KR20210097043A - Thermosetting peeling coating agent, cured product, and thermosetting peeling film and production method thereof - Google Patents

Abstract

An object of the present invention is to provide a thermosetting peeling coating agent, a cured product, and a thermosetting peeling film and a method for manufacturing the same. The present invention comprises a thermosetting peeling coating agent comprising: a (meth)acrylic polymer (A), which is a polymer of a monomer containing a long-chain alkyl group-containing (meth)acrylic acid ester (a1); a melamine resin (B); an acid catalyst (C); and a polyol (D).

Description

Thermosetting release coating agent, cured product, and thermosetting release film and manufacturing method thereof

The present disclosure relates to a thermosetting release coating agent, a cured product, and a thermosetting release film and a method for manufacturing the same.

The release film is a process film for cast film formation such as urethane resin, acrylic resin, vinyl chloride resin, etc., a protective film for an adhesive layer such as an adhesive tape, an adhesive sheet, an adhesive film, and a ceramic green sheet or a printed circuit board for manufacturing electronic parts. It is used as a process film.

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

Japanese Patent Laid-Open No. 2000-119608

However, since the release agent described in the said patent document 1 is not bridge|crosslinked, there existed a subject that solvent resistance was low. In addition, there is a demand for improvement in peeling performance. For example, it is required that the peel force at room temperature (room temperature peel force) and the peel force after heating (peel force after heating) with the pressure-sensitive adhesive layer be small, that is, the change in peel force (peel force difference) due to heating is small. . Furthermore, it is also calculated|required that the residual adhesive rate of the adhesive layer after peeling is high.

An object to be solved by the present invention is to provide a thermosetting release coating agent having good solvent resistance, room temperature peeling strength, peeling strength after heating, peeling force difference, and residual adhesiveness.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be solved by using a specific component, as a result of repeating earnest examination.

The present disclosure provides the following items.

(Item 1)

Unit 1

(Wherein, R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is an alkyl group having 8 to 28 carbon atoms)

A polymer comprising (A),

melamine resin (B);

acid catalyst (C), and

polyol (D)

A thermosetting release coating agent comprising a.

(Item 2)

The thermosetting release coating agent according to item 1, wherein the polymer (A) contains a hydroxyl group-containing structural unit.

(Item 3)

The hydroxyl group-containing structural unit is,

Unit 2

[Wherein, R ²¹ is a hydrogen atom or a methyl group, R ²² is NHR ^2A' or OR ^2B' ,

R ^2A' is a hydroxyl group-containing alkyl group,

R ^2B' is (R ^2B1' O) _n H

(R ^2B1' is an alkylene group, and n is an integer of 1 or more)

or

R ^2B2' O(C(=O)(CH ₂ ) ₅ O) _m H

(R ^2B2' is an alkylene group, and m is an integer of 1 or more)

am]

The thermosetting release coating agent according to any one of the above items.

(Item 4)

A cured product of the thermosetting release coating agent according to any one of the above items.

(Item 5)

A thermosetting release film comprising a cured product of the thermosetting release coating agent described in the above item and a plastic film.

(Item 6)

A method for producing a thermosetting release film, comprising the step of heating the thermosetting release coating agent according to any one of the above items applied to at least one side of the plastic film.

In the present disclosure, one or a plurality of the features described above may be provided by further combining in addition to the specified combination.

The thermosetting release coating agent according to the present embodiment is excellent in solvent resistance, room temperature peel strength, peel strength after heating, peel strength difference, and residual adhesion rate.

Throughout the present disclosure, numerical ranges such as respective physical property values and content may be appropriately set (eg, by selecting from the values of the upper and lower limits described in each item below). Specifically, in the case where A4, A3, A2, A1 (referred to as A4 > A3 > A2 > A1) as the upper and lower limits of the numerical value α for the numerical value α, the range of the numerical value α is A4 or less and 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 are exemplified.

[Thermal curing release coating agent: also called coating agent]

The present disclosure, structural unit 1

(Wherein, R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is an alkyl group having 8 to 28 carbon atoms)

A polymer comprising (A),

melamine resin (B);

acid catalyst (C), and

polyol (D)

It provides a thermosetting release coating comprising a.

<Polymer (A): Also called component (A)>

(A) A component can be used individually or by 2 or more types.

(composition unit 1)

Structural unit 1 is a (meth)acrylic acid ester (a1) containing a long-chain alkyl group as a monomer

(Wherein, R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is an alkyl group having 8 to 28 carbon atoms)

It is a structural unit included in the polymer (A) when using. The long-chain alkyl group-containing (meth)acrylic acid ester (a1) may be used alone or in combination of two or more.

Examples of the alkyl group include a straight-chain alkyl group, a branched alkyl group, and a cycloalkyl group.

A straight-chain alkyl group is _{represented by the general formula of -C n} H _2n+1 (n is an integer greater than or equal to 1).

The branched alkyl group is a group in which at least one hydrogen atom in the straight-chain alkyl group is substituted with an alkyl group, and does not have a cyclic structure.

Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a cross-linked cycloalkyl group, and a condensed cyclic cycloalkyl group. Also, a group in which at least one hydrogen atom in the cycloalkyl group is substituted with an alkyl group is also referred to as a cycloalkyl group.

In the present disclosure, monocyclic refers to a cyclic structure that does not have a bridged structure therein formed by a covalent bond of carbon. Further, the condensed ring means a cyclic structure in which two or more monocyclic rings share two atoms (that is, only one side of each ring is shared (condensed) with each other). Cross-exchange means a cyclic structure in which two or more monocyclic rings share three or more atoms.

