CN114075388A - Thermosetting release coating agent, cured product, thermosetting release film, and method for producing same - Google Patents
Thermosetting release coating agent, cured product, thermosetting release film, and method for producing same Download PDFInfo
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- CN114075388A CN114075388A CN202110910815.3A CN202110910815A CN114075388A CN 114075388 A CN114075388 A CN 114075388A CN 202110910815 A CN202110910815 A CN 202110910815A CN 114075388 A CN114075388 A CN 114075388A
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract
The invention provides a thermosetting release coating agent, a cured product, a thermosetting release film and a manufacturing method thereof. Disclosed is a thermosetting release coating agent comprising a polymer (A), a melamine resin (B), and an acid catalyst (C), wherein the polymer (A) comprises 40-98% by mass of a structural unit (1) derived from a (meth) acrylate ester having an alkyl group having 4-11 carbon atoms and 2-60% by mass of a structural unit (2) derived from a hydroxyl group-containing (meth) acrylic monomer.
Description
Technical Field
The present disclosure relates to a thermosetting release coating agent, a cured product, a thermosetting release film, and a method for producing the same.
Background
The release film is used as a process film for casting a film such as a urethane resin, an acrylic resin, a vinyl chloride resin, etc., a protective film for an adhesive layer such as an adhesive tape, an adhesive sheet, an adhesive film, etc., and a process film for manufacturing an electronic component such as a ceramic green sheet (printed board), etc.
Various release coating agents have been proposed as release coating agents for producing release films. For example, patent document 1 describes a release treatment agent containing a main agent containing a reaction product of a polymer (a) selected from a vinyl alcohol polymer and polyethyleneimine and a long-chain alkyl isocyanate.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent application laid-open No. 2000-119608
Disclosure of Invention
[ problems to be solved by the invention ]
However, the release agent described in patent document 1 has a problem of low solvent resistance because it is not crosslinked. In addition, improvements are also required in the peeling force at room temperature (room-temperature peeling force) and the peeling force after heating (peeling force after heating) of the adhesive layer. Further, the residual adhesion rate after peeling is also required to be high. The problem to be solved by the present invention is to provide a thermosetting release coating agent which is excellent in solvent resistance, room-temperature release force, post-heating release force, and residual adhesion rate.
[ means for solving problems ]
The present inventors have made extensive studies and, as a result, have found that the problems can be solved by using specific ingredients.
According to the present disclosure, the following items are provided.
(item 1)
A thermosetting release coating agent comprising:
a polymer (A),
Melamine resin (B) and
an acid catalyst (C) which is a metal halide,
wherein the polymer (A) contains 40 to 98 mass% of the structural unit 1
[ solution 4]
(in the formula, R11Is a hydrogen atomOr methyl, R12Alkyl group having 4 to 11 carbon atoms)
And
2 to 60 mass% of structural unit 2
[ solution 5]
(in the formula, R21Is a hydrogen atom or a methyl group, R22Is NHR2' OR OR2′，R2' is a hydroxyl-containing alkyl group).
(item 2)
The thermosetting release coating agent according to the item, comprising a polyol (D) (excluding the polymer (A)).
(item 3)
The thermosetting release coating agent according to the item, wherein the polyol (D) comprises a polyol (D1), and the polyol (D1) comprises a structural unit D1
[ solution 6]
(in the formula, RD1Is a hydrogen atom or a methyl group, RD2An alkyl group having 12 to 28 carbon atoms).
(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 the cured product according to the above item and a plastic film.
(item 6)
A method for manufacturing a thermosetting release film, comprising: a step of applying the thermosetting release coating agent according to any one of the above items to at least one surface of a plastic film and heating the same.
In the present disclosure, the one or more features may be provided in further combination, in addition to the explicit combinations.
[ Effect of the invention ]
The thermally curable release coating agent of the present embodiment is excellent in solvent resistance, room temperature release force, peeling force after heating, and residual adhesion rate.
Detailed Description
In the entire disclosure, the ranges of numerical values such as the physical property values and the contents may be appropriately set (for example, selected from the upper limit and the lower limit described in the following items). Specifically, as for the numerical value α, when A4, A3, a2, a1 (A4 > A3 > a2 > a1) and the like are exemplified as the upper limit and the lower limit of the numerical value α, the range of the numerical value α may be exemplified by 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 release coating agent: also referred to as coating agent ]
The present disclosure provides a thermosetting release coating agent comprising:
a polymer (A),
Melamine resin (B) and
an acid catalyst (C) which is a metal halide,
wherein the polymer (A) contains 40 to 98 mass% of the structural unit 1
[ solution 7]
(in the formula, R11Is a hydrogen atom or a methyl group, R12Alkyl group having 4 to 11 carbon atoms)
And
2 to 60 mass% of structural unit 2
[ solution 8]
(in the formula, R21Is a hydrogen atom or a methyl group, R22Is NHR2' OR OR2′，R2' is a hydroxyl-containing alkyl group).
< polymer (a): also referred to as component (A) >
(A) The components can be used singly or in combination of two or more.
(structural unit 1)
The structural unit 1 is obtained by using a (meth) acrylate (a1) containing an alkyl group having 4 to 11 carbon atoms as a monomer
[ solution 9]
(in the formula, R11Is a hydrogen atom or a methyl group, R12Alkyl group having 4 to 11 carbon atoms)
In the case of (2), a structural unit contained in the polymer (A). The (meth) acrylate (a1) containing an alkyl group having 4 to 11 carbon atoms can 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.
Straight chain alkyl radical consisting ofnH2n+1(n is an integer of 1 or more).
The branched alkyl group is a group having no cyclic structure in which at least one hydrogen atom of a linear alkyl group is substituted with an alkyl group.
Examples of the cycloalkyl group include monocyclic cycloalkyl groups, crosslinked cycloalkyl groups, and fused ring cycloalkyl groups. Further, a group in which at least one hydrogen atom of a cycloalkyl group is substituted with an alkyl group is also considered to be a cycloalkyl group.
