Release coating agent, cured product, and laminate

Abstract

[Problem] To provide a release coating agent, a cured product, and a laminate. [Technical means] A release coating agent comprising: a block polymer comprising a long-chain block and a block containing a hydroxyl group, the long-chain block comprising a (meth) acrylate unit containing a C10-28 alkyl group, and the block containing a hydroxyl group comprising an alkyl (meth) acrylate unit containing a hydroxyl group.

Description

Technical Field

[0001] The present disclosure relates to a release coating agent, a cured product, and a laminate. Background Art

[0002] Release films are used as process films for casting films of urethane resins, acrylic resins, vinyl chloride resins, etc., as protective films for adhesive layers such as adhesive tapes, adhesive sheets, and adhesive films, and as process films for manufacturing electronic components such as ceramic green sheets and printed circuit boards.

[0003] Various release coating agents have been proposed for producing release films. For example, Patent Document 1 describes a release treatment agent comprising a base agent containing a reaction product of a polymer (A) selected from vinyl alcohol polymers or polyethyleneimine and a long-chain alkyl isocyanate. [Prior art literature] [Patent Document]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-119608 Summary of the Invention [Problems to be solved by the invention]

[0005] The problem to be solved by the present invention is to provide a release coating agent that can produce a cured product having good room temperature release strength, release strength after heating, and low migration properties. [Technical means to solve the problem]

[0006] According to the present disclosure, the following items are provided. (Item 1) A release coating agent, comprising: a block polymer, The block polymer comprises a long-chain block and a hydroxyl-containing block, wherein the long-chain block comprises a (meth)acrylate unit containing a C10-28 alkyl group. The hydroxyl group-containing block includes a hydroxyl group-containing alkyl (meth)acrylate unit. (Item 2) The release coating agent according to the above item, wherein the block polymer comprises a (meth)acrylate unit containing a C1-9 alkyl group. (Item 3) A cured product of the release coating agent according to any one of the above items. (Item 4) A laminate comprising the cured product according to the above item.

[0007] In the present disclosure, one or more features may be provided in further combinations other than the combinations explicitly shown. [Beneficial Effects]

[0008] The cured product of the present invention exhibits good room temperature peel strength, peel strength after heating, and low migration properties. DETAILED DESCRIPTION

[0009] Throughout the present disclosure, the ranges of the values ​​of various physical property values, contents, etc. can be appropriately set (for example, selected from the values ​​described in the following items). Specifically, regarding the numerical value α, when A3, A2, A1 (assuming A3>A2>A1) and the like are cited as the numerical value α, the range of the numerical value α can be exemplified by A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less, and the like.

[0010] As long as the problems to be solved by the present invention are solved, the components, conditions, numerical values, etc. are not particularly limited.

[0011] "αβ amount (A / B)" refers to the β amount (α) of A relative to 100α of B. Examples of α include mass %, mole %, and parts by mass. Examples of β amount include content and usage amount. "Mass % content (A / B)" refers to the content (mass %) of A relative to 100% of B.

[0012] "γ ratio (A / B)" refers to the γ ratio calculated by the formula "A÷B". Examples of the γ ratio include mass ratio and molar ratio.

[0013] The "non-volatile content" refers to the total mass of components other than the organic solvent and water. In one embodiment, the "non-volatile content of A" refers to the total mass of components remaining when 1 g of A is heated at 105°C to a constant weight.

[0014] “(Meth)acrylic acid” means “acrylic acid and / or methacrylic acid.” “(Meth)acrylate” means “acrylate and / or methacrylate.” “(Meth)acryloyl” means “acryloyl and / or methacryloyl.”

[0015] "C..." means "having a carbon number..." For example, "C1-6 alkyl" means an alkyl group having 1 to 6 carbon atoms. "C6 alkyl" means an alkyl group having 6 carbon atoms.

[0016] Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and a cycloalkyl group.

[0017] Examples of the straight-chain alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0018] Examples of the branched alkyl group include isopropyl, sec-butyl, isobutyl, tert-butyl, 2-ethylhexyl, diethylpentyl, trimethylbutyl, trimethylpentyl, and trimethylhexyl.

[0019] Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a bridged ring cycloalkyl group, a condensed ring cycloalkyl group, etc. Furthermore, a group in which at least one hydrogen atom of a cycloalkyl group is substituted by an alkyl group is also considered to be a cycloalkyl group.

[0020] "Monocyclic ring" refers to a ring structure formed by covalent carbon bonds without an internal bridge structure. "Fused ring" refers to a ring structure in which two or more monocyclic rings share two atoms (i.e., only one side of each ring is shared (fused)). "Bridged ring" refers to a ring structure in which two or more monocyclic rings share three or more atoms.

[0021] Examples of the monocyclic cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, and 3,5,5-trimethylcyclohexyl.

[0022] Examples of the bridged cycloalkyl group include tricyclodecanyl, adamantyl, and norbornyl.

[0023] Furthermore, the alkyl group also includes a combination of a linear alkyl group, a branched alkyl group, and a cycloalkyl group. Examples of such a combination include a cycloalkylalkyl group and the like.

[0024] The cycloalkylalkyl group is represented by the following formula. R calkyl -R alkyl - (Where R calkyl Represents a cycloalkyl group. alkyl represents an alkyl group.)

[0025] Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

[0026] Examples of the linear alkylene group include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decylene.

[0027] Examples of the branched alkylene group include diethylpentylene, trimethylbutylene, trimethylpentylene, and trimethylhexylene.

[0028] Examples of the cycloalkylene group include monocyclic cycloalkylene groups, bridged cycloalkylene groups, and condensed cycloalkylene groups. In addition, one or more hydrogen atoms of the cycloalkylene group may be substituted with a linear or branched alkyl group.

[0029] Examples of the monocyclic cycloalkylene group include cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, and 3,5,5-trimethylcyclohexylene.

[0030] Examples of the bridged ring cycloalkylene group include tricyclodecanylene, adamantylene, and norbornylene.

[0031] Examples of the fused-ring cycloalkylene group include bicyclodecanylene and the like.

[0032] Furthermore, the alkylene group also includes a combination of a linear alkylene group, a branched alkylene group, and a cycloalkylene group. Examples of such a combination include cycloalkylenealkylene groups and alkylenecycloalkylenealkylene groups.