An alkyl group having 8 to 28 carbon atoms includes an octyl group, a nonyl group, a decamethyl group, an undecyl group, a dodecyl group (lauryl group), a tridecyl group, a tetradecyl group (myristyl group), a pentadecyl group, and a hexadecyl group (palmi group). tyl group), heptadecyl group, octadecyl group (stearyl group), nonadecyl group, eicosyl group, heneicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octa Kosyl group and the like are exemplified.

The upper and lower limits of the carbon number of the alkyl group of R ¹² are 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9 and 8 are exemplified. In one embodiment, 8-28 are preferable and, as for the said carbon number, 12-28 are more preferable.

Long-chain alkyl group-containing (meth)acrylic acid esters are octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 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, docosyl (meth) acrylate, tricosyl (meth) acrylate, tetracosyl (meth) acrylate, pentacosyl (meth) acrylic Rate, 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, isostearyl (meth) acrylate, and the like. Among them, lauryl (meth)acrylate and stearyl (meth)acrylate are particularly preferable from the viewpoints of availability and light peeling.

The upper and lower limits of the content of the structural unit 1 with respect to 100 mass % of the polymer (A) are 100, 99, 98, 97, 96, 95, 94, 92, 91, 90, 88, 87, 85, 83, 82, 81, 80, 79, 77, 75, 73, 71, 70, 69, 67, 65, 63, 60, 59, 58, 55, 50, 49, 45, 43, 40, 38, 35, 33, 31, 30 mass % etc. are illustrated. In one embodiment, 30-100 mass % is preferable and, as for the said content, 35-99 mass % is more preferable.

The upper and lower limits of the content of the structural unit 1 with respect to 100 mol% of the polymer (A) are 100, 99, 98, 97, 96, 95, 94, 92, 91, 90, 88, 85, 80, 77, 75, 70, 65, 60, 58, 55, 50, 45, 40, 38, 35, 30, 25, 20 mol% etc. are illustrated. In one embodiment, as for the said content, 20-100 mol% etc. are illustrated.

(Constituent unit containing hydroxyl group)

In one embodiment, the said polymer (A) contains a hydroxyl-containing structural unit. The hydroxyl group-containing structural unit is a structural unit contained in the polymer (A) when a hydroxyl group-containing monomer is used as the monomer. A hydroxyl-containing monomer can be used individually or in 2 or more types. Examples of the hydroxyl group-containing structural unit include the following structural unit 2 and a structural unit derived from a monomer having two or more hydroxyl groups.

In the present disclosure, even if the polymer (A) has two or more hydroxyl groups (-OH), the polymer (A) is treated as not applicable to the following polyol (D).

(composition unit 2)

Structural unit 2 is a hydroxyl group-containing (meth)acrylic monomer (a2) as a monomer

[Wherein, R ²¹ is a hydrogen atom or a methyl group, R ²² is NHR ^2A' or OR ^2B' ,

R ^2A' is a hydroxyl group-containing alkyl group,

R ^2B' is (R ^2B1' O) _n H

(R ^2B1' is an alkylene group, and n is an integer of 1 or more)

or

R ^2B2' O(C(=O)(CH ₂ ) ₅ O) _m H

(R ^2B2' is an alkylene group, and m is an integer of 1 or more)

am]

It is a structural unit included in the polymer (A) when using. The hydroxyl group-containing (meth)acrylic monomer (a2) may be used alone or in combination of two or more.

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

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

The hydroxyl group-containing (meth)acrylic monomer (a2) is a hydroxyl group-containing (meth)acrylic ester, polyalkylene glycol mono(meth)acrylate, caprolactone-modified hydroxyalkyl (meth)acrylate, hydroxyl group-containing (meth)acrylamide etc. are exemplified.

The hydroxyl group-containing (meth)acrylic ester is a monomer in which R ²² of the ^{hydroxyl group-containing (meth)acrylic monomer (a2) is OR 2B1'} OH, ie, R ^2B' is a hydroxyl group-containing alkyl group. The meaning of the symbol is the same as above.

The hydroxyl group-containing (meth)acrylic ester is 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 1, 4- cyclohexane dimethanol mono (meth)acrylate, etc. are illustrated.

Polyalkylene glycol mono(meth)acrylate is a monomer in which R ²² of the hydroxyl group-containing (meth)acrylic monomer (a2) is O(R ^2B1' O) _n H. The meaning of the symbol is the same as above. In one embodiment, n is preferably 1 or more, more preferably ^{1-60, and R 2B1'} is preferably an ethylene group or a propylene group.

Commercially available polyalkylene glycol mono(meth)acrylates are Bremmer PE-90, Bremma 200, Bremma 350, Bremma PME-400, Bremma AE-400, Bremma PME-1000, and Bremma PME-1000. Remma PME-2000 (manufactured by NOF CORPORATION) and the like are exemplified.

Caprolactone-modified hydroxyalkyl (meth)acrylate is a monomer in which R ²² of the ^{hydroxyl group-containing (meth)acrylic monomer (a2) is OR 2B2′} O(C(=O)(CH ₂ ) ₅ O) _m H. The meaning of the symbol is the same as above. In one embodiment, 1 or more of m are preferable, 1-6 are more preferable, and 1-3 are still more preferable. R ^2B2' is preferably an alkylene group having 2 to 6 carbon atoms, more preferably an ethylene group.