In the present disclosure, a monocyclic ring refers to a cyclic structure formed by covalent bonds of carbon and having no internal bridge structure. A fused ring refers to a cyclic structure in which two or more monocyclic rings share two atoms (i.e., share only one side of each ring (fused) with each other). A crosslinked ring refers to a cyclic structure in which two or more monocyclic rings have three or more atoms in total.
R12Examples of the upper limit and the lower limit of the number of carbon atoms in the alkyl group in (b) include 11, 10, 9, 8, 7, 6, 5 and 4. In one embodiment, the number of carbons is preferably 4 to 11.
R12Preferably an alkyl group having 4 to 11 carbon atoms, more preferably an alkyl group having 4 to 8 carbon atomsMore preferably, it is butyl or 2-ethylhexyl.
Examples of the alkyl group having 4 to 11 carbon atoms include a straight-chain alkyl group, a branched alkyl group, and a cycloalkyl group such as a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decamethyl group, and an undecyl group.
Examples of the (meth) acrylate having 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 having 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, cyclohexyl (meth) acrylate, and the like.
Examples of the upper limit and the lower limit of the content of the constitutional unit 1 relative to 100 mass% of the polymer (a) may include 98 mass%, 97 mass%, 96 mass%, 95 mass%, 90 mass%, 89 mass%, 88.3 mass%, 88 mass%, 85 mass%, 80 mass%, 77 mass%, 76.7 mass%, 76 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 59 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, and the like, relative to the mass of the polymer (a). In one embodiment, the content is preferably 40% by mass to 98% by mass.
Examples of the upper limit and the lower limit of the content of the constitutional unit 1 relative to 100 mol% of the polymer (a) include 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% and the like. In one embodiment, the content may be 50 mol% to 90 mol%.
(structural unit 2)
The structural unit 2 is obtained by using a hydroxyl group-containing (meth) acrylic monomer (a2)
[ solution 10]
(in the formula, R21Is a hydrogen atom or a methyl group, R22Is NHR2′OR OR2′，R2′Is a hydroxyl-containing alkyl group)
In the case of (2), a structural unit contained in the polymer (A). The hydroxyl group-containing (meth) acrylic monomer (a2) may be used alone or in combination of two or more.
In the present disclosure, "a hydroxyl-containing alkyl group" is a group in which one hydrogen atom of an alkyl group is substituted with a hydroxyl group. Examples of the hydroxyl group-containing alkyl group include a hydroxyl group-containing straight-chain alkyl group, a hydroxyl group-containing branched alkyl group, a hydroxyl group-containing cycloalkyl group and the like.
In the present disclosure, the upper limit and the lower limit of the number of carbon atoms of the hydrocarbon group having no carbon atom (alkyl group, alkylene group, arylene group, arylenealkylenearylene group, etc.) are exemplified by 30, 29, 25, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc.
Examples of the hydroxyl group-containing (meth) acrylic monomer (a2) include hydroxyl group-containing (meth) acrylates and hydroxyl group-containing (meth) acrylamides.
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.
Examples of the upper limit and the lower limit of the content of the constitutional unit 2 relative to 100 mass% of the polymer (a) include 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 17 mass%, 15 mass%, 12 mass%, 11.7 mass%, 10 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, and the like. In one embodiment, the content is preferably 2 to 60% by mass.
Examples of the upper limit and the lower limit of the content of the constitutional unit 2 relative to 100 mol% of the polymer (a) include 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% and the like. In one embodiment, the content may be 10 mol% to 50 mol%.
Examples of the upper limit and the lower limit 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) include 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 and the like. In one embodiment, the mass ratio is preferably 0.7 to 49.
Examples of the upper limit and the lower limit of the mass ratio (molar ratio) of the structural unit 1 and the structural unit 2 of the polymer (a) (mass of the structural unit 1/mass of the structural unit 2) include 9, 8, 7.3, 7, 6.9, 6, 5.3, 5, 4.8, 4, 3.3, 3.2, 3, 2, 1 and the like. In one embodiment, the mass ratio (molar ratio) is preferably 1 to 9.
(structural unit 3)
In one embodiment, the polymer (A) may comprise structural units 3
[ solution 11]
(in the formula, R31Is a hydrogen atom or a methyl group, R32An alkyl group having 1 to 3 carbon atoms).
The structural unit 3 is obtained by using a short chain alkyl group-containing (meth) acrylate (a3)
[ solution 12]
(in the formula, R31Is a hydrogen atom or a methyl group, R32Alkyl group having 1 to 3 carbon atoms)
In the case of (2), a structural unit contained in the polymer (A). The short chain alkyl group-containing (meth) acrylates may be used singly or in combination of two or more.
Examples of the alkyl group having 1 to 3 carbon atoms include a straight-chain alkyl group such as methyl, ethyl and propyl, a branched alkyl group and a cycloalkyl group.
Examples of the upper limit and the lower limit of the content of the constitutional unit 3 with respect to 100 mass% of the polymer (a) include 30 mass%, 25 mass%, 24 mass%, 20 mass%, 15 mass%, 12 mass%, 11.6 mass%, 11 mass%, 10 mass%, 9 mass%, 7 mass%, 5 mass%, 3 mass%, 2 mass%, 1 mass%, 0 mass%, and the like. In one embodiment, the content is preferably 0 to 30% by mass.
Examples of the upper limit and the lower limit of the content of the constitutional unit 3 relative to 100 mol% of the polymer (a) include 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%, and the like. In one embodiment, the content is preferably 0 to 30 mol%.
(structural unit 4)
In one embodiment, the polymer (A) may comprise structural units 4
[ solution 13]
(in the formula, R41Is a hydrogen atom or a methyl group, R42An alkyl group having 12 to 28 carbon atoms).
The structural unit 4 is obtained by using a long-chain alkyl group-containing (meth) acrylate as a monomer
[ solution 14]
(in the formula, R41Is a hydrogen atom or a methyl group, R42Alkyl group having 12 to 28 carbon atoms)
In the case of (2), a structural unit contained in the polymer (A). The long-chain alkyl group-containing (meth) acrylates may be used singly or in combination of two or more.
Examples of the alkyl group having 12 to 28 carbon atoms include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl 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, and octacosyl group.
