% of the polymer (A) can be 90 mol%, 88 mol%, 85 mol%, 84 mol%, 80 mol%, 77 mol%, 76 mol%, 75 mol%, 70 mol%, 67 mol%, 65 mol%, 60 mol%, 55 mol%, 54 mol%, 50 mol%, etc. In one embodiment, the content can be 50 mol% to 90 mol%, etc.

(Structural unit 2) Structural unit 2 is obtained by using a hydroxyl-containing (meth) acrylic monomer (a2) as a monomer. (wherein R ²¹ is a hydrogen atom or a methyl group, R ²² is NHR ^2' or OR ^2' , and R ^2' is a hydroxyl-containing alkyl group), the structural unit contained in the polymer (A). The hydroxyl-containing (meth)acrylic monomer (a2) may be used alone or in combination of two or more.

In the present disclosure, "hydroxyl-containing alkyl group" refers to a group in which one hydrogen atom of an alkyl group is substituted with a hydroxyl group. Examples of the hydroxyl-containing alkyl group include a hydroxyl-containing straight chain alkyl group, a hydroxyl-containing branched alkyl group, and a hydroxyl-containing cycloalkyl group.

In the present disclosure, the upper and lower limits of the carbon number of a alkyl group (alkyl, alkylene, arylene, arylene alkylene arylene, etc.) are not mentioned, and examples thereof include 30, 29, 25, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, and 1.

Examples of the hydroxyl group-containing (meth)acrylic monomer (a2) include hydroxyl group-containing (meth)acrylates and hydroxyl group-containing (meth)acrylamide.

Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, and glycerol mono(meth)acrylate.

Examples of the hydroxyl group-containing (meth)acrylamide include N-(2-hydroxyethyl) (meth)acrylamide, N-(1-methyl-2-hydroxyethyl) (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, and N-(2-hydroxypropyl) (meth)acrylamide.

The upper and lower limits of the content of the structural unit 2 relative to 100% by mass of the polymer (A) can be exemplified by 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 17% by mass, 15% by mass, 12% by mass, 11.7% by mass, 10% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, etc. In one embodiment, the content is preferably 2% by mass to 60% by mass.

The upper and lower limits of the content of the structural unit 2 relative to 100 mol% of the polymer (A) can be 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 23 mol%, 20 mol%, 19 mol%, 18 mol%, 17 mol%, 16 mol%, 15 mol%, 14 mol%, 13 mol%, 12 mol%, 11 mol%, 10 mol%, etc. In one embodiment, the content can be 10 mol% to 50 mol%, etc.

The upper and lower limits of the mass ratio of the structural unit 1 to the structural unit 2 of the polymer (A) (mass of the structural unit 1/mass of the structural unit 2) can be exemplified by 49, 45, 40, 35, 30, 25, 20, 19, 17, 15, 13, 10, 8, 7.5, 7, 6.6, 6, 5, 4, 3.5, 3.3, 3, 2, 1, 0.9, 0.7, etc. In one embodiment, the mass ratio is preferably 0.7 to 49.

The upper and lower limits of the mass ratio (molar ratio) of the structural unit 1 to the structural unit 2 of the polymer (A) (mass ratio of structural unit 1/mass ratio of structural unit 2) can be exemplified by 9, 8, 7.3, 7, 6.9, 6, 5.3, 5, 4.8, 4, 3.3, 3.2, 3, 2, 1, etc. In one embodiment, the mass ratio (molar ratio) is preferably 1 to 9.

(Structural unit 3) In one embodiment, the polymer (A) may include structural unit 3 [Chemical 11] (wherein, R ³¹ is a hydrogen atom or a methyl group, and R ³² is an alkyl group having 1 to 3 carbon atoms).

Structural unit 3 is a monomer using a (meth)acrylate (a3) containing a short-chain alkyl group [Chemical 12] (wherein R ³¹ is a hydrogen atom or a methyl group, and R ³² is an alkyl group having 1 to 3 carbon atoms), the structural unit contained in the polymer (A). The short-chain alkyl-containing (meth)acrylate may be used alone or in combination of two or more.

Examples of the alkyl group having 1 to 3 carbon atoms include linear alkyl groups, branched alkyl groups, and cycloalkyl groups such as methyl group, ethyl group, and propyl group.

The upper and lower limits of the content of the structural unit 3 relative to 100% by mass of the polymer (A) can be exemplified by 30% by mass, 25% by mass, 24% by mass, 20% by mass, 15% by mass, 12% by mass, 11.6% by mass, 11% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass, 3% by mass, 2% by mass, 1% by mass, 0% by mass, etc. In one embodiment, the content is preferably 0% by mass to 30% by mass.

The upper and lower limits of the content of the structural unit 3 relative to 100 mol% of the polymer (A) can be 30 mol%, 28 mol%, 25 mol%, 23 mol%, 20 mol%, 19 mol%, 17 mol%, 15 mol%, 13 mol%, 11 mol%, 10 mol%, 5 mol%, 1 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 30 mol%.

(Structural unit 4) In one embodiment, the polymer (A) may include structural unit 4 [Chemical 13] (wherein, R ⁴¹ is a hydrogen atom or a methyl group, and R ⁴² is an alkyl group having 12 to 28 carbon atoms).

Structural unit 4 is a monomer using a (meth)acrylate containing a long-chain alkyl group [Chemical 14] (wherein R ⁴¹ is a hydrogen atom or a methyl group, and R ⁴² is an alkyl group having 12 to 28 carbon atoms) , the structural unit contained in the polymer (A). The long-chain alkyl-containing (meth)acrylate may be used alone or in combination of two or more.