Commercial products of caprolactone-modified hydroxyalkyl (meth)acrylate are "PLACCEL FM1", "PLACCEL FM2", "Placcel FM1D", "Placcel FM2D", "Placcel FM3", and "Placcel FM3". Cell FM3X", "Plaque Cell FM4", "Plaque Cell FM-5", "Plaque Cell FA1", "Plaque Cell FA2", "Plaque Cell FA1D", "Plaque Cell FA1DDM", "Plaque Cell FA2D", "Plaque Cell FA2D", "Plaque Cell FA1D" Cell FA3", "Place Cell FA4", "Place Cell FA5" (all manufactured by Daicel Corporation) and the like are exemplified.

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

As a monomer provided with two or more hydroxyl groups, glycerol mono(meth)acrylate etc. are illustrated.

The upper limit and the lower limit of the content of the hydroxyl group-containing structural unit with respect to 100 mass% of the polymer (A) are 70, 69, 67, 65, 62, 60, 59, 57.55, 54, 53, 51 with respect to the mass of the polymer (A). , 50, 49, 47, 45, 44, 42, 40, 39, 37, 35, 34, 33, 31, 30, 29, 27, 25, 23, 21, 20, 18, 15, 12, 10, 9 , 7, 5, 4, 3, 2, 1, 0.9, 0.5, 0.1, 0 mass % etc. are illustrated. In one embodiment, 0-70 mass % is preferable and, as for the said content, 1-65 mass % is more preferable.

The upper and lower limits of the content of the hydroxyl group-containing structural unit with respect to 100 mol% of the polymer (A) are 80, 79, 77, 75, 73, 71, 70, 69, 67, 65, 63, 62, 60, 59, 57 , 55, 53, 50, 49, 47, 45, 42, 40, 39, 37, 35, 31, 30, 29, 27, 25, 23, 20, 18, 15, 12, 10, 9, 7, 5 , 4, 3, 2, 1, 0.9, 0.5, 0.1, 0 mol% and the like are exemplified. In one embodiment, as for content of the hydroxyl-containing structural unit with respect to 100 mol% of polymer (A), 0-80 mol% is preferable.

The upper and lower limits of the mass ratio of the hydroxyl group-containing structural unit and the structural unit 1 (the mass of the hydroxyl group-containing structural unit/the mass of the structural unit 1) in the polymer (A) are 2.3, 2.1, 2, 1.9, 1.7, 1.5, 1.3 , 1.1, 1, 0.9, 0.7, 0.5, 0.3, 0.1, 0, and the like are exemplified. In one embodiment, the mass ratio is preferably 0 to 2.3.

The upper and lower limits of the substance amount ratio (molar ratio) of the hydroxyl group-containing structural unit and the structural unit 1 (substance amount of the hydroxyl group-containing structural unit/substance amount of the structural unit 1) in the polymer (A) are 4, 3.9, 3.7, 3.5, 3.3 , 3.1, 3, 2.9, 2.7, 2.5, 2.3, 2, 1.9, 1.7, 1.5, 1.3, 1.1, 1, 0.9, 0.7, 0.5, 0.3, 0.1, 0, and the like are exemplified. In one embodiment, as for the said substance amount ratio (molar ratio), 0-4 are preferable.

(composition unit 3)

In one embodiment, the polymer (A) is

Unit 3

(Wherein, R ³¹ is a hydrogen atom or a methyl group, and R ³² is an alkyl group having 1 to 7 carbon atoms)

may include.

Structural unit 3 is a (meth)acrylic acid ester (a3) containing a short-chain alkyl group as a monomer

(Wherein, R ³¹ is a hydrogen atom or a methyl group, and R ³² is an alkyl group having 1 to 7 carbon atoms)

It is a structural unit included in the polymer (A) when using.

Examples of the alkyl group having 1 to 7 carbon atoms include linear, branched, and cycloalkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group.

As for the upper limit and the lower limit of content of the structural unit 3 with respect to 100 mass % of polymer (A), 30, 25, 20, 15, 10, 9, 7, 5, 4, 2, 1, 0 mass % etc. are illustrated. In one embodiment, as for the said content, 0-30 mass % is preferable.

The upper and lower limits of the content of the structural unit 3 with respect to 100 mol% of the polymer (A) are 30, 29, 27, 25, 23, 21, 20, 19, 17, 15, 13, 10, 9, 7, 5, 4, 2, 1, 0 mol%, etc. are illustrated. In one embodiment, as for the said content, 0-30 mol% is preferable.

(Structural units other than Structural Units 1-3: Also called other constituent units)

In one embodiment, the polymer (A) may contain structural units other than structural units 1 to 3.

Structural units other than structural units 1 to 3 are poly(meth)acrylic acid, styrene, alkenyl (meth)acrylate, (meth)acrylamide, (meth)acrylonitrile, ethylene glycol di(meth)acrylate, etc. When using a functional (meth)acrylate etc. as a monomer, the structural unit etc. contained in a polymer (A) are illustrated.

As for content of other structural units with respect to 100 mass % of polymer (A), less than 10 mass %, less than 5 mass %, less than 2 mass %, less than 1 mass %, less than 0.1 mass %, 0 mass % etc. are illustrated. In addition, the content of other structural units with respect to 100% by mass of the hydroxyl group-containing structural unit and any one of the structural units 1 to 3 is less than 10% by mass, less than 5% by mass, less than 2% by mass, less than 1% by mass, Less than 0.1 mass %, 0 mass %, etc. are illustrated.

Examples of the content of other structural units relative to 100 mol% of the polymer (A) include less than 10 mol%, less than 5 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, and 0 mol%. In addition, the content of other structural units with respect to 100 mol% of the hydroxyl group-containing structural unit and any one of structural units 1 to 3 is less than 10 mol%, less than 5 mol%, less than 2 mol%, less than 1 mol%, Less than 0.1 mol%, 0 mol%, etc. are illustrated.