Examples of the long-chain alkyl group-containing (meth) acrylate 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, docosyl (meth) acrylate, tricosyl (meth) acrylate, ditetradecyl (meth) acrylate, pentacosyl (meth) acrylate, hexacosyl (meth) acrylate, heptacosyl (meth) acrylate, dioctadecyl (meth) acrylate, isododecyl (meth) acrylate, isotridecyl (meth) acrylate, and mixtures thereof, Isomyristyl (meth) acrylate, isopentadecyl (meth) acrylate, isocetyl (meth) acrylate, isoheptadecyl (meth) acrylate, isostearyl (meth) acrylate, and the like. Among them, lauryl (meth) acrylate and stearyl (meth) acrylate are particularly preferable in terms of ease of obtaining and light exfoliation.
Examples of the upper limit and the lower limit of the content of the structural unit 4 with respect to 100% by mass of the polymer (a) include 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 3% by mass, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the content is preferably 0 to 9% by mass.
Examples of the upper limit and the lower limit of the content of the structural unit 4 in 100 mol% of the polymer (a) include 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0 mol%, and the like. In one embodiment, the content is preferably 0 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 a structural unit other than the structural units 1 to 4.
Examples of the structural unit other than the structural units 1 to 4 include structural units included in the polymer (a) when a polyfunctional (meth) acrylate such as (meth) acrylic acid, styrene, alkenyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, or ethylene glycol di (meth) acrylate is used as a monomer.
The content of the other structural unit with respect to 100% by mass of the polymer (a) may 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, and the like. The content of the other constituent unit with respect to 100% by mass of any one of the constituent units 1 to 3 may be, for example, less than 5% by mass, less than 2% by mass, less than 1% by mass, less than 0.1% by mass, or 0% by mass.
Examples of the content of the other structural unit in 100 mol% of the polymer (a) include less than 5 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, 0 mol%, and the like. Examples of the content of the other constituent unit in 100 mol% of any one of the constituent units 1 to 3 include less than 5 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, and 0 mol%.
< physical Properties of Polymer (A) and the like >
Examples of the upper and lower limits of the number average molecular weight of the polymer (a) include 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, 12000, 11200, 10000, 9000, 8000 and the like. In one embodiment, the number average molecular weight is preferably 8000 to 80000.
Examples of the upper limit and the lower limit of the weight average molecular weight of the polymer (a) include 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. In one embodiment, the weight average molecular weight is preferably 20000 to 200000.
The weight average molecular weight and the number average molecular weight can be determined as polystyrene equivalent values measured by Gel Permeation Chromatography (GPC) in an appropriate solvent, for example. Specific conditions include the following.
The machine is as follows: the product name is "HLC-8220" (manufactured by Tosoh (stock))
Pipe column: the product name "PL gel Mixed-C (PLGel MIXED-C)" (manufactured by Agilent Technology) X2 roots
Developing solvent, flow rate: tetrahydrofuran, 1.0 mL/min
Measuring temperature: 40 deg.C
A detector: refractive Index (RI)
The standard is as follows: monodisperse polystyrene
Polymer concentration: 0.2 percent of
Examples of the upper limit and the lower limit of the hydroxyl value of the polymer (A) include 300mgKOH/g, 275mgKOH/g, 250mgKOH/g, 225mgKOH/g, 210mgKOH/g, 203mgKOH/g, 200mgKOH/g, 175mgKOH/g, 150mgKOH/g, 125mgKOH/g, 100mgKOH/g, 75mgKOH/g, 52mgKOH/g, 50mgKOH/g, 40mgKOH/g, 35mgKOH/g, 30mgKOH/g, 25mgKOH/g, 22mgKOH/g, 20mgKOH/g, 15mgKOH/g, 10mgKOH/g, 9mgKOH/g, 7mgKOH/g, 5mgKOH/g, 4mgKOH/g, 2mgKOH/g, and 1 mgKOH/g. In one embodiment, the hydroxyl value of the polymer (A) is preferably 1mgKOH/g to 300mgKOH/g from the viewpoint of achieving both of the releasability and the solvent resistance.
The hydroxyl value can be measured by a method according to Japanese Industrial Standard (JIS) K1557-1.
Examples of the method for producing the polymer (a) include various known radical polymerization methods. The radical polymerization can be obtained by heating in the presence of a radical polymerization initiator.
Examples of the radical polymerization initiator include: inorganic peroxides such as hydrogen peroxide, ammonium persulfate, and potassium persulfate; organic peroxides such as benzoyl peroxide, dicumyl peroxide, lauryl peroxide and the like; azo compounds such as 2, 2 '-azobisisobutyronitrile and dimethyl-2, 2' -azobisisobutyronitrile. The radical polymerization initiator may be used alone or in combination of two or more. The amount of the radical polymerization initiator used is preferably about 1 to 10 parts by mass per 100 parts by mass of the total monomer components.
In the production of the polymer (A), a chain transfer agent may be used, if necessary. 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. The amount of the chain transfer agent used is preferably about 0 to 5 parts by mass per 100 parts by mass of the total monomer components.
Examples of the upper limit and the lower limit of the content of the polymer (a) with respect to 100 mass% of the solid content of the coating agent include 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 2 mass%, 1 mass%, and the like. In one embodiment, the content is preferably 2 to 80% by mass.
< melamine resin: also referred to as (B) component >
(B) The components can be used singly or in combination of two or more.
(B) The component (A) may be exemplified by a composition containing a melamine compound derived from
[ solution 15]
(in the formula, Rm1～Rm6Each independently selected from hydrogen atom, hydroxymethyl group, methoxymethyl group, ethoxymethyl group, n-butoxymethyl group and isobutoxymethyl group)
Melamine resin of the structural unit of (3), and the like. In one embodiment, the average degree of polymerization of the component (B) is 1.1 to 10.
The component (B) is preferably a melamine resin containing a structural unit derived from methylated melamine and/or butylated melamine, in terms of excellent balance between curability of the coating agent and compatibility with the component (a) and the component (D) described later. Methylated melamine means said Rm1～Rm6At least one of which is methoxymethyl (-CH2OCH3), butylated melamine means that said R ism1～Rm6At least one of which is n-butoxymethyl (-CH)2OCH2CH2CH2CH3) Isobutoxymethyl (-CH)2OCH(CH3)CH2CH3) A compound of any one of.