Examples of the alkyl group having 12 to 28 carbon atoms include dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl), nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, and octacosyl.

Examples of the (meth)acrylate containing a long chain alkyl group include lauryl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, palmityl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, behenyl (meth)acrylate, tricosyl (meth)acrylate, tetracosyl (meth)acrylate, pentacosyl (meth)acrylate, hexacosyl (meth)acrylate, heptacosyl (meth)acrylate, octacosyl (meth)acrylate, isododecyl (meth)acrylate, isotridecyl (meth)acrylate, isomyristyl (meth)acrylate, isopentadecyl (meth)acrylate, isohexadecyl (meth)acrylate, isoheptadecyl (meth)acrylate, and isostearyl (meth)acrylate. Among them, lauryl (meth)acrylate and stearyl (meth)acrylate are particularly preferred in terms of easy availability and easy peeling.

The upper and lower limits of the content of the structural unit 4 relative to 100% by mass of the polymer (A) can be exemplified by 9%, 8%, 7%, 6%, 5%, 3%, 4%, 2%, 1%, 0%, etc. In one embodiment, the content is preferably 0% to 9% by mass.

The upper and lower limits of the content of the structural unit 4 relative to 100 mol% of the polymer (A) can be 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 9 mol%.

(Structural units other than structural units 1 to 4: also referred to as other structural units) In one embodiment, the polymer (A) may contain structural units other than structural units 1 to 4.

Examples of structural units other than structural units 1 to 4 include structural units contained in the polymer (A) when polyfunctional (meth)acrylates such as (meth)acrylic acid, styrene, alkenyl (meth)acrylate, (meth)acrylamide, (meth)acrylonitrile, and ethylene glycol di(meth)acrylate are used as monomers.

The content of other structural units relative to 100% by mass of polymer (A) can be exemplified by less than 5% by mass, less than 2% by mass, less than 1% by mass, less than 0.1% by mass, 0% by mass, etc. In addition, the content of other structural units relative to 100% by mass of any one of structural units 1 to 3 can be exemplified by less than 5% by mass, less than 2% by mass, less than 1% by mass, less than 0.1% by mass, 0% by mass, etc.

The content of other structural units relative to 100 mol% of polymer (A) can be exemplified by less than 5 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, 0 mol%, etc. In addition, the content of other structural units relative to 100 mol% of any one of structural units 1 to 3 can be exemplified by less than 5 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, 0 mol%, etc.

<Physical properties of polymer (A)> The upper and lower limits of the number average molecular weight of polymer (A) can be 80,000, 75,000, 60,000, 50,000, 40,000, 30,000, 25,000, 24,700, 24,000, 23,000, 20,000, 19,500, 19,000, 18,500, 18,000, 17,500, 17,000, 16,500. , 16000, 15800, 15700, 15500, 15000, 14900, 14500, 14400, 14300, 14200, 14000, 13800, 13700, 13600, 13500, 13000, 12500, 12000, 11500, 11200, 11000, 10000, 9000, 8000, etc. In one embodiment, the number average molecular weight is preferably 8000-80000.

The upper and lower limits of the weight average molecular weight of the polymer (A) are 200000, 190000, 170000, 150000, 100000, 90000, 75000, 60000, 59000, 57000, 55000, 54400, 54000, 53000, 52500, 52300, 52000, 51000, 50000, 49000, 48000, 47200, 47000, 46200, 4600 0, 45300, 45000, 44000, 43000, 42800, 42000, 41000, 40100, 40000, 39500, 39000, 38100, 38000, 37500, 37400, 37000, 36000, 35000, 34000, 33000, 32300, 32000, 31000, 30000, 29000, 25000, 24000, 22000, 20000, etc. In one embodiment, the weight average molecular weight is preferably 20000 to 200000.

The weight average molecular weight and number average molecular weight can be obtained as polystyrene conversion values measured by gel permeation chromatography (GPC) in an appropriate solvent. Detailed conditions include the following conditions. Model: Product name "HLC-8220" (manufactured by Tosoh Co., Ltd.) Column: Product name "PLgel MIXED-C" (manufactured by Agilent Technology) × 2 Developing solvent, flow rate: tetrahydrofuran, 1.0 mL/min Measurement temperature: 40°C Detector: Refractive index (RI) Standard: Monodisperse polystyrene Polymer concentration: 0.2%

The upper limit and the lower limit of the hydroxyl value of the polymer (A) can be exemplified by 300 mgKOH/g, 275 mgKOH/g, 250 mgKOH/g, 225 mgKOH/g, 210 mgKOH/g, 203 mgKOH/g, 200 mgKOH/g, 175 mgKOH/g, 150 mgKOH/g, 125 mgKOH/g, 100 mgKOH/g, 75 mgKOH/g, 52 mgKOH/g, 50 mgKOH/g, 40 mgKOH/g, 35 mgKOH/g, 30 mgKOH/g, 25 mgKOH/g, 22 mgKOH/g, 20 mgKOH/g, 15 mgKOH/g, 10 mgKOH/g, 9 mgKOH/g, 7 mgKOH/g, 5 mgKOH/g, 4 mgKOH/g, 2 mgKOH/g, 1 In one embodiment, the hydroxyl value of the polymer (A) is preferably 1 mgKOH/g to 300 mgKOH/g from the viewpoint of achieving both stripping properties and solvent resistance.

The hydroxyl value can be measured by the method according to Japanese Industrial Standard (JIS) K1557-1.

The method for producing the polymer (A) may be exemplified by various known radical polymerizations, etc. Radical polymerization can be achieved by heating in the presence of a radical polymerization initiator.