<Physical properties of polymer (A), etc.>

The upper and lower limits of the number average molecular weight of the polymer (A) are 80000, 75000, 60000, 50000, 40000, 30000, 25000, 24700, 24000, 23000, 20000, 19500, 19000, 18500, 18000, 17500, 17000, 16500, 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. do. In one embodiment, the number average molecular weight is preferably 8000 to 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, 46000, 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 and the like are exemplified. In one embodiment, the weight average molecular weight is preferably 20000 to 20000.

A weight average molecular weight and a number average molecular weight can be calculated|required as polystyrene conversion values measured in the appropriate solvent by gel permeation chromatography (GPC), for example. As for detailed conditions, the following etc. are illustrated.

Model: Product name "HLC-8220" (manufactured by Tosoh Corporation)

Column: Product name "PLgel MIXED-C" (manufactured by Agilent Technologies, Inc.) × 2

Developing solvent, flow rate: tetrahydrofuran, 1.0 mL/min

Measuring temperature: 40℃

Detector: RI

Standard: monodisperse polystyrene

Polymer concentration: 0.2%

The upper and lower limits of the hydroxyl value of the polymer (A) are 300, 275, 250, 225, 210, 203, 200, 175, 150, 125, 100, 75, 52, 50, 40, 35, 30, 25, 22 , 20, 15, 10, 9, 7, 5, 4, 2, 1 mgKOH/g and the like. In one embodiment, as for the hydroxyl value of a polymer (A), 1-300 mgKOH/g is preferable from a viewpoint of making peelability and solvent resistance compatible.

A hydroxyl value is measured by the method based on JISK1557-1.

As for the manufacturing method of a polymer (A), various well-known radical polymerization etc. are illustrated. Radical polymerization is achieved by heating in the presence of a radical polymerization initiator.

The radical polymerization initiator is an inorganic peroxide such as hydrogen peroxide, ammonium persulfate and potassium persulfate, an organic peroxide such as benzoyl peroxide, dicumyl peroxide, lauryl peroxide, 2,2'-azobisisobutyronitrile, dimethyl- Azo compounds, such as 2,2'- azobisisobutyrate, etc. are illustrated. A radical polymerization initiator may be used individually or in 2 or more types. As for the usage-amount of a radical polymerization initiator, about 1-10 mass parts is preferable with respect to 100 mass parts of all monomer components.

When producing the polymer (A), if necessary, a chain transfer agent may be used. Examples of the chain transfer agent include lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and α-methylstyrene dimer. The chain transfer agent may be used alone or in combination of two or more. As for the usage-amount of a chain transfer agent, about 0-5 mass parts is preferable with respect to 100 mass parts of all monomer components.

The upper limit and the lower limit of content of the polymer (A) with respect to 100 mass % of coating agent solid content are 30, 29, 28.8, 28, 27, 25, 23, 20, 19, 17, 15, 14.4, 14, 12, 10, 9.6 , 9.5, 9, 8, 7, 5, 4.8, 4, 2, 1 mass %, etc. are illustrated. In one embodiment, as for the said content, 1-30 mass % is preferable.

<Melamine resin: also called (B) component>

(B) A component can be used individually or by 2 or more types.

(B) A component is the following melamine compound

(Wherein, R ^m1 to ^{R m6} are each independently selected from a hydrogen atom, a methylol group, a methoxymethyl group, an ethoxymethyl group, an n-butoxymethyl group, and an isobutoxymethyl group)

A melamine resin including a structural unit derived from is exemplified. In one embodiment, the average degree of polymerization of (B) component is 1.1-10.

(B) component is a melamine resin containing a structural unit derived from a methylated melamine and/or a butylated melamine at the point which is excellent in the sclerosis|hardenability of a coating agent, and the compatibility balance with (A) component and (D)component mentioned later is preferable In the methylated melamine ^{, at least one of the R m1} to ^{R m6} is a methoxymethyl group (—CH ₂ OCH ₃ ), and in the butylated melamine ^{, at least one of the R m1} to ^{R m6} is an n-butoxymethyl group (—CH ₂ OCH). ₂ CH ₂ CH ₂ CH ₃ ) and an isobutoxymethyl group (—CH ₂ OCH(CH ₃ )CH ₂ CH ₃ ) respectively.

The component (B) is preferably a resin containing a structural unit derived from full ether type methylated melamine in which all ^{of the above R m1} to ^{R m6 are methoxymethyl groups (hereinafter, full ether type methylated melamine resin) from the viewpoint of excellent curability.} and, in terms of compatibility with component (A) and component (D), ^{all of said R m1} to ^{R m6} are any one of n-butoxymethyl group and isobutoxymethyl group, a structural unit derived from full ether type butylated melamine Resin (hereinafter, full ether type butylated melamine resin) is preferable. ^{Further, from the viewpoint} of excellent balance between curability and compatibility with component (A) and component (D), ^{at least one of R m1} to R m6 is a methoxymethyl group, and the remainder is n-butoxymethyl group and isobutoxy group, respectively. A resin containing a structural unit derived from full ether type methyl-butylated melamine as any one of the methyl groups (hereinafter, full ether type methyl/butylated melamine resin) is preferred.