The component (B) preferably contains a component derived from the above-mentioned R in view of excellent curabilitym1～Rm6The resin containing all ether-type methylated melamine structural units all having methoxymethyl groups (hereinafter, all ether-type methylated melamine resin) is preferably one containing structural units derived from the above-mentioned R component in view of compatibility with the components (A) and (D)m1～Rm6All are n-butoxyformazanAnd a resin having a structural unit of a full ether-type butylated melamine having either one of the methyl group and the isobutoxymethyl group (hereinafter, a full ether-type butylated melamine resin). In addition, in terms of excellent balance between curability and compatibility with the component (A) and the component (D), the resin composition preferably contains a compound derived from the above-mentioned Rm1～Rm6A resin having a structural unit of a full ether type methyl-butylated melamine in which at least one of (a) and (b) is a methoxymethyl group and the others are each either a n-butoxymethyl group or an isobutoxymethyl group (hereinafter, a full ether type methyl-butylated melamine resin).
(B) Examples of the component(s) may include Seimel (CYMEL)300, Seimel (CYMEL)301, Seimel (CYMEL)303LF, Seimel (CYMEL)350, Seimel (CYMEL)370N, Seimel (CYMEL)771, Seimel (CYMEL)325, Seimel (CYMEL)327, Seimel (CYMEL)703, Seimel (CYMEL)712, Seimel (CYMEL)701, Seimel (CYMEL)266, Seimel (CYMEL)267, Seimel (CYMEL)285, Seimel (CYMEL)232, Seimel (CYMEL)235, Seimel (CYMEL)236, Seimel (CYMEL)238, Seimel (CYMEL)272, Seimel (CYMEL)212, Seimel (CYMEL)254, Seimel (CYMEL)253, Seimel (CYMEL)202, Seimel (CYMEL)207, Seimel (CYMEL)202, and Nikavalkayaki MW Nicagac (Nikalac) MW-30HM, Nicagac (Nikalac) MW-390, Nicagac (Nikalac) MW-100LM, Nicagac (Nikalac) MX-750LM, Nicagac (Nikalac) MW-22, Nicagac (Nikalac) MS-21, Nicagac (Nikalac) MS-11, Nicagac (Nikalac) MW-24X, Nicagac (Nikalac) MS-001, Nicagac (Nikalac) MX-002, Nicagac (Nikalac) MX-730, Nikalac (Nikalac) MX-750, Nicagac (Nikalac) MX-708, Nicagac (Nikalac) MX-706, Nikalac (Niclac) MX-042, Niclac (Nikalac) MX-417, Nikalac) MX-035, Nikalac (Nikalac) MX-55, Nikalac) MX-035, Nikalac (Nikalac) MX-410, Nikalac) MX-55, Nikalac) MX-035, Nikalac (Nikalac) MX-042, Nikalac) MX-43, Nikalac) MX-80, Nikalac (Nikalac) MX-035, Nikalac) MX-60, Nikalac MX-80, Nikalac MX-8, Nikalac MX-80, Nikalac MX-III, Nikalac) and Nikalac MX-III, Youshang (U-VAN)20SB, Youshang (U-VAN)20SE60, Youshang (U-VAN)21R, Youshang (U-VAN)22R, Youshang (U-VAN)122, Youshang (U-VAN)125, Youshang (U-VAN)220, Youshang (U-VAN)225, Youshang (U-VAN)228, Youshang (U-VAN)2020 (manufactured by Tri-well chemistry (Strand), above), yamadai (AMIDIR) J-820-60, Yamadai (AMIDIR) L-109-65, Yamadai (AMIDIR) L-117-60, Yamadai (AMIDIR) L-127-60, Yamadai (AMIDIR)13-548, Yamadai (AMIDIR) G-821-60, Yamadai (AMIDIR) L-110-60, Yamadai (AMIDIR) L-125-60, and Yamadai (AMIDIR) L-166-60B (manufactured by Diesen (DIC) (Strand Co., Ltd.).
Examples of the upper limit and the lower limit of the content of the melamine resin (B) with respect to 100 mass% of the solid content of the coating agent include 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, and the like. In one embodiment, the content is preferably 20 to 70% by mass, and more preferably 25 to 60% by mass.
< acid catalyst: also referred to as component (C) >
(C) The components can be used singly or in combination of two or more.
(C) Examples of the component (B) include inorganic acids, organic acids, and thermal acid generators.
Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
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, isoprene sulfonic acid, camphorsulfonic acid, hexane sulfonic acid, octane sulfonic acid, nonanesulfonic acid, decane sulfonic acid, hexadecane sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid, cumene sulfonic acid, dodecylbenzene sulfonic acid, naphthalene sulfonic acid, and nonylnaphthalene sulfonic acid.
Examples of the organic phosphoric acid include Methyl phosphate (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, dinonylphenyl phosphate, and the like.
Examples of the thermal acid generator include sulfonium salts, benzothiazole salts, ammonium salts, and phosphonium salts.
In one embodiment, the acid catalyst (C) is preferably an organic acid, and more preferably an organic sulfonic acid and/or an organic phosphoric acid, from the viewpoint of compatibility with a resin such as the polymer (a) and the melamine resin (B).
Examples of the upper limit and the lower limit of the content of the acid catalyst (C) with respect to 100 mass% of the solid content of the coating agent include 10 mass%, 9.5 mass%, 9 mass%, 8.5 mass%, 8 mass%, 7.5 mass%, 7 mass%, 6.5 mass%, 6 mass%, 5.5 mass%, 5 mass%, 4.5 mass%, 4 mass%, 3.9 mass%, 3.8 mass%, 3.5 mass%, 3 mass%, 2.5 mass%, 2 mass%, 1.5 mass%, 1 mass%, and the like. In one embodiment, the content is preferably 1 to 10% by mass.
< polyol: also referred to as (D) component >
In one aspect, the coating agent may include a polyol. (D) The components can be used singly or in combination of two or more.
In the present disclosure, "polyol" refers to a compound having two or more hydroxyl groups (-OH).