Examples of free radical polymerization initiators include: inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, etc.; organic peroxides such as benzoyl peroxide, diisopropylbenzene peroxide, lauryl peroxide, etc.; azo compounds such as 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyronitrile, etc. The free radical polymerization initiator can be used alone or in combination of two or more. The amount of the free radical polymerization initiator used is preferably about 1 to 10 parts by mass relative to 100 parts by mass of all monomer components.

When producing the polymer (A), a chain transfer agent may be used as needed. Examples of the chain transfer agent include lauryl mercaptan, dodecyl mercaptan, 2-hydroxybenzothiazole, bromotrichloromethane, α-methylstyrene dimer, and the like. The chain transfer agent may be used alone or in combination of two or more. The amount of the chain transfer agent used is preferably about 0 to 5 parts by mass based on 100 parts by mass of all monomer components.

The upper and lower limits of the content of the polymer (A) relative to 100% by mass of the solid component of the coating agent can be exemplified by 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, etc. In one embodiment, the content is preferably 2% by mass to 80% by mass.

<Melamine resin: also referred to as component (B)> Component (B) may be used alone or in combination of two or more.

The component (B) may include, for example, a melamine compound [Chemical 15] derived from the following: (wherein R ^m1 to R ^m6 are independently selected from hydrogen atom, hydroxymethyl group, methoxymethyl group, ethoxymethyl group, n-butoxymethyl group and iso-butoxymethyl group) melamine resin etc. In one embodiment, the average polymerization degree of component (B) is 1.1 to 10.

In terms of excellent balance between curability of the coating agent and compatibility with component (A) and component (D) described later, component (B) is preferably a melamine resin containing structural units derived from methylated melamine and/or butylated melamine. Methylated melamine refers to a compound in which at least one of R ^m1 to R ^m6 is a methoxymethyl group (-CH ₂ OCH ₃ ), and butylated melamine refers to a compound in which at least one of R ^m1 to R ^m6 is a n-butoxymethyl group (-CH ₂ OCH ₂ CH ₂ CH ₂ CH ₃ ) or an iso-butoxymethyl group (-CH ₂ OCH(CH ₃ )CH ₂ CH ₃ ).

In terms of excellent curability, the component (B) is preferably a resin containing a structural unit derived from fully ether type methylated melamine in which all of R ^m1 to R ^m6 are methoxymethyl groups (hereinafter referred to as fully ether type methylated melamine resin), and in terms of compatibility with the components (A) and (D), it is preferably a resin containing a structural unit derived from fully ether type butylated melamine in which all of R ^m1 to R ^m6 are either n-butoxymethyl groups or iso-butoxymethyl groups (hereinafter referred to as fully ether type butylated melamine resin). In terms of excellent balance between curability and compatibility with components (A) and (D), a resin containing a structural unit derived from fully ether type methyl-butylated melamine in which at least one of R ^m1 to R ^m6 is a methoxymethyl group and the others are either n-butoxymethyl or iso-butoxymethyl groups (hereinafter referred to as fully ether type methyl-butylated melamine resin) is preferred.

Examples of commercially available products of component (B) include CYMEL 300, CYMEL 301, CYMEL 303LF, CYMEL 350, CYMEL 370N, CYMEL 771, CYMEL 325, CYMEL 327, CYMEL 703, CYMEL 712, CYMEL 701, CYMEL 266, CYMEL 267, CYMEL 268, CYMEL 269, CYMEL 270N, CYMEL 271, CYMEL 272, CYMEL 273, CYMEL 274, CYMEL 275, CYMEL 276, CYMEL 277, CYMEL 278, CYMEL 279, CYMEL 280, CYMEL 281, CYMEL 282, CYMEL 283, CYMEL 284, CYMEL 285 L) 267, Cymel 285, Cymel 232, Cymel 235, Cymel 236, Cymel 238, Cymel 272, Cymel 212, Cymel 253, Cymel 254, Cymel 202, Cymel 207, MYCOAT 506 (All the above are from Allnex Japan) Japan) (co., Ltd.), Nikalac MW-30M, Nikalac MW-30, Nikalac MW-30HM, Nikalac MW-390, Nikalac MW-100LM, Nikalac MX-750LM, Nikalac MW-22, Nikalac MS-21, Nikalac MS-11, Nikalac lac) MW-24X, Nikalac MS-001, Nikalac MX-002, Nikalac MX-730, Nikalac MX-750, Nikalac MX-708, Nikalac MX-706, Nikalac MX-042, Nikalac MX-035, Nikalac MX-45, Nikalac MX-43, Nikalac MX-417, Nikalac MX-410 (all manufactured by Sanwa Chemical Co., Ltd.), U-VAN 20SB, U-VAN 20SE60, U-VAN 21R, U-VAN 22R, U-VAN 122, U-VAN 125, U-VAN 220, U-VAN 225, U-VAN 228, U-VAN 2020 (all manufactured by Mitsui Chemicals Co., Ltd. Co., Ltd.), AMIDIR J-820-60, AMIDIR L-109-65, AMIDIR L-117-60, AMIDIR L-127-60, AMIDIR 13-548, AMIDIR G-821-60, AMIDIR L-110-60, AMIDIR L-125-60, AMIDIR L-166-60B (all manufactured by DIC (Co., Ltd.)), etc.

The upper and lower limits of the content of the melamine resin (B) relative to 100% by mass of the solid component of the coating agent can be exemplified by 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, etc. In one embodiment, the content is preferably 20% by mass to 70% by mass, and more preferably 25% by mass to 60% by mass.

<Acid catalyst: also referred to as component (C)> Component (C) can be used alone or in combination of two or more.