(B) Commercial products of component are Cymel 300, Cymel 301, Cymel 303LF, Cymel 350, Cymel 370N, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712. , Cymel 701, Cymel266, Cymel267, Cymel285, Cymel232, Cymel235, Cymel236, Cymel238, Cymel272, Cymel212, Cymel253, Cymel254, Cymel Mel 202, Cymel 207, My Coat 506 (above, Allnex Japan Inc.), NIKALAC MW-30M, NIKALAC MW-30, NIKALAC MW-30HM, Nika Rock MW-390, Nika Rock MW-100LM, Nika Rock MX-750LM, Nika Rock MW-22, Nika Rock MS-21, Nika Rock MS-11, Nika Rock MW-24X, Nika Rock MS-001, Nika Rock MX -002, Nikarak MX-730, Nikalac MX-750, Nikarak MX-708, Nikarak MX-706, Nikarak MX-042, Nikarak MX-035, Nikarak MX-45, Nikarak MX-43 , Nikalac MX-417, Nikalac MX-410 (above, manufactured by SANWA CHEMICAL CO., LTD.), U-VAN 20SB, Yuban 20SE60, Yuban 21R, Yuban 22R, Yuban 122, Yuban 125, Yuban 220, Yuban 225, Yuban 228, Yuban 2020 (above, manufactured by Mitsui Chemicals, Inc.), AMIDIR J-820-60, AMIDIR L- 109-65, Amedia L-117-60, Amedia L-127-60, Amedia 13-548, Amedia G-821-60, Amedia L-110-60, Amedia L-125-60, Amedia L-166-60B (above, the product of DIC Corporation) etc. are illustrated.

The upper limit and the lower limit of content of the melamine resin (B) with respect to 100 mass % of coating agent solid content are 70, 69, 67, 65, 63, 61, 60, 59, 57, 55, 53, 51, 50, 49, 48.1, 48, 47, 45, 44, 42, 41, 40.4, 40, 39, 38.5, 38, 37, 35, 32.5, 31, 30, 29, 28.8, 28, 27.5, 25, 23, 21, 20% by mass, etc. This is exemplified. In one embodiment, 20-70 mass % is preferable and, as for the said content, 25-60 mass % is more preferable.

<Acid catalyst: also called (C) component>

(C) A component can be used individually or by 2 or more types.

(C) As for a component, an inorganic acid, an organic acid, a thermal acid generator, etc. are illustrated.

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

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

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

Organic sulfonic acid silver 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, nonylnaphthalenesulfonic acid, and the like.

Organic silver phosphate, methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate , Stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate , diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, bisnonylphenyl acid phosphate and the like are exemplified.

A sulfonium salt, a benzothiazolium salt, an ammonium salt, a phosphonium salt etc. are illustrated as a thermal acid generator.

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

The upper limit and the lower limit of content of the acid catalyst (C) with respect to 100 mass % of coating agent solid content are 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, 3.9, 3.8, 3.5 , 3, 2.5, 2, 1.5, 1 mass %, etc. are illustrated. In one embodiment, as for the said content, 1-10 mass % is preferable.

<Polyol: Also called (D)component>

(D) A component can be used individually or by 2 or more types.

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

(D) Examples of the component include alkylene polyol, dimer diol, hydrogenated dimer diol, castor oil-based polyol, hydroxyl group-containing fatty acid alkylene glycol ester, polyether polyol, polyester polyol, polycarbonate polyol, and polyolefin polyol.

(alkylene polyol)

In the present disclosure, "alkylene polyol" means a compound consisting of an alkylene group and two or more hydroxyl groups.

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

The straight-chain alkylene polyol includes ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and the like are exemplified.

Branched alkylene polyol, neopentyl glycol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,4-dibutyl-1,5-pentanediol, 3 -methyl-1,5-pentanediol, 1,2-propanediol, 1,2-butanediol, pentaerythritol, trimethylolpropane, etc. are illustrated.

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

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 tricyclodecane dimethanol.

(dimerdiol)

Dimer diol refers to a product obtained by reducing a reaction product of a cyclic and/or acyclic dimer acid and methanol generally obtained by dimerizing a higher unsaturated fatty acid. As for the dimerization reaction of a higher unsaturated fatty acid, the method etc. which are described in Unexamined-Japanese-Patent No. 9-136861 are illustrated. In addition, hydrogenated dimer diol is what made dimer diol hydrogen addition-react.

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

Unsaturated monocarboxylic acids 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, elaidin. acid, vaccenic acid, eicosenoic acid, erucic acid, cetolenic acid, brassidic acid, and the like are exemplified. Among these, oleic acid and/or linoleic acid are preferable.

(Caster oil-based polyol)

Examples of castor oil-based polyols include glycerin hydroxyl group-containing fatty acid (poly)esters.

The glycerol hydroxyl group-containing fatty acid (poly)ester means a (poly)ester (monoester, diester, triester) obtained by reacting at least one hydroxyl group of glycerin with a hydroxyl group-containing fatty acid.

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

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

Hydroxy group-containing saturated long-chain fatty acids include hydroxylauryl acid, hydroxytridecylic acid, hydroxymyristylic acid, hydroxypentadecylic acid, hydroxypalmitylic acid, hydroxyheptadecylic acid, hydroxystearylic acid, hydroxy Nonadecylic acid, hydroxyeicosylic acid, hydroxyheneicosylic acid, hydroxydocosylic acid, hydroxytricosylic acid, hydroxytetracosylic acid, hydroxypentacosylic acid, hydroxyhexacosylic acid, hydroxyheptacosylic acid, hydroxy Hydroxyoctacosylic acid, hydroxyisododecylic acid, hydroxyisotridecylic acid, hydroxyisomyristylic acid, hydroxyisopentadecylic acid, hydroxyisohexadecylic acid, hydroxyisoheptadecylic acid, hydroxyisoste aryl acid, aleuritic acid, and the like are exemplified.