(D) Examples of the component (A) include alkylene polyols, dimer diols, hydrogenated dimer diols, castor oil polyols, hydroxyl-containing fatty acid alkylene polyol esters, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, and mixtures thereof,
Comprising structural element D1
[ solution 16]
(in the formula, RD1Is a hydrogen atom or a methyl group, RD2Alkyl group having 12 to 28 carbon atoms)
The polyol (D1), and the like.
(polyol (D1))
Examples of the polyol (D1) include a polymer comprising the structural unit D1 and the hydroxyl group-containing structural unit D2.
Structural element D1
The structural unit D1 is obtained by using a long-chain alkyl group-containing (meth) acrylate as a monomer
[ solution 17]
(in the formula, RD1Is a hydrogen atom or a methyl group, RD2Alkyl group having 12 to 28 carbon atoms)
In the case of (2), a structural unit contained in the polyol (D1). The long-chain alkyl group-containing (meth) acrylates may be used singly or in combination of two or more.
Examples of the long chain alkyl group-containing (meth) acrylate include the above-mentioned compounds.
Examples of the upper limit and the lower limit of the content of the structural unit D1 based on 100 mass% of the polymer (D1) include 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 90 mass%, 88 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, and the like. In one embodiment, the content may be 50 to 99% by mass.
Structural unit D2 containing a hydroxyl group
The hydroxyl group-containing structural unit D2 can be exemplified by the structural unit 2 and the like.
Examples of the upper limit and the lower limit of the content of the structural unit D2 based on 100 mass% of the polymer (D1) include 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 12 mass%, 10 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, and the like. In one embodiment, the content may be 1 to 50% by mass.
(alkylene polyol)
In the present 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 polyols, branched alkylene polyols, and cycloalkylene polyols.
Examples of the linear alkylene polyol include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 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, trimethylolpropane and the like.
As the cycloalkylene polyol, monocyclic cycloalkylene glycol, crosslinked cycloalkylene glycol and the like can be exemplified.
Examples of the monocyclic cycloalkylidene polyol include 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, and 2, 2' -bis (4-hydroxycyclohexyl) propane.
Examples of the crosslinked cycloalkylidene polyol include tricyclodecanedimethanol and the like.
(dimer diol)
The dimer diol is generally a substance obtained by reducing a reaction product of a cyclic and/or acyclic dimer acid obtained by dimerizing a higher unsaturated fatty acid and methanol. Examples of the dimerization reaction of higher unsaturated fatty acids include the method described in Japanese patent laid-open No. 9-136861. The hydrogenated dimer diol is obtained by hydrogenation reaction of the dimer diol.
In the production of 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 (linoleic acid), eicosadienoic acid, docosadienoic acid, linolenic acid (linolenic acid), arachidonic acid (arachidonic acid), myristoleic acid (myristoleic acid), palmitoleic acid (palmitoleic acid), oleic acid (olenic acid), elaidic acid (elaidic acid), octadecenoic acid (vaccenic acid), eicosenoic acid (eicosenoic acid), erucic acid (erucic acid), cetylenic acid (cetoeic acid), brassidic acid (brassidic acid), and the like. Of these, oleic acid and/or linoleic acid are preferred.
(Castor oil polyol)
Examples of the castor oil-based polyol include (poly) fatty acid esters having a glycerin hydroxyl group.
The glycerin hydroxyl group-containing fatty acid (poly) ester refers to a (poly) ester (monoester, diester, triester) obtained by reacting one or more hydroxyl groups of glycerin with a hydroxyl group-containing fatty acid.
The hydroxyl group-containing fatty acid is preferably a long-chain fatty acid containing a hydroxyl group and having 12 or more carbon atoms (for example, 12 to 30 carbon atoms, 12 to 24 carbon atoms, 12 to 20 carbon atoms, etc.).
Examples of the long-chain fatty acid containing a hydroxyl group include a saturated long-chain fatty acid containing a hydroxyl group, an unsaturated long-chain fatty acid containing a hydroxyl group, and the like.
Examples of the saturated long-chain fatty acid having a hydroxyl group include hydroxylauric acid, hydroxytridecyl acid, hydroxymyristic acid, hydroxypentadecyl acid, hydroxypalmitic acid, hydroxyheptadecyl acid, hydroxystearic acid, hydroxynonadecyl acid, hydroxyeicosanoic acid, hydroxyheneicosyl acid, hydroxydocosanoic acid, hydroxytricosanoic acid, hydroxytetracosanoic acid, hydroxypentacosanoic acid, hydroxyhexacosanoic acid, hydroxyheptacosanoic acid, hydroxyoctacosanoic acid, hydroxyisododecanoic acid, hydroxyisotridecyl acid, hydroxyisomyristic acid, hydroxyisopentadecyl acid, hydroxyisocetylic acid, hydroxyisoheptadecyl acid, hydroxyisostearic acid, and aleuritic acid (aleuritic acid).
Examples of the hydroxyl group-containing unsaturated long-chain fatty acid include a hydroxyl group-containing monounsaturated long-chain fatty acid, a hydroxyl group-containing diunsaturated long-chain fatty acid, a hydroxyl group-containing triunsaturated long-chain fatty acid, a hydroxyl group-containing tetraunsaturated long-chain fatty acid, a hydroxyl group-containing pentaunsaturated long-chain fatty acid, and a hydroxyl group-containing hexaunsaturated long-chain fatty acid.
Examples of the hydroxyl group-containing monounsaturated long-chain fatty acid include ricinoleic acid, hydroxymyristoleic acid, hydroxypalmitoleic acid, hydroxycedaric acid (hydroxysapienic acid), hydroxyoleic acid, hydroxyelaidic acid, hydroxyoctadecenoic acid, hydroxyeicosenoic acid (hydroxygadolenic acid), hydroxyeicosenoic acid (hydroxyeicosenoic acid), hydroxysinapic acid, and hydroxynervonic acid (hydroxynervonic acid).
Examples of the hydroxyl group-containing di-unsaturated long-chain fatty acid include hydroxylinoleic acid, hydroxyeicosadienoic acid, hydroxydocosadienoic acid and the like.