[0033] The cycloalkylenealkylene group is represented by the following formula. -R calkylene -R alkylene - (Where R calkylene Represents a cycloalkylene group. alkylene represents an alkylene group.)

[0034] The alkylenecycloalkylenealkylene group is represented by the following formula. -R alkylene -R calkylene -R alkylene - (Where R calkylene Represents a cycloalkylene group. alkylene represents an alkylene group.)

[0035] [Release coating agent: coating agent] The present disclosure relates to a release coating agent, comprising: a block polymer, wherein the block polymer comprises a long-chain block and a hydroxyl-containing block, the long-chain block comprises a (meth)acrylate unit containing a C10-28 alkyl group, and the hydroxyl-containing block comprises a hydroxyl-containing alkyl (meth)acrylate unit.

[0036] Block polymers The block polymers may be used alone or in combination of two or more.

[0037] "Block polymer" refers to a polymer in which two or more different polymers are linked by covalent bonds. Examples of the form (block polymer) include the following. In the following, "-" refers to a covalent bond. (homopolymer of monomer A) - (homopolymer of monomer B) (Homopolymer of monomer A) - (Homopolymer of monomer B) - (Homopolymer of monomer A) (Homopolymer of monomer A) - (Homopolymer of monomer B) - (Homopolymer of monomer C) (Random polymer of monomer A and monomer B) - (Homopolymer of monomer C) (Homopolymer of monomer C) - (Random polymer of monomer A and monomer B) - (Homopolymer of monomer C) (Homopolymer of monomer C) - (Random polymer of monomer A and monomer B) - (Homopolymer of monomer D)

[0038] (Long chain block) The long chain block comprises a (meth)acrylate unit containing a C10-28 alkyl group. In one embodiment, the long chain block does not comprise a hydroxyl group-containing alkyl (meth)acrylate unit.

[0039] In one embodiment, the long chain block comprises a (meth)acrylate unit containing a C1-9 alkyl group.

[0040] Examples of the mass % content (long chain block / block polymer) include 99 mass %, 97 mass %, 95 mass %, 90 mass %, 85 mass %, 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 %, and 10 mass %. In one embodiment, the content is preferably 10 to 99 mass %, more preferably 10 to 90 mass %.

[0041] (Hydroxy-containing block) The hydroxyl group-containing block includes a hydroxyl group-containing alkyl (meth)acrylate unit. In one embodiment, the hydroxyl group-containing block does not include a C10-28 alkyl group-containing (meth)acrylate unit.

[0042] In one embodiment, the hydroxyl group-containing block comprises a (meth)acrylate unit containing a C1-9 alkyl group.

[0043] Examples of the mass % content (hydroxyl-containing block / block polymer) include 90 mass %, 85 mass %, 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 %, 3 mass %, and 1 mass %. In one embodiment, the content is preferably 1 to 90 mass %, more preferably 10 to 90 mass %.

[0044] (Other blocks) The other blocks do not contain a (meth)acrylate unit containing a C10-28 alkyl group, nor do they contain an alkyl (meth)acrylate unit containing a hydroxyl group.

[0045] In one embodiment, the other blocks include (meth)acrylate units containing a C1-9 alkyl group.

[0046] Examples of the mass % content (other blocks / block polymers) include 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 50 mass %.

[0047] (Meth)acrylate units containing C10-28 alkyl groups The (meth)acrylate containing a C10-28 alkyl group may be used alone or in combination of two or more.

[0048] Examples of the (meth)acrylate containing a C10-28 alkyl group include (meth)acrylate containing a C10-28 linear alkyl group.

[0049] Examples of the (meth)acrylate containing a C10-28 straight-chain alkyl group include 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, tetracosyl (meth)acrylate, and octadecyl (meth)acrylate.

[0050] Examples of the mass% content (C10-28 alkyl group-containing (meth)acrylate unit / block polymer) include 99 mass%, 97 mass%, 95 mass%, 90 mass%, 88 mass%, 87 mass%, 85 mass%, 83 mass%, 82 mass%, 81 mass%, 80 mass%, 79 mass%, 77 mass%, 75 mass%, 73 mass%, 71 mass%, 70 mass%, 69 mass%, 67 mass%, 65 mass%, 63 mass%, 60 mass%, 59 mass%, 58 mass%, 55 mass%, 50 mass%, 49 mass%, 45 mass%, 43 mass%, 40 mass%, 38 mass%, 35 mass%, 33 mass%, 31 mass%, and 30 mass%. In one embodiment, the content is preferably 30% to 99% by mass, more preferably 30% to 90% by mass, and further preferably 30% to 80% by mass (low transferability), greater than 80% by mass and less than 99% by mass (light peelability).

[0051] Examples of the mol% content (C10-28 alkyl group-containing (meth)acrylate unit / block polymer) include 95 mol%, 90 mol%, 85 mol%, 80 mol%, 79 mol%, 77 mol%, 75 mol%, 73 mol%, 71 mol%, 70 mol%, 69 mol%, 67 mol%, 65 mol%, 63 mol%, 61 mol%, 60 mol%, 59 mol%, 58 mol%, 55 mol%, 50 mol%, 49 mol%, 45 mol%, 43 mol%, 40 mol%, 38 mol%, 35 mol%, 33 mol%, 31 mol%, 30 mol%, 25 mol%, and 20 mol%. In one embodiment, the content is preferably 20 mol% to 95 mol%, more preferably 20 mol% to 80 mol%, and further preferably 20 mol% to 60 mol% (low transferability), greater than 60 mol% and less than 95 mol% (light peeling).

[0052] Examples of the mass% content (C10-28 alkyl group-containing (meth)acrylate unit / long-chain block) include 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 92 mass%, 91 mass%, 90 mass%, 88 mass%, 87 mass%, 85 mass%, 83 mass%, 82 mass%, 81 mass%, 80 mass%, 79 mass%, 77 mass%, 75 mass%, 73 mass%, 71 mass%, 70 mass%, 69 mass%, 67 mass%, 65 mass%, 63 mass%, 60 mass%, 59 mass%, 58 mass%, 55 mass%, 50 mass%, 49 mass%, 45 mass%, 43 mass%, 40 mass%, 38 mass%, 35 mass%, 33 mass%, 31 mass%, and 30 mass%. In one embodiment, the content is preferably 30% by mass to 100% by mass, more preferably 40% by mass to 100% by mass, and even more preferably 50% by mass to 100% by mass.