Hydroxyl group-containing unsaturated long-chain fatty acids include hydroxyl group-containing monounsaturated long-chain fatty acids, hydroxyl group-containing diunsaturated long-chain fatty acids, hydroxyl group-containing triunsaturated long-chain fatty acids, hydroxyl group-containing tetraunsaturated long-chain fatty acids, hydroxyl group-containing pentaunsaturated long-chain fatty acids, hydroxyl group-containing hexaunsaturated long-chain fatty acids, etc. is exemplified

Hydroxyl group-containing monounsaturated long-chain fatty acids include ricinoleic acid, hydroxymyristoleic acid, hydroxypalmitoleic acid, hydroxysapienoic acid, hydroxyoleic acid, hydroxyelaidic acid, hydroxyvaccenic acid, and hydroxygadoleic acid. , hydroxyeicosenoic acid, hydroxyerucic acid, hydroxynervonic acid, and the like are exemplified.

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

Examples of the hydroxyl group-containing triunsaturated long-chain fatty acid include hydroxylinolenic acid, hydroxypinolenic acid, hydroxyeleostearic acid, hydroxyimidic acid, and hydroxyeicosatrienoic acid.

Examples of the hydroxyl group-containing tetraunsaturated long-chain fatty acid include hydroxystearidonic acid, hydroxyarachidonic acid, and hydroxyadrenic acid.

Examples of the hydroxyl group-containing pentaunsaturated long-chain fatty acid include hydroxyboseopentaenoic acid, hydroxyeicosapentaenoic acid, hydroxyosbondic acid, hydroxyclupanodonic acid, and hydroxytetracosapentaenoic acid.

Examples of the hydroxyl group-containing hexaunsaturated long-chain fatty acid include hydroxydocosahexaenoic acid and hydroxynisinic acid.

(Hydroxy group-containing fatty acid alkylene glycol ester)

In the present disclosure, "hydroxyl group-containing fatty acid alkylene glycol ester" means an ester obtained by reacting a hydroxyl group-containing fatty acid with an alkylene polyol.

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

(polyether polyol)

In the present disclosure, "polyether polyol" means a compound having, for example, two or more hydroxyl groups and two or more repeating units including ether bonds in succession.

In one embodiment, the polyetherpolyol has the structure

HO—(R ^Ether —O—) _n H

^(Wherein , R Ether is an alkylene group, an arylene group, or an arylenealkylenearylene group, and n is an integer of 2 or more)

is indicated by

Examples of the alkylene group include a straight-chain alkylene group, a branched alkylene group, and a cycloalkylene group.

A straight-chain alkylene group, - (CH _{2) n} - is represented by the general formula (n is an integer of 1 or more). The straight-chain alkylene group includes a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, a n-nonylene group, and a n-deca group. A methylene group etc. are illustrated.

The branched alkylene group is a group in which at least one hydrogen atom of the straight-chain alkylene group is substituted with an alkyl group. Examples of the branched alkylene group include an i-propylene group, a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, and a trimethylhexylene group.

Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a cross-linked cycloalkylene group, and a condensed cyclic cycloalkylene group. In the cycloalkylene group, one or more hydrogen atoms may be substituted with a straight-chain or branched alkyl group.

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

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

Examples of the condensed cyclic cycloalkylene group include a bicyclodecylene group.

Examples of the arylene group include a phenylene group, a naphthylene group, and a fluorenylene group.

The arylene alkylene arylene group,

—R ^arylene —R ^alkylene —R ^arylene —

^(Wherein , R ^arylene represents an arylene group, and R alkylene represents an alkylene group)

is a group represented by

Examples of the arylene alkylene arylene group include a phenylene dimethyl methylene phenylene group.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and an alkylene oxide adduct of polyol.

Commercially available polyether polyols are ADECA polyether GM-30, ADECA polyether P-400, ADEKA polyether G-400, ADEKA polyether T-400, ADEKA polyether AM-302 (above, right or wrong). ADEKA Corporation product) etc. are illustrated.

(polyester polyol)

In the present disclosure, "polyester polyol" means a compound having two or more hydroxyl groups and two or more consecutive repeating units including ester bonds. In addition, polycaprolactone polyol is a kind of polyester polyol.

In one embodiment, the polyester polyol has the following structural formula

HO—{R ^aEster —OC( ^{═O)—R bEster} —C(═O)O} _m —R ^cEster —OH

^(Wherein , R aEster , R ^bEster and R ^cEster are each independently an alkylene group or an arylene group, and m is an integer of 2 or more)

is indicated by

Examples of the polyester polyol include a reaction product of a polycarboxylic acid or an anhydride thereof and a polyol.

As for polycarboxylic acid, dicarboxylic acid etc. are illustrated.

Silver dicarboxylic acid, 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-methyladiic acid Dicarboxylic acids such as finic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, etc. This is exemplified.

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

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

(polycarbonate polyol)

In the present disclosure, "polycarbonate polyol" refers to a compound having two or more hydroxyl groups and two or more repeating units including carbonate bonds.

In one embodiment, the polycarbonate polyol has the following structural formula

HO—{R ^aCarbo —OC(═O)O} _p —R ^bCarbo —OH

^(Wherein , R aCarbo and R ^bCarbo are each independently an alkylene group, and p is an integer of 2 or more)

is indicated by

Examples of the polycarbonate polyol include a reaction product of a polyol and phosgene, and a ring-opened polymer of a cyclic carbonate (such as an alkylene carbonate).

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

Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate.

(polyolefin polyol)

Examples of the polyolefin polyol include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorinated products thereof. As a commercial item of polyolefin polyol, NISSO-PB GI-1000 (Nippon Soda Co., Ltd. product) etc. are illustrated.

((D) physical properties of component, etc.)