Examples of the hydroxyl group-containing tri-unsaturated long-chain fatty acid include hydroxy linolenic acid, hydroxy pinolenic acid (hydropinolenic acid), hydroxy eleostearic acid (hydroeleostearic acid), hydroxy mead acid (hydromead acid), and hydroxy eicosatrienoic acid (hydroeicosatrienoic acid).
Examples of the hydroxyl group-containing tetraunsaturated long-chain fatty acid include hydroxystearidonic acid (hydroxystearic acid), hydroxyarachidonic acid, hydroxydocosatetraenoic acid (hydroxyadrenic acid), and the like.
Examples of the hydroxyl group-containing pentaunsaturated long-chain fatty acid include hydroxyoctadecatrienoic acid (hydroxyoctadecanoic acid), hydroxyeicosapentaenoic acid (hydroxyeicosapentaenoic acid), hydroxydocosapentaenoic acid (hydroxyisobornic acid), hydroxy oleic acid (hydroxyeicosapentaenoic acid), and hydroxytetracosapentaenoic acid (hydroxytetracosapentaenoic acid).
Examples of the hydroxyl group-containing hexaunsaturated long-chain fatty acid include hydroxydocosahexaenoic acid (hydroxydocosahexaenoic acid), hydroxytetracosahexaenoic acid (hydroxynisinic acid), and the like.
(hydroxyl-containing fatty acid alkylene polyol ester)
In the present disclosure, "hydroxyl-containing fatty acid alkylene polyol ester" refers to an ester obtained by reacting a hydroxyl-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" 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 formula
HO-(REther-O-)nH
(in the formula, REtherIs alkylene, arylene, or arylenealkylenearylene, and n is an integer of 2 or more).
Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.
Straight chain alkylene is composed of- (CH)2)n- (n is an integer of 1 or more). Examples of the linear alkylene group include 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, an n-nonylene group, and an n-decamethylene group.
The branched alkylene group is a group in which at least one hydrogen atom of a linear alkylene group is substituted with an alkyl group. Examples of the branched alkylene group include isopropylene, diethylpentylene, trimethylbutylene, trimethylpentylene, and trimethylhexylene.
Examples of the cycloalkylene group include monocyclic cycloalkylene group, crosslinked cyclic cycloalkylene group, fused cyclic cycloalkylene group and the like. In addition, one or more hydrogen atoms of the cycloalkylene group may be substituted with a straight-chain alkyl group or a branched alkyl group.
Examples of the monocyclic cycloalkylene group include cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclodecylene group, 3, 5, 5-trimethylcyclohexylene group and the like.
Examples of the crosslinked cycloalkylene group include a tricyclodecanyl group, an adamantylene group, and a norbornyl group.
Examples of the fused ring cycloalkylene group include bicyclodecylene and the like.
Examples of the arylene group include a phenylene group, a naphthylene group, and a fluorenylene group.
Arylenealkylenearylene is a compound of
-Rarylene-Ralkylene-Rarylene-
(in the formula, RaryleneRepresents an arylene group, RalkyleneRepresents an alkylene group)
The indicated radicals.
As the arylene alkylenearylene group, for example, a phenylenedimethylmethylenephenylene group and the like can be exemplified.
Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and alkylene oxide adducts of polyols.
Examples of commercially available Polyether polyols include Adeka Polyether (Adeka Polyether) GM-30, Adeka Polyether (Adeka Polyether) P-400, Adeka Polyether (Adeka Polyether) G-400, Adeka Polyether (Adeka Polyether) T-400, and Adeka Polyether (Adeka Polyether) AM-302 (manufactured by Adeka (R)) and the like.
(polyester polyol)
In the present disclosure, "polyesterol" refers to a compound having two or more hydroxyl groups and two or more repeating units containing an ester bond in succession. In addition, polycaprolactone polyol is one of the polyester polyols.
In one embodiment, the polyester polyol is represented by the following structural formula
HO-{RaEster-OC(＝O)-RbEster-C(＝O)O}m-RcEster-OH
(in the formula, RaEster、RbEsterAnd RcEsterEach independently an alkylene group or an arylene group, and m is an integer of 2 or more).
Examples of the polyester polyol include reaction products of a polycarboxylic acid or an anhydride thereof and a polyhydric alcohol.
Examples of the polycarboxylic acid include dicarboxylic acids.
Examples of the dicarboxylic acid include dicarboxylic acids such as 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-methylpentanedioic acid, 2-methyloctane diacid, 3, 8-dimethyldecanedioic acid, 3, 7-dimethyldecanedioic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid.
Examples of the polycarboxylic acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, and the like.
Examples of the polyol include the alkylene polyols described above.
(polycarbonate polyol)
In the present disclosure, "polycarbonate polyol" refers to a compound having two or more hydroxyl groups and two or more repeating units containing a carbonate bond.
In one embodiment, the polycarbonate polyol is represented by the following structural formula
HO-{RaCarbo-OC(＝O)O}p-RbCarbo-OH
(in the formula, RaCarboAnd RbCarboEach independently an alkylene group, and p is an integer of 2 or more).
Examples of the polycarbonate polyol include a reaction product of a polyol and phosgene (phosgene), a ring-opened polymer of a cyclic carbonate (alkylene carbonate, etc.), and the like.
Examples of the polyol include the alkylene polyols described above.
Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. Examples of commercially available polycarbonate polyols include Eternacal (ETERNACOLL) UH-50, Eternacal (ETERNACOLL) PH-50 (manufactured by UK Seisakusho Co., Ltd.), Duranol (Duranol) T5625, Durano (Durano1) T5652, and Duranol (Duranol) G3452 (manufactured by Asahi Kasei (Ski Co., Ltd.).
(polyolefin polyol)
Examples of the polyolefin polyol include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorides thereof. As a commercially available polyolefin polyol, Nixol (NISSO) -PB GI-1000 (manufactured by Nippon Caoda Co., Ltd.) and the like can be exemplified.
(physical Properties of component (D))
(D) Examples of the upper limit and the lower limit of the molecular weight of the component (a) include 50000, 40000, 30000, 20000, 10000, 5000, 4000, 3500, 3001, 3000, 2500, 2000, 1500, 1000, 500, 250, and 100. In one embodiment, the molecular weight is preferably 100 to 50000.