[0053] The mol% content (C10-28 alkyl group-containing (meth)acrylate unit / long chain block) is, for example, 100 mol%, 99 mol%, 98 mol%, 97 mol%, 96 mol%, 95 mol%, 94 mol%, 92 mol%, 91 mol%, 90 mol%, 88 mol%, 87 mol%, 85 mol%, 83 mol%, 82 mol%, 81 mol%, 80 mol%, 79 mol%, 77 mol%, %, 75 mol%, 73 mol%, 71 mol%, 70 mol%, 69 mol%, 67 mol%, 65 mol%, 63 mol%, 60 mol%, 59 mol%, 58 mol%, 55 mol%, 50 mol%, 49 mol%, 45 mol%, 43 mol%, 40 mol%, 38 mol%, 35 mol%, 33 mol%, 31 mol%, 30 mol%, 25 mol%, 23 mol%, 20 mol%, etc. In one embodiment, the content is preferably 20 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, and even more preferably 50 mol% to 100 mol%.

[0054] Hydroxyl-containing alkyl (meth)acrylate units The hydroxyl group-containing alkyl (meth)acrylate may be used alone or in combination of two or more.

[0055] Examples of the hydroxyl group-containing alkyl (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, glycerol mono(meth)acrylate, and caprolactone adducts thereof.

[0056] The mass% content (hydroxyl group-containing alkyl (meth)acrylate unit / block polymer) is, for example, 90 mass%, 89 mass%, 87 mass%, 85 mass%, 83 mass%, 81 mass%, 80 mass%, 79 mass%, 77 mass%, 75 mass%, 73 mass%, 71 mass%, 70 mass%, 69 mass%, 67 mass%, 65 mass%, 63 mass%, 60 mass%, 59 mass%, 58 mass%, %, 55% by mass, 53% by mass, 50% by mass, 49% by mass, 45% by mass, 43% by mass, 40% by mass, 38% by mass, 35% by mass, 33% by mass, 31% by mass, 30% by mass, 29% by mass, 27% by mass, 25% by mass, 23% by mass, 21% by mass, 20% by mass, 19% by mass, 18% by mass, 15% by mass, 12% by mass, 10% by mass, 5% by mass, 1% by mass, etc. In one embodiment, the content is preferably 1% by mass to 90% by mass, more preferably 10% by mass to 70% by mass, further preferably 1% by mass or more and less than 20% by mass (light peeling) and 20% by mass to 70% by mass (low transferability).

[0057] Examples of the mol% content (hydroxyl-containing alkyl (meth)acrylate unit / block polymer) include 80 mol%, 79 mol%, 77 mol%, 75 mol%, 73 mol%, 71 mol%, 70 mol%, 69 mol%, 67 mol%, 65 mol%, 63 mol%, 60 mol%, 59 mol%, 58 mol%, 55 mol%, 50 mol%, 49 mol%, 45 mol%, 43 mol%, 40 mol%, 38 mol%, 35 mol%, 33 mol%, 31 mol%, 30 mol%, 25 mol%, 20 mol%, 18 mol%, 15 mol%, 12 mol%, 10 mol%, 9 mol%, 7 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1.5 mol%, 1.1 mol%, and 1 mol%. In one embodiment, the content is preferably 1 mol% to 80 mol%, more preferably 1 mol% or more and less than 40 mol% (easy peeling) or 40 mol% to 80 mol% (low migration).

[0058] The mass% content (hydroxyl group-containing alkyl (meth)acrylate unit / hydroxyl group-containing block) includes, for example, 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 92 mass%, 91 mass%, 90 mass%, 88 mass%, 87 mass%, 85 mass%, 83 mass%, 82 mass%, 81 mass%, 80 mass%, 79 mass%, 77 mass%, 75 mass%, 73 mass%, 71 mass%, 70 mass%, 69 mass%, 67 mass%, 65 mass%, 63 mass%, 60 mass%, 59 mass%, 69 mass%, 67 mass%, 65 mass%, 63 mass%, 60 mass%, 69 ... %, 58% by mass, 55% by mass, 50% by mass, 49% by mass, 45% by mass, 43% by mass, 40% by mass, 38% by mass, 35% by mass, 33% by mass, 31% by mass, 30% by mass, 29% by mass, 27% by mass, 25% by mass, 23% by mass, 21% by mass, 20% by mass, 18% by mass, 15% by mass, 12% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1.5% by mass, 1.1% by mass, 1% by mass, 0.9% by mass, 0.5% by mass, 0.1% by mass, etc. In one embodiment, the content is preferably 0.1% to 100% by mass.

[0059] The mol% content (hydroxyl group-containing alkyl (meth)acrylate unit / hydroxyl group-containing block) includes, for example, 100 mol%, 99 mol%, 98 mol%, 97 mol%, 96 mol%, 95 mol%, 94 mol%, 92 mol%, 91 mol%, 90 mol%, 88 mol%, 87 mol%, 85 mol%, 83 mol%, 82 mol%, 81 mol%, 80 mol%, 79 mol%, 77 mol%, 75 mol%, 73 mol%, 71 mol%, 70 mol%, 69 mol%, 67 mol%, 65 mol%, 63 mol%, %, 60 mol%, 59 mol%, 58 mol%, 55 mol%, 50 mol%, 49 mol%, 45 mol%, 43 mol%, 40 mol%, 38 mol%, 35 mol%, 33 mol%, 31 mol%, 30 mol%, 25 mol%, 20 mol%, 18 mol%, 15 mol%, 12 mol%, 10 mol%, 9 mol%, 7 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1.5 mol%, 1.1 mol%, 1 mol%, 0.9 mol%, 0.5 mol%, 0.1 mol%, etc. In one embodiment, the content is preferably 0.1 mol% to 100 mol%.