(D) 3000, 2500, 2000, 1500, 1000, 500, 250, 100 etc. are illustrated as for the upper limit and minimum of the molecular weight of a component. In one embodiment, the molecular weight is preferably 100 to 3000.

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

(D) The upper limit and the lower limit of the hydroxyl value of the component are 1500, 1400, 1300, 1255, 1250, 1200, 1100, 1000, 900, 800, 778, 750, 700, 600, 500, 400, 300, 250, 200 , 150, 100, 90, 75, 50, 40 mgKOH/g and the like. In one embodiment, the hydroxyl value is preferably 40 to 1500 mgKOH/g.

The upper limit and the lower limit of content of polyol (D) in 100 mass % of coating agent solid content are 65, 63, 62.5, 61, 60, 59, 58, 57.7, 57.5, 57, 55, 53, 52.9, 52, 51, 50, 49, 48.1, 48, 47, 45, 43, 41, 40, 39, 38.5, 37, 35, 32, 31.3, 31, 30, 29, 27.5, 27, 26.4, 26, 25, 23, 21, 20 mass % and the like are exemplified. In one embodiment, as for the said content, 20-65 mass % is preferable.

<Organic solvent (E): also called (E) component>

In one embodiment, the coating agent may include an organic solvent (E). (E) A component can be used individually or by 2 or more types.

(E) As for component, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, butyl acetate, toluene, xylene, isopropyl alcohol, ethanol, a butanol, etc. are illustrated. Among these, from a soluble viewpoint of resin, methyl ethyl ketone, methyl isobutyl ketone, isopropyl alcohol, ethyl acetate, butyl acetate, and toluene are preferable.

In one embodiment, as for content of (E) component in a coating agent, the grade from a viewpoint of application|coating suitability to solid content concentration of a coating agent being 1-50 mass % is preferable. By setting it as such a numerical range, it can make it easy to balance sclerosis|hardenability and pot life of a cured film.

<additive>

The said coating agent can contain the thing which does not correspond to any of the said (A)-(E) components as an additive.

Additives include binders, defoamers, non-slip agents, preservatives, rust inhibitors, pH adjusters, antioxidants, pigments, dyes, lubricants, leveling agents, conductive agents, polybutadiene, polyisoprene, polychloroprene, polypentadiene, polybutene, polyiso Butylene, polystyrene, isoprene/butadiene copolymer, styrene/isoprene copolymer, polyolefin and derivatives thereof, etc., silicone resins, isocyanate group-containing compounds, epoxy group-containing compounds, amines, carboxylic acid anhydrides, and long-chain alkyl group-containing alcohols are exemplified. The said binder is not specifically limited, Well-known acrylic resin, a urethane resin, a polyester resin, an epoxy resin, an alkyd resin, etc. are illustrated.

In one embodiment, as for content of an additive, less than 1 mass %, less than 0.1 mass %, less than 0.01 mass %, 0 mass %, etc. are illustrated with respect to 100 mass % of coating agents. Moreover, less than 1 mass %, less than 0.1 mass %, less than 0.01 mass %, 0 mass % etc. are illustrated with respect to 100 mass % of any component in (A)-(E) component.

The coating agent can be produced by dispersing and mixing the components (A) to (D) and, if necessary, the component (E) and additives by various known means. In addition, the order of addition of each component is not specifically limited. In addition, as the dispersion/mixing means, various well-known devices (emulsification disperser, ultrasonic dispersion device, etc.) can be used.

[Cured material]

The present disclosure provides a cured product of the thermosetting release coating agent.

In one embodiment, the cured product is a thermosetting product of the thermosetting release coating agent. Examples of curing conditions include those described later.

[thermal curing release film]

The present disclosure provides a thermosetting release film comprising a cured product of the thermosetting release coating agent and a plastic film.

The plastic film is polycarbonate, polymethyl methacrylate, polystyrene, polyethylene terephthalate (PET), polyethylene naphthalate, polyimide, polyolefin, nylon, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin. , films made of plastics such as norbornene-based resins are exemplified, and among these, polyethylene terephthalate is preferable from the viewpoints of performance such as transparency, dimensional stability, mechanical properties, and chemical resistance.

The plastic film may be subjected to surface treatment (corona discharge, etc.) if necessary. Moreover, the layer by coating agents other than the thermosetting peeling coating agent of this indication may be formed on the single side|surface or both surfaces of the plastic film.

[Manufacturing method of thermosetting release film]

The present disclosure provides a method of manufacturing a thermosetting release film comprising a step of heating the thermally curable release coating agent applied to at least one side of a plastic film.

Examples of the coating method include spray, roll coater, reverse roll coater, gravure coater, knife coater, bar coater, and dot coater.

The application amount is not particularly limited. The amount used is preferably about 0.1 to 10 g/m 2 , and more preferably 0.2 to 5 g/m 2 .

As the heating method, drying with a circulating air dryer or the like is exemplified. As drying (curing) conditions, the time at about 90-170 degreeC is about 30 second - about 2 minutes, etc. are illustrated.

(Example)

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples. However, the description of the preferred embodiment and the following examples are provided for the purpose of illustration only, and not for the purpose of limiting the present invention. Accordingly, the scope of the present invention is not limited to the embodiments specifically described in this specification nor to the examples, but is limited only by the claims. In addition, in each Example and Comparative Example, unless otherwise specified, numerical values such as parts and % are based on mass.