Examples of the component (C) include inorganic acids, organic acids, and thermal acid generators.

Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like.

Examples of the organic acid include organic carboxylic acids, organic sulfonic acids, and organic phosphoric acids.

Examples of the organic carboxylic acid include oxalic acid, acetic acid, and formic acid.

Examples of the organic sulfonic acid include methanesulfonic acid, trifluoromethanesulfonic acid, isoprenesulfonic acid, camphorsulfonic acid, hexanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, hexadecanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cumenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and nonylnaphthalenesulfonic acid.

Examples of the organic phosphoric acid include methyl acid phosphate, ethyl phosphate, propyl phosphate, isopropyl phosphate, butyl phosphate, butoxyethyl phosphate, octyl phosphate, 2-ethylhexyl phosphate, decyl phosphate, lauryl phosphate, stearyl phosphate, oleyl phosphate, behenyl phosphate, phenyl phosphate, nonylphenyl phosphate, cyclohexyl phosphate, phenoxyethyl phosphate, alkoxypolyethylene glycol phosphate, bisphenol A phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, diisopropyl phosphate, dibutyl phosphate, dioctyl phosphate, di-2-ethylhexyl phosphate, dioctyl phosphate, dilauryl phosphate, distearyl phosphate, diphenyl phosphate, and dinonylphenyl phosphate.

Examples of the thermal acid generator include cobalt salts, benzothiazole salts, ammonium salts, and phosphonium salts.

In one embodiment, the acid catalyst (C) is preferably an organic acid, more preferably an organic sulfonic acid and/or an organic phosphoric acid, from the viewpoint of compatibility with the polymer (A) and the melamine resin (B) and other resins.

The upper and lower limits of the content of the acid catalyst (C) relative to 100% by mass of the solid component of the coating agent can be exemplified by 10% by mass, 9.5% by mass, 9% by mass, 8.5% by mass, 8% by mass, 7.5% by mass, 7% by mass, 6.5% by mass, 6% by mass, 5.5% by mass, 5% by mass, 4.5% by mass, 4% by mass, 3.9% by mass, 3.8% by mass, 3.5% by mass, 3% by mass, 2.5% by mass, 2% by mass, 1.5% by mass, 1% by mass, etc. In one embodiment, the content is preferably 1% by mass to 10% by mass.

<Polyol: also referred to as component (D)> In one embodiment, the coating agent may include a polyol. Component (D) may be used alone or in combination of two or more.

In the present disclosure, "polyol" refers to a compound having two or more hydroxyl groups (-OH).

Examples of the component (D) include alkylene polyols, dimer diols, hydrogenated dimer diols, castor oil-based polyols, hydroxyl-containing fatty acid alkylene polyol esters, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, and structural units D1 [Chemical 16] (wherein ^RD1 is a hydrogen atom or a methyl group, and ^RD2 is an alkyl group having 12 to 28 carbon atoms) and the like.

(Polyol (D1)) Polyol (D1) may be exemplified by a polymer including a structural unit D1 and a hydroxyl group-containing structural unit D2.

・Structural unit D1 Structural unit D1 is a monomer using a (meth)acrylate containing a long-chain alkyl group [Chemical 17] (wherein R ^D1 is a hydrogen atom or a methyl group, and R ^D2 is an alkyl group having 12 to 28 carbon atoms), the structural unit contained in the polyol (D1). The (meth)acrylate containing a long-chain alkyl group may be used alone or in combination of two or more.

Examples of the long-chain alkyl group-containing (meth)acrylate include the above-mentioned compounds.

The upper and lower limits of the content of the structural unit D1 relative to 100% by mass of the polymer (D1) can be exemplified by 99% by mass, 98% by mass, 97% by mass, 96% by mass, 95% by mass, 90% by mass, 88% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, etc. In one embodiment, the content can be exemplified by 50% by mass to 99% by mass, etc.

・Hydroxy-containing structural unit D2 Examples of the hydroxyl-containing structural unit D2 include the structural unit 2 and the like.

The upper and lower limits of the content of the structural unit D2 relative to 100% by mass of the polymer (D1) can be exemplified by 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 12% by mass, 10% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, etc. In one embodiment, the content can be exemplified by 1% by mass to 50% by mass, etc.

(Alkylene polyol) In this disclosure, "alkylene polyol" refers to a compound containing an alkylene group and two or more hydroxyl groups.

Examples of the alkylene polyol include linear alkylene polyol, branched alkylene polyol, and cycloalkylene polyol.

Examples of the linear alkyl polyol include ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol.

Examples of the branched alkylene polyol include neopentyl glycol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,4-dibutyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, propylene glycol, 1,2-butanediol, pentaerythritol, and trihydroxymethylpropane.

Examples of the cycloalkylene polyol include monocyclic cycloalkylene glycol and cross-linked cycloalkylene glycol.

Examples of the monocyclic cycloalkylene polyol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2,2′-bis(4-hydroxycyclohexyl)propane.

Examples of the cross-linked cycloalkylene polyol include tricyclodecanedimethanol and the like.

(Dimer diol) Dimer diol generally refers to a substance obtained by reducing a reaction product of a cyclic and/or non-cyclic dimer acid obtained by dimerizing a higher unsaturated fatty acid with methanol. The dimerization reaction of higher unsaturated fatty acids can be exemplified by the method described in Japanese Patent Laid-Open No. 9-136861. In addition, hydrogenated dimer diol is obtained by subjecting dimer diol to a hydrogenation reaction.

When producing the dimer diol, the higher unsaturated fatty acid may be used alone or in combination of two or more. Examples of the higher unsaturated fatty acid include unsaturated monocarboxylic acids having 14 to 22 carbon atoms.