[0060] (Meth)acrylate units containing C1-9 alkyl groups In one embodiment, the block polymer may optionally include a C1-9 alkyl group-containing (meth)acrylate unit. The C1-9 alkyl group-containing (meth)acrylate may be used alone or in combination of two or more.

[0061] Examples of the C1-9 alkyl group-containing (meth)acrylate include C1-9 linear alkyl group-containing (meth)acrylate.

[0062] Examples of the (meth)acrylate containing a C1-9 linear alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, and nonyl (meth)acrylate.

[0063] Examples of the mass % content (C1-9 alkyl group-containing (meth)acrylate units / block polymer) include 30 mass %, 29 mass %, 27 mass %, 25 mass %, 23 mass %, 21 mass %, 20 mass %, 18 mass %, 15 mass %, 12 mass %, 10 mass %, 9 mass %, 7 mass %, 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1.5 mass %, 1.1 mass %, 1 mass %, 0.9 mass %, 0.5 mass %, 0.1 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 30 mass %.

[0064] Examples of the mole % content (C1-9 alkyl group-containing (meth)acrylate units / block polymer) include 35 mol%, 30 mol%, 25 mol%, 20 mol%, 18 mol%, 15 mol%, 12 mol%, 10 mol%, 9 mol%, 7 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1.5 mol%, 1.1 mol%, 1 mol%, 0.9 mol%, 0.5 mol%, 0.1 mol%, and 0 mol%. In one embodiment, the content is preferably 0 mol% to 35 mol%.

[0065] Examples of the mass % content (C1-9 alkyl group-containing (meth)acrylate unit / long chain block) include 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 35 mass %.

[0066] Examples of the mole % content (C1-9 alkyl group-containing (meth)acrylate unit / long chain block) include 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, and 0 mol%. In one embodiment, the content is preferably 0 mol% to 50 mol%.

[0067] Examples of the mass % content (C1-9 alkyl group-containing (meth)acrylate unit / hydroxyl group-containing block) include 55 mass %, 50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 55 mass %.

[0068] Examples of the mole % content (C1-9 alkyl group-containing (meth)acrylate unit / hydroxyl group-containing block) include 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, and 0 mol%. In one embodiment, the content is preferably 0 mol% to 50 mol%.

[0069] Examples of the mass% content (C1-9 alkyl group-containing (meth)acrylate unit / other blocks) include 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 92 mass%, 91 mass%, 90 mass%, 88 mass%, 87 mass%, 85 mass%, 83 mass%, 82 mass%, 81 mass%, 80 mass%, 79 mass%, 77 mass%, 75 mass%, 73 mass%, 71 mass%, 70 mass%, 69 mass%, 67 mass%, 65 mass%, 63 mass%, 60 mass%, and 59 mass%. %, 58 mass%, 55 mass%, 50 mass%, 49 mass%, 45 mass%, 43 mass%, 40 mass%, 38 mass%, 35 mass%, 33 mass%, 31 mass%, 30 mass%, 29 mass%, 27 mass%, 25 mass%, 23 mass%, 21 mass%, 20 mass%, 18 mass%, 15 mass%, 12 mass%, 10 mass%, 9 mass%, 7 mass%, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1.5 mass%, 1.1 mass%, 1 mass%, 0.9 mass%, 0.5 mass%, 0.1 mass%, 0 mass%, etc. In one embodiment, the content is preferably 0 mass% to 100 mass%.

[0070] The mol% content (C1-9 alkyl group-containing (meth)acrylate unit / other blocks) includes, for example, 100 mol%, 99 mol%, 98 mol%, 97 mol%, 96 mol%, 95 mol%, 94 mol%, 92 mol%, 91 mol%, 90 mol%, 88 mol%, 87 mol%, 85 mol%, 83 mol%, 82 mol%, 81 mol%, 80 mol%, 79 mol%, 77 mol%, 75 mol%, 73 mol%, 71 mol%, 70 mol%, 69 mol%, 67 mol%, 65 mol%, and 63 mol%. %, 60 mol%, 59 mol%, 58 mol%, 55 mol%, 50 mol%, 49 mol%, 45 mol%, 43 mol%, 40 mol%, 38 mol%, 35 mol%, 33 mol%, 31 mol%, 30 mol%, 25 mol%, 20 mol%, 18 mol%, 15 mol%, 12 mol%, 10 mol%, 9 mol%, 7 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1.5 mol%, 1.1 mol%, 1 mol%, 0.9 mol%, 0.5 mol%, 0.1 mol%, 0 mol%, etc. In one embodiment, the content is preferably 0 mol% to 100 mol%.

[0071] ·Monomer units other than the above: other monomer units The block polymer may optionally contain monomer units other than those described above (other monomer units). Other monomers may be used alone or in combination of two or more.

[0072] Examples of other monomers include (meth)acrylic acid, alkenyl (meth)acrylates, (meth)acrylamide, (meth)acrylonitrile, polyfunctional (meth)acrylates, and polycyclic aliphatic hydrocarbon group-containing monomers.

[0073] Examples of the mass % content (other monomer units / block polymer), mass % content (other monomer units / long-chain block), mass % content (other monomer units / hydroxyl-containing block), and mass % content (other monomer units / other blocks) include less than 5 mass %, less than 4 mass %, less than 3 mass %, less than 2 mass %, less than 1 mass %, less than 0.1 mass %, and 0 mass %.

[0074] Examples of the mol% content (other monomer units / block polymer), mol% content (other monomer units / long-chain block), mol% content (other monomer units / hydroxyl-containing block), and mol% content (other monomer units / other blocks) include less than 5 mol%, less than 4 mol%, less than 3 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, and 0 mol%.

[0075] Examples of the content in parts by mass (other monomer units / (meth)acrylate units containing C10-28 alkyl groups), the content in parts by mass (other monomer units / hydroxyl group-containing alkyl (meth)acrylate units), and the content in parts by mass (other monomer units / (meth)acrylate units containing C1-9 alkyl groups) include less than 5% by mass, less than 4% by mass, less than 2% by mass, less than 1% by mass, less than 0.1% by mass, and 0% by mass.