Preparation Example 1

To a four-necked flask equipped with a stirrer, reflux cooling tube, nitrogen inlet tube, thermometer, and dropping funnel, 40 parts of stearyl acrylate, 55 parts of lauryl acrylate, and 5 parts of 2-hydroxylethyl methacrylate were added, and as an initiator 2 parts of azobisisobutyronitrile and 153 parts of methyl ethyl ketone were put as a solvent, it heated up gradually to 80 degreeC, it was made to react for 9 hours, and the polymer solution with a solid content concentration of 40% was obtained.

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

SA: stearyl acrylate

SMA: Stearyl Methacrylate

LA: lauryl acrylate

LMA: Lauryl Methacrylate

2EHA: 2-ethylhexyl acrylate

HEMA: 2-hydroxylethyl methacrylate

HEA: 2-hydroxylethyl acrylate

HBA: 4-hydroxylbutyl acrylate

GLM: Glycerin Monomethacrylate

BA: butyl acrylate

MMA: methyl methacrylate

MAA: methacrylic acid

The unit of hydroxyl value is mgKOH/g.

Example 1

(A) 10 parts in terms of solid content of the polymer prepared in Production Example 1 as component, (B) 30 parts of full ether type methylated melamine resin (product name "Cymel 303LF": Allnex Japan Co., Ltd. product) as component (B) 4 parts of para-toluenesulfonic acid as component C) and 60 parts of hydrogenated dimerdiol (product name "Pripol 2033", manufactured by Croda Japan KK) as component (D) were added, diluted with toluene to obtain solid content It mix|blended so that it might become 10%. Next, this solution was applied to a polyethylene terephthalate film (thickness 75 mu m) so that the dry coating film had a film thickness of 1 mu m, followed by drying at 120 DEG C for 1 minute to obtain a release film.

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

Methylated melamine resin: Product name 「Cymel 303LF」, full ether type methylated melamine resin, Allnex Japan Co., Ltd.

Butylated melamine resin: Product name 「Yuban 20SE60」, full ether type butylated melamine resin, Mitsui Chemicals Co., Ltd.

Methyl-butylated melamine resin: Product name "Nikalac MX-45", full ether type methyl-butylated melamine resin, manufactured by Sanwa Chemical Co., Ltd.

Hydrogenated dimerdiol: Product name 「Pripol2033」, manufactured by Croda Japan Co., Ltd., number average molecular weight 540

Castor oil modified polyol: Product name 「URIC F-97」, manufactured by ITOH OIL CHEMICALS CO., LTD.

GM-30: Product name 「Adeka Polyether GM-30」, manufactured by Adeka Corporation, polyether polyol number average molecular weight 300

PCL312: Product name 「Placcel 312」, manufactured by Daicel Corporation, polycaprolactone polyol number average molecular weight 1250

Duranol T4671: Product name 「DURANOL T4671」, Asahi Kasei Corp., polycarbonate polyol number average molecular weight 1000

(solvent resistance)

The cured product layer of the release film was rubbed with a cotton swab dipped in methyl ethyl ketone, and solvent resistance was evaluated.

○: Even after rubbing 50 times, the base material is not exposed.

(triangle|delta): When rubbing 10-49 times, a base material is exposed.

x: When rubbed 1 to 9 times, the base material is exposed.

(Room temperature peeling force)

A polyester adhesive tape (manufactured by Nitto Denko Corporation, 31B tape: width 25 mm) was bonded to the release film while being compressed with a roller of 2 kg, and stored at 23° C. for 1 hour. Next, the tape was pulled at an angle of 180° at a peeling speed of 0.3 m/min, and the force required for peeling (N/25 mm) was measured.

(Peel force after heating)

A polyester adhesive tape (manufactured by Nitto Denko Co., Ltd., 31B tape: width 25 mm) was bonded to the release film while being compressed with a roller of 2 kg, and stored at 70° C. for 20 hours. Next, the tape was pulled at an angle of 180° at 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 (manufactured by Nitto Denko Co., Ltd., 31B tape: width 20 mm) was bonded to the release film, and stored at 23° C. for 1 day. After storage, the tape was removed and adhered to the SUS plate with a 2 kg roller. Next, the tape was pulled from the SUS plate at an angle of 180° at a peeling rate of 0.3 m/min, and the force required for peeling was measured. As a blank, the peeling force when the tape was directly bonded to the SUS plate and peeled off under the same conditions was measured, and the ratio (%) of the former peeling force to the latter peeling force was determined as the residual adhesive rate. It shows that the adhesive force of a tape does not fall, so that this value is large.

Claims (6)

Unit 1

(Wherein, R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is an alkyl group having 8 to 28 carbon atoms)
A polymer comprising (A),
melamine resin (B);
acid catalyst (C), and
polyol (D)
A thermosetting release coating agent comprising a.
According to claim 1,
The thermosetting release coating agent in which the said polymer (A) contains a hydroxyl-containing structural unit.
3. The method of claim 2,
The hydroxyl group-containing structural unit is,
Unit 2

[Wherein, R ²¹ is a hydrogen atom or a methyl group, R ²² is NHR ^2A' or OR ^2B' ,
R ^2A' is a hydroxyl group-containing alkyl group,
R ^2B' is (R ^2B1' O) _n H
(R ^2B1' is an alkylene group, and n is an integer of 1 or more)
or
R ^2B2' O(C(=O)(CH ₂ ) ₅ O) _m H
(R ^2B2' is an alkylene group, and m is an integer of 1 or more)
am]
A thermal curing release coating agent.
A cured product of the thermosetting release coating agent of any one of claims 1 to 3.
A cured product of the thermosetting release coating agent of claim 4 and a plastic film
thermosetting peeling film.
Claims 1 to 3, comprising the step of heating the heat-curable release coating agent of any one of claims 1 to 3 applied to at least one side of the plastic film
A method for producing a thermosetting release film.