Examples of the unsaturated monocarboxylic acid having 14 to 22 carbon atoms include tetradecadienoic acid, hexadecadienoic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, arachidonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, eicosenoic acid, erucic acid, cetoleic acid, and brassidic acid. Among these, oleic acid and/or linoleic acid are preferred.

(Castor oil-based polyol) Examples of castor oil-based polyol include fatty acid (poly)esters containing glycerol hydroxyl groups.

Glycerol hydroxyl-containing fatty acid (poly)ester refers to a (poly)ester (monoester, diester, triester) obtained by reacting one or more hydroxyl groups of glycerol with a hydroxyl-containing fatty acid.

The hydroxyl-containing fatty acid is preferably a hydroxyl-containing long-chain fatty acid having 12 or more carbon atoms (e.g., 12 to 30 carbon atoms, 12 to 24 carbon atoms, 12 to 20 carbon atoms, etc.).

Examples of the hydroxyl-containing long-chain fatty acid include hydroxyl-containing saturated long-chain fatty acids and hydroxyl-containing unsaturated long-chain fatty acids.

Examples of the saturated long-chain fatty acid containing a hydroxyl group include hydroxylauric acid, hydroxytridecyl acid, hydroxymyristic acid, hydroxypentadecanyl acid, hydroxypalmitic acid, hydroxyheptadecanyl acid, hydroxystearic acid, hydroxynonadecanyl acid, hydroxyeicosyl acid, hydroxyheneicosyl acid, hydroxybehenic acid, hydroxytricosyl acid, hydroxytetracosyl acid, and hydroxytetracosyl acid. acid, hydroxypentacosyl acid, hydroxyhexacosyl acid, hydroxyheptacosyl acid, hydroxyoctacosyl acid, hydroxyisododecyl acid, hydroxyisotridecyl acid, hydroxyisomyristic acid, hydroxyisopentadecanyl acid, hydroxyisohexadecyl acid, hydroxyisoheptadecanyl acid, hydroxyisostearic acid, aleuritic acid, and the like.

Examples of the hydroxyl-containing unsaturated long-chain fatty acids include hydroxyl-containing monounsaturated long-chain fatty acids, hydroxyl-containing diunsaturated long-chain fatty acids, hydroxyl-containing triunsaturated long-chain fatty acids, hydroxyl-containing tetraunsaturated long-chain fatty acids, hydroxyl-containing pentaunsaturated long-chain fatty acids, hydroxyl-containing hexaunsaturated long-chain fatty acids, and the like.

Examples of the hydroxyl-containing monounsaturated long-chain fatty acid include ricinoleic acid, hydroxymyristic acid, hydroxypalmitoleic acid, hydroxysapienic acid, hydroxyoleic acid, hydroxyelaidic acid, hydroxyoctadecenoic acid, hydroxygadoleic acid, hydroxyeicosenoic acid, hydroxyerucic acid, and hydroxynervonic acid.

Examples of the hydroxyl-containing diunsaturated long-chain fatty acid include hydroxylinolenic acid, hydroxyeicosadienoic acid, and hydroxydocosadienoic acid.

Examples of the hydroxyl-containing triunsaturated long-chain fatty acid include hydroxylinolenic acid, hydroxy pinolenic acid, hydroxy eleostearic acid, hydroxy mead acid, and hydroxy eicosatrienoic acid.

Examples of the hydroxyl-containing tetraunsaturated long-chain fatty acid include hydroxy stearidonic acid, hydroxy arachidonic acid, and hydroxy docosatetraenoic acid.

Examples of the hydroxyl-containing pentaunsaturated long-chain fatty acid include hydroxy bosseopentaenoic acid, hydroxy eicosapentaenoic acid, hydroxy osbond acid, hydroxy clupanodonic acid, and hydroxy tetracosapentaenoic acid.

Examples of the hydroxyl-containing hexaunsaturated long-chain fatty acid include hydroxy docosahexaenoic acid and hydroxy nisinic acid.

(Hydroxy fatty acid alkylene polyol ester) In this disclosure, "hydroxy fatty acid alkylene polyol ester" refers to an ester obtained by reacting a hydroxy fatty acid with an alkylene polyol.

Examples of the hydroxyl group-containing fatty acid and alkylene polyol include those mentioned above.

(Polyether polyol) In this disclosure, "polyether polyol" refers to, for example, a compound having two or more hydroxyl groups and two or more repeating units containing ether bonds in succession.

In one embodiment, the polyether polyol is represented by the following structural formula HO-(R ^Ether -O-) _n H (wherein, R ^Ether is an alkylene group, an arylene group, or an arylene alkylene arylene group, and n is an integer greater than 2).

Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

The linear alkyl group is represented by the general formula -(CH ₂ ) _n - (n is an integer greater than or equal to 1). Examples of the linear alkyl group include methylene, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decamethylene.

The branched alkylene group is a group in which at least one hydrogen atom of a linear alkylene group is substituted by an alkyl group. Examples of the branched alkylene group include isopropylene, diethylpentylene, trimethylbutylene, trimethylpentylene, and trimethylhexylene.

Examples of the cycloalkylene group include monocyclic cycloalkylene groups, crosslinked cycloalkylene groups, condensed cycloalkylene groups, etc. In addition, one or more hydrogen atoms of the cycloalkylene group may be substituted with a linear alkyl group or a branched alkyl group.

Examples of the monocyclic cycloalkylene group include cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, and 3,5,5-trimethylcyclohexylene.

Examples of the cross-linked cycloalkylene group include tricyclodecylene, adamantylene, and norbornylene.