[0076] Examples of the molar content (other monomer units / (meth)acrylate units containing C10-28 alkyl groups), the molar content (other monomer units / hydroxyl-containing alkyl (meth)acrylate units), and the molar content (other monomer units / (meth)acrylate units containing C1-9 alkyl groups) include less than 5 mol%, less than 4 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, and 0 mol%.

[0077] <Physical Properties, etc.: Block Polymers> Examples of the number average molecular weight Mn (block polymer) include 100,000, 90,000, 80,000, 75,000, 70,000, 65,000, 60,000, 55,000, 50,000, 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 15,000, 10,000, and 5,000. In one embodiment, the number average molecular weight is preferably 5,000 to 100,000.

[0078] Examples of the weight average molecular weight Mw (block polymer) include 200,000, 190,000, 180,000, 170,000, 160,000, 150,000, 140,000, 130,000, 120,000, 110,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 15,000, 10,000, and 5,000. In one embodiment, the weight average molecular weight is preferably 5,000 to 200,000.

[0079] Examples of the molecular weight distribution Mw / Mn (block polymer) include 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, and 1.0. In one embodiment, the molecular weight distribution is preferably 1.0 to 2.0.

[0080] The weight average molecular weight and number average molecular weight can be determined as polystyrene-equivalent values ​​measured in an appropriate solvent by gel permeation chromatography (GPC), for example. Detailed conditions include the following. Model: Product name "HLC-8220" (manufactured by Tosoh Co., Ltd.) Column: PLgel MIXED-C (manufactured by Agilent Technology) x 2 Developing solvent, flow rate: tetrahydrofuran, 1.0 mL / min Measurement temperature: 40°C Detector: refractive index (RI) Standard: Monodisperse polystyrene Polymer concentration: 0.2%

[0081] Examples of the hydroxyl value (block polymer) include 300 mgKOH / g, 275 mgKOH / g, 250 mgKOH / g, 225 mgKOH / g, 200 mgKOH / g, 175 mgKOH / g, 150 mgKOH / g, 125 mgKOH / g, 100 mgKOH / g, 75 mgKOH / g, 50 mgKOH / g, and 25 mgKOH / g. In one embodiment, the hydroxyl value is preferably 25 to 300 mgKOH / g.

[0082] The hydroxyl value can be measured by a method in accordance with Japanese Industrial Standard (JIS) K0070 (neutralization titration method).

[0083] When the input amounts of monomers used in polymer production are accurately determined and the polymerization rate is high, the hydroxyl value can be calculated using the following formula. Hydroxyl value = [(the input mass of the hydroxyl-containing monomer in 1 g of the total monomer input × the number of hydroxyl groups in one molecule of the hydroxyl-containing monomer) / molecular weight of the hydroxyl-containing monomer] × 56.11 (molecular weight of KOH) × 1000 <Production Method (Block Polymer)> Examples of the production method (block polymer) include living radical polymerization.

[0084] Examples of living radical polymerization include RAFT polymerization (Reversible Addition / Fragmentation chain Transfer Polymerization).

[0085] Examples of the RAFT agent include thiocarbonates, dithiobenzoates, and xanthates.

[0086] Examples of thiocarbonates include benzylbutyl trithiocarbonate, S,S-dibenzyl trithiocarbonate, 4-cyano-4-[(dodecylthiocarbonylthio)thio]pentanoic acid, 2-cyano-2-[(dodecylthiocarbonylthio)thio]propane, 4-cyano-4-[(dodecylthiocarbonylthio)thio]pentanol, cyanomethyldodecyl trithiocarbonate, and bis(dodecylthiocarbonylthio)disulfide.

[0087] Examples of dithiobenzoic acid esters include 2-cyano-2-propylbenzodisulfide, 4-cyano-4-[(thiobenzoyl)thio]pentanoic acid, and ethyl-2-methyl-2-(phenylthiocarbonylthio)acetate.

[0088] Examples of xanthate include dithiocarbonates such as ethyl 2-[(ethoxythiocarbonyl)thio]propionate, O-ethyl-S-2-cyano-2-propyl-dithiocarbonate, O-ethyl-S-benzyl-dithiocarbonate, and O-ethyl-S-cyanomethyl-dithiocarbonate.

[0089] The amount used in parts by mass (RAFT agent / monomer in each stage) is preferably 0.1 to 10 parts by mass.

[0090] The radical polymerization initiator may be used alone or in combination of two or more. Examples of the radical polymerization initiator include inorganic peroxides, organic peroxides, and azo compounds.

[0091] Examples of the inorganic peroxide include hydrogen peroxide, ammonium persulfate, and potassium persulfate.

[0092] Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, and lauroyl peroxide.

[0093] Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and dimethyl 2,2'-azobisisobutyrate.

[0094] The amount used in parts by mass (radical polymerization initiator / monomer in each stage) is preferably 1 to 10 parts by mass.

[0095] The polymerization temperature (each stage) is preferably 50°C to 140°C.

[0096] The polymerization time (each stage) is preferably 1 to 10 hours.

[0097] In one embodiment, the block polymer is a RAFT polymer. In one embodiment, the long chain block is present on the sulfur containing terminal side (RAFT agent side).

[0098] In one embodiment, the block polymer does not contain peroxy groups.

[0099] The mass % content (block polymer / coating agent non-volatile component) includes, for example, 95 mass %, 90 mass %, 85 mass %, 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 %, 4 mass %, 2 mass %, 1 mass %, etc. In one embodiment, the content is preferably 1 mass % to 95 mass %, more preferably 4 mass % to 20 mass %. The reasons for this are, for example, reduced peeling force after heating and low transferability.

[0100] Cross-linking agent In one embodiment, the coating agent may optionally contain a crosslinking agent. The crosslinking agent may be used alone or in combination of two or more.

[0101] Examples of the cross-linking agent include a melamine cross-linking agent and an isocyanate cross-linking agent.

[0102] Examples of the mass % content (crosslinking agent / coating agent non-volatile component) include 55 mass %, 50 mass %, 45 mass %, 44 mass %, 43 mass %, 42 mass %, 41 mass %, 40 mass %, 39 mass %, 38 mass %, 37 mass %, 36 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 1 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 55 mass %.

[0103] (Melamine crosslinking agent) The melamine cross-linking agent may be used alone or in combination of two or more.