In the present disclosure, the abbreviation "molecular weight" refers to any of the formula weight or number average molecular weight. In the case where the structure of a compound can be uniquely expressed by a specific chemical formula (i.e., molecular weight distribution of 1), the molecular weight refers to the formula weight. On the other hand, in the case where the structure of the compound cannot be uniquely expressed by a specific chemical formula (i.e., molecular weight distribution is more than 1), the molecular weight refers to a number average molecular weight.
(D) Examples of the upper limit and the lower limit of the hydroxyl group value of the component include 1300mgKOH/g, 1200mgKOH/g, 1100mgKOH/g, 1000mgKOH/g, 900mgKOH/g, 800mgKOH/g, 750mgKOH/g, 700mgKOH/g, 600mgKOH/g, 500mgKOH/g, 400mgKOH/g, 300mgKOH/g, 250mgKOH/g, 200mgKOH/g, 150mgKOH/g, 100mgKOH/g, 90mgKOH/g, 75mgKOH/g, 50mgKOH/g, 40mgKOH/g and the like. In one embodiment, the hydroxyl value is preferably from 40mgKOH/g to 1300 mgKOH/g.
Examples of the upper limit and the lower limit of the content of the polyol (D) in 100 mass% of the solid content of the coating agent include 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, and the like. In one embodiment, the content is preferably 20 to 65% by mass.
< organic solvent (E): also referred to as (E) component >
In one aspect, 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, isopropanol, ethanol, butanol, and the like. Among these, methyl ethyl ketone, methyl isobutyl ketone, isopropyl alcohol, ethyl acetate, butyl acetate, and toluene are preferable from the viewpoint of the solubility of the resin.
In one embodiment, the content of the organic solvent in the coating agent is preferably about 1% by mass to 50% by mass of the solid content concentration of the coating agent from the viewpoint of coating suitability. By setting the above numerical range, the balance between the curing properties and the pot life of the cured film can be easily obtained.
The thermosetting release coating agent can be used as a thermosetting release coating agent for sheet molding, a thermosetting release coating agent for green sheet production, a thermosetting release coating agent for adhesion, a thermosetting release coating agent for labels, a thermosetting release coating agent for medical use, a thermosetting release coating agent for office supplies, and the like.
< additives >
The coating agent may contain, as an additive, an agent that does not conform to any of the components (A) to (E).
Examples of the additive include a binder, an antifoaming agent, an anti-slip agent, a preservative, a rust preventive, a pH adjuster, an antioxidant, a pigment, a dye, a lubricant, a leveling agent, a conductive agent, polybutadiene, polyisoprene, polychloroprene, polypentadiene, polybutene, polyisobutylene, polystyrene, an isoprene-butadiene copolymer, a styrene-isoprene copolymer, a polyolefin and a derivative thereof, a silicone resin, an isocyanate group-containing compound, an epoxy group-containing compound, an amine, a carboxylic anhydride, and a long chain alkyl group-containing alcohol. The binder is not particularly limited, and may be exemplified by known acrylic resins, urethane resins, polyester resins, epoxy resins, alkyd resins, and the like.
In one embodiment, the content of the additive may be less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, 0% by mass, or the like, based on 100% by mass of the coating agent. Examples thereof include less than 1 mass%, less than 0.1 mass%, less than 0.01 mass%, 0 mass%, and the like, based on 100 mass% of any of the components (a) to (E).
The coating agent can be produced by dispersing and mixing the components (a) to (C), and if necessary, the components (D) to (E) and additives by using various known means. The order of addition of the components is not particularly limited. In addition, various known apparatuses (an emulsion dispersing machine, an ultrasonic dispersing apparatus, etc.) can be used as the dispersing/mixing means.
[ cured product ]
The present disclosure provides a cured product of the thermal-curing release coating agent.
In one embodiment, the hardened substance is a thermally hardened substance of the thermally hardened release coating agent. Examples of the curing conditions include those described below.
[ thermosetting Release film ]
The present disclosure provides a thermosetting release film including the cured product and a plastic film.
Examples of the plastic film include films made 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, norbornene resin, and the like, and among these, polyethylene terephthalate is preferable in terms of transparency, dimensional stability, mechanical properties, chemical resistance, and the like.
The plastic film may be subjected to surface treatment (corona discharge or the like) as required. The plastic film may be provided with a layer formed of a coating agent other than the thermosetting release coating agent of the present disclosure on one surface or both surfaces thereof.
[ method for producing thermosetting Release film ]
The present disclosure provides a method for manufacturing a thermosetting release film, including: and a step of applying the thermosetting release coating agent to at least one surface of the plastic film and heating the coated plastic film.
Examples of the coating method include spraying, roll coater, reverse roll coater, gravure coater, knife coater, bar coater, and dot coater.
The amount of coating is not particularly limited. The coating amount is preferably 0.1g/m in mass after drying2～10g/m2About the same amount, more preferably 0.2g/m2～5g/m2The amount of (c).
Examples of the heating method include drying by a circulating air dryer and the like. The drying (curing) conditions may be exemplified by about 90 to 170 ℃ and about 30 seconds to 2 minutes.
[ examples ]
The present invention will be described in detail below with reference to examples and comparative examples. However, the description of the preferred embodiments and the following examples are provided for illustrative purposes only and are not intended to limit the present invention. Therefore, the scope of the present invention is not limited to the embodiments specifically described in the present specification and the examples, but is defined only by the claims. In each of examples and comparative examples, unless otherwise specified, parts,% and the like are based on mass.
Production example 1
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 put into a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer and a dropping funnel, and the temperature was gradually raised to 80 ℃ to carry out a reaction for 9 hours, thereby obtaining a polymer solution having a solid content of 40%.
The production was carried out in the same manner as in production example 1 except that the components and amounts were changed as shown in the following table, for example.