Examples of the fused cycloalkylene group include dicyclodecylene and the like.

Examples of the aryl group include phenylene group, naphthylene group, fluorylene group, and the like.

Arylene Group Alkylene Group The arylene group is a group represented by -R ^arylene -R ^alkylene -R ^arylene - (wherein, R ^arylene represents an arylene group, and R ^alkylene represents an alkylene group).

Examples of the arylene group include phenylene, dimethylmethylenephenylene, and the like.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and alkylene oxide adducts of polyols.

Examples of commercially available products of polyether polyols include Adeka Polyether GM-30, Adeka Polyether P-400, Adeka Polyether G-400, Adeka Polyether T-400, and Adeka Polyether AM-302 (all manufactured by Adeka Co., Ltd.).

(Polyester polyol) In this disclosure, "polyester polyol" refers to a compound having two or more hydroxyl groups and two or more repeating units containing ester bonds in succession. In addition, polycaprolactone polyol is a type of polyester polyol.

In one embodiment, the polyester polyol is represented by the following structural formula HO-{ ^RaEster -OC(=O) ^-RbEster -C(=O)O} _m - ^RcEster -OH (wherein, ^RaEster , ^RbEster and ^RcEster are independently an alkylene group or an arylene group, and m is an integer greater than 2).

Examples of the polyester polyol include reaction products of polycarboxylic acid or its anhydride and polyol.

Examples of the polycarboxylic acid include dicarboxylic acid and the like.

Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and cyclohexane dicarboxylic acid.

Examples of the polycarboxylic anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, and trimellitic anhydride.

Examples of the polyol include the above-mentioned alkylene polyols.

(Polycarbonate polyol) In this disclosure, "polycarbonate polyol" refers to a compound having two or more hydroxyl groups and two or more repeating units containing carbonate bonds.

In one embodiment, the polycarbonate polyol is represented by the following structural formula HO-{ ^RaCarbo -OC(=O)O} _p - ^RbCarbo -OH (wherein, ^RaCarbo and ^RbCarbo are independently alkylene groups, and p is an integer greater than 2).

Examples of the polycarbonate polyol include reaction products of a polyol and phosgene, and ring-opening polymers of cyclic carbonates (such as alkyl carbonates).

Examples of the polyol include the above-mentioned alkylene polyols.

Examples of the alkyl carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, etc. Examples of commercially available polycarbonate polyols include ETERNACOLL UH-50, ETERNACOLL PH-50 (both manufactured by Ube Industries, Ltd.), Duranol T5625, Duranol T5652, Duranol G3452 (both manufactured by Asahi Kasei Co., Ltd.), etc.

(Polyolefin polyol) Polyolefin polyols include polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorides thereof having two or more hydroxyl groups. Commercially available products of polyolefin polyols include NISSO-PB GI-1000 (manufactured by Nippon Soda Co., Ltd.).

(Physical properties of component (D)) The upper and lower limits of the molecular weight of component (D) can be 50,000, 40,000, 30,000, 20,000, 10,000, 5,000, 4,000, 3,500, 3,001, 3,000, 2,500, 2,000, 1,500, 1,000, 500, 250, 100, etc. In one embodiment, the molecular weight is preferably 100 to 50,000.

In the present disclosure, when simply referred to as "molecular weight", it refers to either the formula weight or the number average molecular weight. When the structure of the compound can be uniquely expressed by a specific chemical formula (i.e., the molecular weight distribution is 1), the molecular weight refers to the formula weight. On the other hand, when the structure of the compound cannot be uniquely expressed by a specific chemical formula (i.e., the molecular weight distribution is greater than 1), the molecular weight refers to the number average molecular weight.

The upper limit and lower limit of the hydroxyl value of the component (D) may be 1300 mgKOH/g, 1200 mgKOH/g, 1100 mgKOH/g, 1000 mgKOH/g, 900 mgKOH/g, 800 mgKOH/g, 750 mgKOH/g, 700 mgKOH/g, 600 mgKOH/g, 500 mgKOH/g, 400 mgKOH/g, 300 mgKOH/g, 250 mgKOH/g, 200 mgKOH/g, 150 mgKOH/g, 100 mgKOH/g, 90 mgKOH/g, 75 mgKOH/g, 50 mgKOH/g, 40 mgKOH/g, etc. In one embodiment, the hydroxyl value is preferably 40 mgKOH/g to 1300 mgKOH/g.

The upper and lower limits of the content of the polyol (D) in 100% by mass of the solid content of the coating agent can be 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20% by mass, etc. In one embodiment, the content is preferably 20% to 65% by mass.

<Organic solvent (E): also referred to as component (E)> In one embodiment, the coating agent may include an organic solvent. The organic solvent may be used alone or in combination of two or more.

Examples of the organic solvent include methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, butyl acetate, toluene, xylene, isopropyl alcohol, ethanol, butanol, etc. Among these, methyl ethyl ketone, methyl isobutyl ketone, isopropyl alcohol, ethyl acetate, butyl acetate, and toluene are preferred from the viewpoint of the solubility of the resin.

In one embodiment, from the viewpoint of coating compatibility, the content of the organic solvent in the coating agent is preferably 1 mass % to 50 mass % of the solid content of the coating agent. By setting the value within the above range, a balance between the curability and the pot life of the cured film can be easily achieved.

The thermosetting peeling coating can be used as a thermosetting peeling coating for sheet molding, a thermosetting peeling coating for green sheet manufacturing, a thermosetting peeling coating for adhesion, a thermosetting peeling coating for labels, a thermosetting peeling coating for medical use, a thermosetting peeling coating for office supplies, and the like.