[0104] Examples of the melamine cross-linking agent include melamine resins containing a structural unit derived from the following melamine compound.

ML1

[0105] In one embodiment, the average degree of polymerization of the melamine resin is preferably 1.1 to 10.

[0106] As the melamine resin, preferably, methylated melamine resin and butylated melamine resin are mentioned, and more preferably, fully ether type methylated melamine resin, fully ether type butylated melamine resin and fully ether type methyl·butylated melamine resin are mentioned.

[0107] "Methylated melamine" refers to the above R m1 ~R m6 A melamine compound wherein at least one of the R m1 ~R m6 A melamine compound containing only methoxymethyl groups. "Methylated melamine resin" refers to a resin composed solely of structural units derived from methylated melamine. "Fully ether methylated melamine resin" refers to a resin composed solely of structural units derived from fully ether methylated melamine.

[0108] "Butylated melamine" refers to the above R m1 ~R m6 A melamine compound wherein at least one of the R m1 ~R m6 Melamine compounds containing either n-butoxymethyl or isobutoxymethyl groups. "Butylated melamine resin" refers to a resin composed solely of structural units derived from butylated melamine. "Fully ether butylated melamine resin" refers to a resin composed solely of structural units derived from fully ether butylated melamine.

[0109] "Fully ether methyl butylated melamine" refers to the above R m1 ~R m6 A melamine compound in which at least one of the methyl groups is a methoxymethyl group and the remaining methyl groups are either n-butoxymethyl or isobutoxymethyl groups. A "full ether type methyl butylated melamine resin" refers to a resin composed only of structural units derived from full ether type methyl butylated melamine.

[0110] Marketplace (three-component resin) examples include Cymel 300, Cymel 301, Cymel 303LF, Cymel 350, Cymel 370N, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, Cymel 701, Cymel 266, Cymel 267, Cymel 285, Cymel 232, Cymel 235, Cymel 236, Cymel 238, Cymel 272, Cymel 212, Cymel 253, Cymel 254 , Cymel 202, Cymel 207, Mycoat 506 (all manufactured by Allnex Japan Co., Ltd.), Nikalac MW-30M, Nikalac MW-30, Nikalac MW-30HM, Nikalac MW-390, Nikalac MW-100LM, Nikalac MX-750LM, Nikalac MW-22, Nikalac MS-21, Nikalac MS-11, Nikalac MW-24X, Nikalac MS-001, Nikalac M X-002, Nikalac MX-730, Nikalac MX-750, Nikalac MX-708, Nikalac MX-706, Nikalac MX-042, Nikalac MX-035, Nikalac MX-45, Nikalac MX-43, Nikalac MX-417, Nikalac MX-410 (all manufactured by Sanwa Chemical Co., Ltd.), U-Ban 20SB, U-Ban 20SE60, U-Ban 21R, U-Ban 22R, U-Ban 122, U-BAN 125, U-BAN 220, U-BAN 225, U-BAN 228, U-BAN 2020 (all manufactured by Mitsui Chemicals, Inc.), AMIDIA J-820-60, AMIDIA L-109-65, AMIDIA L-117-60, AMIDIA L-127-60, AMIDIA 13-548, AMIDIA G-821-60, AMIDIA L-110-60, AMIDIA L-125-60, AMIDIA L-166-60B (all manufactured by DIC Corporation), etc.

[0111] Examples of the mass % content (melamine crosslinking agent / coating agent non-volatile component) include 55 mass %, 50 mass %, 45 mass %, 44 mass %, 43 mass %, 42 mass %, 41 mass %, 40 mass %, 39 mass %, 38 mass %, 37 mass %, 36 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 4 mass %, 2 mass %, 1 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 55 mass %, more preferably 20 mass % to 55 mass %.

[0112] In one embodiment, the content (N-methylol and N-alkoxymethylol / coating agent non-volatile matter) is preferably greater than 0.3 mmol / g.

[0113] (isocyanate crosslinker) The isocyanate cross-linking agent may be used alone or in combination of two or more.

[0114] Examples of the isocyanate crosslinking agent include polyisocyanate.

[0115] “Polyisocyanate” refers to a compound having two or more isocyanate groups (—N═C═O).

[0116] Examples of the polyisocyanate include linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and biuret forms, isocyanurate forms, allophanate forms, and adduct forms thereof.

[0117] Examples of the linear aliphatic polyisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate.

[0118] Examples of the branched aliphatic polyisocyanate include diethylpentamethylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0119] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, bridged alicyclic polyisocyanate, and condensed alicyclic polyisocyanate.

[0120] Examples of the monocyclic alicyclic polyisocyanate include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexylmethane diisocyanate.

[0121] Examples of the bridged alicyclic polyisocyanate include tricyclodecene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

[0122] Examples of the condensed-ring alicyclic polyisocyanate include dicyclodecene diisocyanate.

[0123] Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanate and condensed-ring aromatic polyisocyanate.

[0124] Examples of the monocyclic aromatic polyisocyanate include dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanates such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, and tetramethyl-m-xylylene diisocyanate.

[0125] Examples of the condensed-ring aromatic polyisocyanate include 1,5-naphthalene diisocyanate.

[0126] Blocked isocyanates can also be used. "Blocked isocyanates" refer to compounds in which the isocyanate groups of a polyisocyanate are protected by a blocking agent.

[0127] Examples of the mass % content (isocyanate crosslinking agent / coating agent non-volatile component) include 55 mass %, 50 mass %, 45 mass %, 44 mass %, 43 mass %, 42 mass %, 41 mass %, 40 mass %, 39 mass %, 38 mass %, 37 mass %, 36 mass %, 35 mass %, 30 mass %, 25 mass %, 20 mass %, 15 mass %, 10 mass %, 5 mass %, 4 mass %, 2 mass %, 1 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 55 mass %.

[0128] Polyols In one embodiment, the coating agent may optionally contain a polyol. The polyol may be used alone or in combination of two or more.

[0129] "Polyol" refers to a compound having two or more hydroxyl groups (-OH).

[0130] Examples of the polyol include alkylene polyols, dimer glycol, hydrogenated dimer glycol, castor oil-based polyols, hydroxyl-containing fatty acid alkylene polyol esters, polyether polyols, polyester polyols, polycarbonate polyols, and polyolefin polyols.