[ Table 1]
< explanation of abbreviations >
BA: acrylic acid butyl ester
2 EHA: 2-ethylhexyl acrylate
HEA: 2-Hydroxyethyl acrylate
HEMA: 2-Hydroxyethyl methacrylate
MMA: methacrylic acid methyl ester
LA: acrylic acid lauryl ester
Example 1
The polymer produced in production example 1 was added as component (a) in an amount of 75 parts in terms of solid content, 25 parts of a full ether type methylated melamine resin (product name "CYMEL (CYMEL)303 LF": manufactured by alinex Japan) as component (B), and 4 parts of p-toluenesulfonic acid as component (C) were added, and the mixture was diluted with toluene to prepare a solid content of 10%. Then, the solution was applied to a polyethylene terephthalate film (film thickness: 75 μm) so that the film thickness of the dried coating film became 1 μm, and dried at 120 ℃ for 1 minute to obtain a release film.
The procedure of example 1 was repeated except that the components and amounts of the examples and comparative examples other than example 1 were changed as shown in the following table.
[ Table 2]
< explanation of abbreviations >
Methylated melamine resin: the product name "Seimel (CYMEL)303 LF", full ether type methylated melamine resin, manufactured by Allnex Japan (Strand)
Hydrogenated dimer diol: the product name "Pripol (Pripol) 2033", manufactured by Nippon Poa (David) and having a number average molecular weight of 540
Pellol (Peeloil) 1050: long chain alkyl pendant based polymers, product name "Peeloil 1050", manufactured by Lion Specialty Chemicals (Lion Specialty Chemicals, Inc.)
(solvent resistance)
The cured layer of the release film was wiped with a cotton swab immersed in methyl ethyl ketone to evaluate the solvent resistance.
O: even if the wiping was performed 50 times, the substrate was not exposed.
And (delta): when the substrate is wiped 10 to 49 times, the substrate is exposed.
X: the substrate was exposed after 1 to 9 times of wiping.
(Room temperature peeling force)
A polyester adhesive tape (31B tape manufactured by Ridong electrician (Strand): 25mm wide) was bonded to a release film while being pressed by a 2kg roller, and stored at 23 ℃ for 1 hour. Subsequently, the tape was stretched at an angle of 180 ℃ at a peeling speed of 0.3 m/min, and the force (N/25mm) required for peeling was measured.
(peeling force after heating)
A polyester adhesive tape (31B tape manufactured by Ridong electrician (Strand): 25mm wide) was bonded to a release film while being pressed by a 2kg roller, and stored at 70 ℃ for 20 hours. Subsequently, the tape was stretched at an angle of 180 ℃ at a peeling speed of 0.3 m/min, and the force (N/25mm) required for peeling was measured.
(residual adhesion ratio)
A polyester adhesive tape (31B tape manufactured by Riston electrician (Strand): 25mm wide) was attached to the release film and stored at 23 ℃ for one day. After storage, the tape was peeled off and attached to a stainless steel (SUS) plate using a 2kg roller. Subsequently, 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 peel force when the tape was directly attached to a SUS plate and peeled off under the same conditions was measured, and the ratio (%) of the former peel force to the latter peel force was determined as the residual adhesion rate. A larger value indicates that the adhesive force of the tape is not reduced.
Claims (6)
1. A thermosetting release coating agent comprising:
a polymer (A),
Melamine resin (B) and
an acid catalyst (C) which is a metal halide,
wherein the polymer (A) comprises 40 to 98 mass% of a structural unit 1,
in the formula, R11Is a hydrogen atom or a methyl group, R12An alkyl group having 4 to 11 carbon atoms;
and
2 to 60 mass% of a structural unit 2,
in the formula, R21Is a hydrogen atom or a methyl group, R22Is NHR2' OR OR2'，R2' is a hydroxyl-containing alkyl group.
2. The thermosetting release coating agent according to claim 1, comprising a polyol (D), wherein the polyol (D) is other than the polymer (a).
3. The thermosetting release coating agent according to claim 2, wherein the polyol (D) comprises polyol (D1), the polyol (D1) comprises structural unit D1,
in the formula, RD1Is a hydrogen atom or a methyl group, RD2Is an alkyl group having 12 to 28 carbon atoms.
4. A cured product of the heat-curable release coating agent according to any one of claims 1 to 3.
5. A thermosetting release film comprising the cured product according to claim 4 and a plastic film.
6. A method for manufacturing a thermosetting release film, comprising: a step of applying the thermosetting release coating agent according to any one of claims 1 to 3 to at least one surface of a plastic film and heating the same.
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| JP2020135505 | 2020-08-11 | ||
| JP2020-135505 | 2020-08-11 |
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| JP (1) | JP7552531B2 (en) |
| KR (1) | KR20220020214A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116478588A (en) * | 2023-04-28 | 2023-07-25 | 太仓斯迪克新材料科技有限公司 | Low-release-force, high-residue and excellent-weather-resistance non-silicon release agent, preparation method thereof and release film |
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| KR20230123268A (en) | 2022-02-16 | 2023-08-23 | 한국철도기술연구원 | Method for detecting rail fracture using image transformation of vibration data measured by distributed acoustic sensing technology |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5714642A (en) * | 1980-06-28 | 1982-01-25 | Shin Etsu Chem Co Ltd | Release film forming agent for silicone pressure-sensitive adhesive |
| JPS5749685A (en) * | 1980-09-10 | 1982-03-23 | Kikusui T-Pu Kk | Nonsilicon releasing agent |
| JP2000119608A (en) | 1998-10-13 | 2000-04-25 | Ashio Sangyo Kk | Release agent |
| JP6756432B2 (en) | 2016-03-14 | 2020-09-16 | リンテック株式会社 | Release agent composition, release sheet and adhesive |
| JP6930110B2 (en) | 2017-01-16 | 2021-09-01 | 荒川化学工業株式会社 | Thermosetting release coating agent, release film and its manufacturing method |
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2021
- 2021-08-06 JP JP2021129458A patent/JP7552531B2/en active Active
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| CN116478588A (en) * | 2023-04-28 | 2023-07-25 | 太仓斯迪克新材料科技有限公司 | Low-release-force, high-residue and excellent-weather-resistance non-silicon release agent, preparation method thereof and release film |
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| KR20220020214A (en) | 2022-02-18 |
| CN114075388B (en) | 2023-10-20 |
| JP2022033003A (en) | 2022-02-25 |
| JP7552531B2 (en) | 2024-09-18 |
| TW202206572A (en) | 2022-02-16 |
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