<Additives> The coating agent may contain an agent that is incompatible with any of the components (A) to (E) as an additive.

Examples of additives include adhesives, defoaming agents, anti-slip agents, preservatives, anti-rust agents, pH adjusters, antioxidants, pigments, dyes, lubricants, leveling agents, conductive agents, polybutadiene, polyisoprene, polychloroprene, polyprene, polybutylene, polyisobutylene, polystyrene, isoprene-butadiene copolymers, styrene-isoprene copolymers, polyolefins and their derivatives, silicone resins, isocyanate group-containing compounds, epoxy group-containing compounds, amines, carboxylic anhydrides, and long-chain alkyl group-containing alcohols. The adhesive is not particularly limited, and examples thereof include known acrylic resins, urethane resins, polyester resins, epoxy resins, alkyd resins, and the like.

In one embodiment, the content of the additive relative to 100% by mass of the coating agent may be less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, or 0% by mass. In addition, the content relative to 100% by mass of any one of the components (A) to (E) may be less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, or 0% by mass.

The coating agent can be produced by dispersing and mixing the components (A) to (C), and the components (D) to (E) and additives as required, using various known means. In addition, the order of adding the components is not particularly limited. In addition, various known devices (emulsifying disperser, ultrasonic disperser, etc.) can be used as the dispersing and mixing means.

[Hardened product] This disclosure provides a cured product of the aforementioned heat-curing stripping coating agent.

In one embodiment, the cured product is a thermally cured product of the thermally cured peeling coating agent. Examples of the curing conditions include the conditions described below.

[Thermosetting peeling film] This disclosure provides a thermosetting peeling film, including the aforementioned hardened material and a plastic film.

Examples of the plastic film include films of plastics such as polycarbonate, polymethyl methacrylate, polystyrene, polyethylene terephthalate (PET), polyethylene naphthalate, polyimide, polyolefin, nylon, epoxy resin, melamine resin, triacetyl cellulose resin, acrylonitrile butadiene styrene (ABS) resin, acrylonitrile styrene (AS) resin, and norbornene-based resins. Among these, polyethylene terephthalate is preferred in terms of performance such as transparency, dimensional stability, mechanical properties, and chemical resistance.

The plastic film may be subjected to surface treatment (corona discharge, etc.) as required. In addition, the plastic film may also be provided with a layer formed by a coating agent other than the thermosetting peeling coating agent disclosed herein on one or both sides thereof.

[Method for manufacturing a heat-curing peeling film] The present disclosure provides a method for manufacturing a heat-curing peeling film, comprising: applying the heat-curing peeling coating agent to at least one side of a plastic film and heating the film.

Examples of the coating method include spraying, roll coating, reverse roll coating, gravure coating, doctor blade coating, rod coating, and spot coating.

The amount of application is not particularly limited, but the amount of application is preferably an amount that gives a mass of about 0.1 g/m ² to 10 g/m ² after drying, and more preferably an amount that gives a mass of 0.2 g/m ² to 5 g/m ² .

The heating method may include drying using a circulating air dryer, etc. The drying (curing) conditions may include about 90°C to 170°C and a time of about 30 seconds to 2 minutes. [Example]

The present invention is specifically described below by way of examples and comparative examples. However, the description in the preferred embodiments and the following examples are provided for the purpose of illustration only and are not provided for the purpose of limiting the present invention. Therefore, the scope of the present invention is neither limited to the embodiments specifically described in this specification nor to the examples, but is limited only by the scope of the invention application. In addition, in each example and comparative example, unless otherwise specified, the values such as parts and % are based on mass.

Preparation Example 1 In a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen inlet tube, a thermometer, and a dropping funnel, 88.3 parts of butyl acrylate, 11.7 parts of 2-hydroxyethyl methacrylate, 2 parts of azobisisobutyronitrile as an initiator, and 153 parts of methyl ethyl ketone as a solvent were added, and the temperature was slowly raised to 80°C. The reaction was carried out for 9 hours to obtain a polymer solution with a solid content concentration of 40%.

Production examples other than Production Example 1 were carried out in the same manner as Production Example 1 except that the components and amounts were changed as shown in the following table.

[Table 1] Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Manufacturing Example 6 Manufacturing Example 7 Manufacturing Example 8 Comparative Manufacturing Example 1 Comparative Manufacturing Example 2 Structural unit 1 BA 88.3 59 89.6 76.7 78.3 3 2EHA 88.3 76.7 76.7 Structural unit 2 HEA 17 11.4 17 HEMA 11.7 11.7 23.3 11.7 23.3 11.7 11.7 Structural unit 3 MMA 11.6 twenty four 10.0 80 Other structural units LA 88.3 Hydroxyl value (mgKOH/g) 50 50 100 50 82 55 100 50 50 82

<Abbreviation> BA: Butyl acrylate 2EHA: 2-ethylhexyl acrylate HEA: 2-hydroxyethyl acrylate HEMA: 2-hydroxyethyl methacrylate MMA: Methyl methacrylate LA: Lauryl acrylate

Example 1 Add 75 parts of the polymer produced in Example 1 as component (A) in terms of solid content, 25 parts of a fully ether-type methylated melamine resin (product name "CYMEL 303LF": manufactured by Allnex Japan) as component (B), and 4 parts of p-toluenesulfonic acid as component (C), and dilute them with toluene to prepare a solid content of 10%. Then, apply the solution to a polyethylene terephthalate film (film thickness 75 μm) in such a way that the film thickness of the dry coating is 1 μm, and dry it at 120°C for 1 minute to obtain a peeling film.