[0131] (Alkylene polyol) The "alkylene polyol" refers to a compound containing an alkylene group and two or more hydroxyl groups.

[0132] Examples of the alkylene polyol include linear alkylene polyol, branched alkylene polyol, and cycloalkylene polyol.

[0133] Examples of the linear alkylene polyol include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol.

[0134] Examples of the branched alkylene polyol include neopentyl glycol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,4-dibutyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, propylene glycol, 1,2-butanediol, pentaerythritol, and trimethylolpropane.

[0135] Examples of the cycloalkylene polyol include monocyclic cycloalkylene polyol and bridged cycloalkylene polyol.

[0136] Examples of the monocyclic cycloalkylene polyol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2,2′-bis(4-hydroxycyclohexyl)propane.

[0137] Examples of the bridged ring cycloalkylene polyol include tricyclodecane dimethanol and the like.

[0138] (Dimer diol) "Dimer diol" refers to a compound obtained by reducing the reaction product of cyclic and / or acyclic dimer acids obtained by dimerizing higher unsaturated fatty acids with methanol. Examples of the dimerization reaction of higher unsaturated fatty acids include the method described in Japanese Patent Application Laid-Open No. 9-136861. "Hydrogenated dimer diol" is a compound obtained by hydrogenating dimer diol.

[0139] When producing 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 C14-22 unsaturated monocarboxylic acids.

[0140] Examples of C14-22 unsaturated monocarboxylic acids include tetradecadienoic acid, hexadecadienoic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, arachidonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, eicosenoic acid, erucic acid, cetoleic acid, and brassidic acid. Among these, oleic acid and / or linoleic acid are preferred.

[0141] (Castor oil-based polyol) Examples of castor oil-based polyols include hydroxyl group-containing fatty acid glycerol (poly)esters.

[0142] The "hydroxyl-containing fatty acid glycerol (poly)ester" refers to, for example, a (poly)ester (monoester, diester, triester) obtained by reacting one or more hydroxyl groups of glycerol with a hydroxyl-containing fatty acid.

[0143] As the hydroxyl-containing fatty acid, preferably a C12 or higher hydroxyl-containing long-chain fatty acid, more preferably a C12-30 hydroxyl-containing long-chain fatty acid, further preferably a C12-24 hydroxyl-containing long-chain fatty acid, and particularly preferably a C12-20 hydroxyl-containing long-chain fatty acid.

[0144] Examples of the hydroxyl group-containing long-chain fatty acid include hydroxyl group-containing saturated long-chain fatty acids and hydroxyl group-containing unsaturated long-chain fatty acids.

[0145] Examples of the hydroxyl-containing saturated long-chain fatty acids include hydroxylauric acid, hydroxytridecyl acid, hydroxymyristic acid, hydroxypentadecanyl acid, hydroxypalmitic acid, hydroxyheptadecanyl acid, hydroxystearic acid, hydroxynonadecanyl acid, hydroxyeicosyl acid, hydroxyheneicosyl acid, hydroxydocosyl acid, hydroxytricosyl acid, hydroxytetracosyl acid, hydroxypentacosyl acid, hydroxyhexacosyl acid, hydroxyheptacosyl acid, hydroxyoctacosyl acid, hydroxyisododecyl acid, hydroxyisotridecyl acid, hydroxyisomyristic acid, hydroxyisopentadecanyl acid, hydroxyisohexadecyl acid, hydroxyisoheptadecanyl acid, hydroxyisostearic acid, and aleuritic acid.

[0146] Examples of the hydroxyl-containing unsaturated long-chain fatty acids include hydroxyl-containing monounsaturated long-chain fatty acids, hydroxyl-containing diunsaturated long-chain fatty acids, hydroxyl-containing triunsaturated long-chain fatty acids, hydroxyl-containing tetraunsaturated long-chain fatty acids, hydroxyl-containing pentaunsaturated long-chain fatty acids, and hydroxyl-containing hexaunsaturated long-chain fatty acids.

[0147] Examples of the hydroxyl-containing monounsaturated long-chain fatty acids include ricinoleic acid, hydroxymyristoleic acid, hydroxypalmitoleic acid, hydroxysapienic acid, hydroxyoleic acid, hydroxyelaidic acid, hydroxyoctadecenoic acid, hydroxygadoleic acid, hydroxyeicosenoic acid, hydroxyerucic acid, and hydroxynervonic acid.

[0148] Examples of the hydroxyl group-containing diunsaturated long-chain fatty acid include hydroxylinolenic acid, hydroxyeicosadienoic acid, and hydroxydocosadienoic acid.

[0149] Examples of the hydroxyl-containing triunsaturated long-chain fatty acid include hydroxylinolenic acid, hydroxypinolenic acid, hydroxyeleostearic acid, hydroxymeadacid, and hydroxyeicosatrienoic acid.

[0150] Examples of the hydroxyl-containing tetraunsaturated long-chain fatty acid include hydroxystearidonic acid, hydroxyarachidonic acid, and hydroxyadrenic acid.

[0151] Examples of the hydroxyl-containing pentaunsaturated long-chain fatty acids include hydroxybosseopentaenoic acid, hydroxy eicosapentaenoic acid, hydroxy osbond acid, hydroxy clupanodonic acid, and hydroxy tetracosapentaenoic acid.

[0152] Examples of the hydroxyl group-containing hexaunsaturated long-chain fatty acid include hydroxydocosahexaenoic acid and hydroxynisinic acid.

[0153] (Hydroxy-containing fatty acid alkylene polyol ester) The "hydroxyl-containing fatty acid alkylene polyol ester" refers to an ester obtained by reacting a hydroxyl-containing fatty acid with an alkylene polyol.

[0154] Examples of the hydroxyl group-containing fatty acid and alkylene polyol include the above-mentioned compounds.

[0155] (Polyether polyol) “Polyether polyol” refers to, for example, a compound having two or more hydroxyl groups and two or more consecutive repeating units containing an ether bond.