In Examples and Comparative Examples other than Example 1, the same procedures as in Example 1 were carried out except that the components and amounts were changed as shown in the following table.

[Table 2] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Comparison Example 1 Comparison Example 2 Comparison Example 3 (A) Manufacturing Example 1 75 Manufacturing Example 2 75 30 20 10 5 10 2.5 Manufacturing Example 3 75 10 Manufacturing Example 4 75 Manufacturing Example 5 75 Manufacturing Example 6 75 10 10 10 Manufacturing Example 7 75 Manufacturing Example 8 75 (A) Other than Comparative Manufacturing Example 1 75 Comparative Manufacturing Example 2 75 Peeloil 1050 75 (B) Methylated melamine resin 25 25 25 25 25 25 25 25 30 35 40 45 40 40 65 50 50 50 25 25 25 (C) p-Toluenesulfonic acid 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 1 2 8 4 4 4 (D) Hydrogenated dimer diol 40 45 50 50 25 25 40 40 40 Cyclohexanedimethanol 25 25 Trihydroxymethylpropane 25 Comparative Manufacturing Example 1 7.5 Solvent resistance (hardening) ○ ○ ○ ○ ○ ○ ○ ○ △ ○ ○ ○ ○ ○ ○ ○ ○ ○ × ○ × Room temperature peeling force (N/25 mm) 3.2 2.3 2.5 2.4 5.1 4.0 3.4 3.6 0.75 1.0 1.7 2.4 0.78 0.73 2.4 3.8 3.7 3.8 0.64 9.4 0.4 Peeling force after heating (N/25 mm) 5.6 3.5 3.2 3.8 6.3 5.6 5.3 6.2 2.2 2.4 2.7 3.0 2.0 1.8 3.6 5.5 5.2 5.1 1.7 Cannot be separated 4.5 Residual attachment rate (%) 92 93 93 91 90 91 92 91 89 91 90 91 91 91 90 90 92 90 90 80 89

<Explanation of abbreviations> Methylated melamine resin: Product name "CYMEL 303LF", full ether type methylated melamine resin, manufactured by Allnex Japan (Co., Ltd.) Hydrogenated dimer diol: Product name "Pripol 2033", manufactured by Japan Croda (Co., Ltd.), number average molecular weight 540 Peeloil 1050: long chain alkyl side group polymer, product name "Peeloil 1050", manufactured by Lion Specialty Chemicals (Co., Ltd.)

(Solvent resistance) The hardened layer of the peeling film was wiped with a cotton swab soaked in methyl ethyl ketone to evaluate the solvent resistance. ○: The base material was not exposed even after wiping 50 times. △: The base material was exposed after wiping 10 to 49 times. ×: The base material was exposed after wiping 1 to 9 times.

(Room temperature peeling force) A polyester adhesive tape (31B tape manufactured by Nitto Denko Co., Ltd.: 25 mm width) was attached to a peeling film while being pressed with a 2 kg roller and stored at 23°C for 1 hour. Then, the tape was stretched at an angle of 180° and a peeling speed of 0.3 m/min, and the force required for peeling (N/25 mm) was measured.

(Peeling force after heating) A polyester adhesive tape (31B tape manufactured by Nitto Denko Co., Ltd.: 25 mm width) was attached to a peeling film while being pressed with a 2 kg roller and stored at 70°C for 20 hours. Then, the tape was stretched at an angle of 180° and a peeling speed of 0.3 m/min, and the force required for peeling (N/25 mm) was measured.

(Residual adhesion rate) A polyester adhesive tape (31B tape manufactured by Nitto Denko Co., Ltd.: 25 mm width) was attached to a release film and stored at 23°C for one day. After storage, the tape was torn off and attached to a stainless steel (SUS) plate using a 2 kg roller. Then, the tape was pulled from the SUS plate at an angle of 180° and a peeling speed of 0.3 m/min, and the force required for peeling was measured. As a blank test, the peeling force when the tape was directly attached to the SUS plate and torn off under the same conditions was measured, and the ratio (%) of the former peeling force to the latter peeling force was calculated as the residual adhesion rate. The larger the value, the less the adhesive force of the tape has decreased.

without

without

Claims (4)

A heat-curing stripping coating agent comprises: a polymer (A), a melamine resin (B), an acid catalyst (C), and a polyol (D), wherein the polyol (D) excludes the polymer (A), wherein the polymer (A) comprises 40% to 98% by mass of a structural unit 1,

In the formula, R ¹¹ is a hydrogen atom or a methyl group, R ¹² is an alkyl group having 4 to 11 carbon atoms; and 2% to 60% by mass of the structural unit 2,

In the formula, R ²¹ is a hydrogen atom or a methyl group, R ²² is NHR ^2' or OR ^2' , R ^2' is an alkyl group containing a hydroxyl group, the polyol (D) is one or more selected from the group consisting of alkylene polyols, dimer diols, hydrogenated dimer diols, castor oil-based polyols, hydroxyl-containing fatty acid alkylene polyol esters, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols and polyols (D1), the polyol (D1) contains 50% to 99% by mass of structural units D1 and 1% to 50% by mass of structural units D2 containing a hydroxyl group, and the structural unit D1 is represented by the following formula:

In the formula, ^RD1 is a hydrogen atom or a methyl group, and ^RD2 is an alkyl group having 12 to 28 carbon atoms. A hardened product, which is a hardened product of the heat-curing stripping coating agent as described in claim 1. A heat-curing peeling film, comprising a hardener as described in claim 2 and a plastic film. A method for manufacturing a heat-curing peeling film, comprising: applying the heat-curing peeling coating agent as described in claim 1 to at least one side of a plastic film and heating it.