[0156] In one embodiment, the polyether polyol is represented by the following structural formula. HO-(R Ether -O-) n H (Where R Ether is an alkylene group, an arylene group, or an arylenealkylenearylene group, and n is an integer greater than 2)

[0157] Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and alkylene oxide adducts of polyols.

[0158] Examples of products (polyether polyols) include Adosol GM-30, Adosol P-400, Adosol G-40 0. Atolu T-400, Atolu AM-302 (the above are manufactured by ADEKA Co., Ltd.), etc.

[0159] (Polyester polyol) "Polyester polyol" refers to a compound having two or more hydroxyl groups and two or more consecutive repeating units containing an ester bond. In addition, polycaprolactone polyol is a type of polyester polyol.

[0160] In one embodiment, the polyester polyol is represented by the following structural formula. HO-{R aEster -OC(=O)-R bEster -C(=O)O} m -R cEster -OH (where R aEster 、R bEster and R cEsterare each independently an alkylene group or an arylene group, and m is an integer greater than or equal to 2).

[0161] Examples of the polyester polyol include reaction products of polycarboxylic acids or their carboxylic anhydrides and polyols.

[0162] Examples of the polycarboxylic acid include dicarboxylic acid.

[0163] Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and cyclohexane dicarboxylic acid.

[0164] Examples of the polycarboxylic acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, and trimellitic anhydride.

[0165] Examples of the polyol include the above-mentioned alkylene polyols.

[0166] (Polycarbonate polyol) “Polycarbonate polyol” refers to a compound having two or more hydroxyl groups and two or more repeating units containing a carbonate bond.

[0167] In one embodiment, the polycarbonate polyol is represented by the following structural formula. HO-{R aCarbo -OC(=O)O} p -R bCarbo -OH (Where R aCarbo and R bCarbo are each independently an alkylene group, and p is an integer greater than or equal to 2).

[0168] Examples of the polycarbonate polyol include reaction products of polyols and phosgene, and ring-opening polymers of cyclic carbonates (such as alkylene carbonates).

[0169] Examples of the polyol include the above-mentioned alkylene polyols.

[0170] Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate.

[0171] Examples of commercially available products (polycarbonate polyols) include ETERNACOLL UH-50 and ETERNACOLL PH-50 (both manufactured by Ube Industries, Ltd.), Duranol T5625, Duranol T5652, and Duranol G3452 (both manufactured by Asahi Kasei Corporation).

[0172] (Polyolefin polyol) Examples of the polyolefin polyol include polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorides thereof, each having two or more hydroxyl groups.

[0173] Examples of commercially available products (polyolefin polyols) include NISSO-PB GI-1000 (manufactured by Nippon Soda Co., Ltd.).

[0174] (Physical Properties, etc. (Polyol)) Examples of the molecular weight (polyol) include 50,000, 40,000, 30,000, 20,000, 10,000, 5,000, 4,000, 3,500, 3,001, 3,000, 2,500, 2,000, 1,500, 1,000, 500, 250, and 100. In one embodiment, the molecular weight is preferably 100 to 50,000.

[0175] When simply referred to as "molecular weight," the molecular weight refers to either the formula weight or the number average molecular weight. When the structure of a compound can be uniquely represented by a specific chemical formula (i.e., the molecular weight distribution is 1), the molecular weight refers to the formula weight. On the other hand, when the structure of a compound cannot be uniquely represented by a specific chemical formula (i.e., the molecular weight distribution is greater than 1), the molecular weight refers to the number average molecular weight.

[0176] Examples of the hydroxyl value (polyol) include 1300 mgKOH / g, 1200 mgKOH / g, 1100 mgKOH / g, 1000 mgKOH / g, 900 mgKOH / g, 800 mgKOH / g, 750 mgKOH / g, 700 mgKOH / g, 600 mgKOH / g, 500 mgKOH / g, 400 mgKOH / g, 300 mgKOH / g, 250 mgKOH / g, 200 mgKOH / g, 150 mgKOH / g, 100 mgKOH / g, 90 mgKOH / g, 75 mgKOH / g, 50 mgKOH / g, and 40 mgKOH / g. In one embodiment, the hydroxyl value is preferably 40 to 1300 mgKOH / g.

[0177] Examples of the mass % content (polyol / coating agent non-volatile component) include 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 %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 65 mass %.

[0178] Curing catalyst The coating agent may optionally contain a curing catalyst. The curing catalyst may be used alone or in combination of two or more.

[0179] Examples of the curing catalyst include acid catalysts.

[0180] Examples of the acid catalyst include inorganic acids, organic acids, and thermal acid generators.

[0181] Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.

[0182] Examples of the organic acid include organic carboxylic acid, organic sulfonic acid, and organic phosphoric acid.

[0183] Examples of the organic carboxylic acid include oxalic acid, acetic acid, and formic acid.

[0184] Examples of the organic sulfonic acid include methanesulfonic acid, trifluoromethanesulfonic acid, isoprenesulfonic acid, camphorsulfonic acid, hexanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, hexadecanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cumenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and nonylnaphthalenesulfonic acid.

[0185] An example of organic phosphoric acid is methyl acid phosphate. 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, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, dinonylphenyl acid phosphate, etc.

[0186] Examples of the thermal acid generator include sulfonium salts, benzothiazole salts, ammonium salts, and phosphonium salts.

[0187] Examples of the mass % content (curing catalyst / coating agent non-volatile component) include 5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 5 mass %.

[0188] Organic solvents In one embodiment, the coating agent may optionally contain an organic solvent. The organic solvent may be used alone or in combination of two or more.

[0189] Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, alkyl halide solvents, and amide solvents.

[0190] Examples of the ketone solvent include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

[0191] Examples of the aromatic solvent include toluene and xylene.

[0192] Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol.

[0193] Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol.

[0194] Examples of the glycol ether solvent include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, and ethylene glycol mono-tert-butyl ether.

[0195] Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

[0196] Examples of the petroleum-based solvent include Solbeso #100 (manufactured by Exxon) and Solbeso #150 (manufactured by Exxon).

[0197] Examples of the alkyl halide solvent include chloroform.

[0198] Examples of the amide solvent include dimethylformamide.

[0199] Examples of the mass % content (organic solvent / coating agent) include 99 mass %, 95 mass %, 90 mass %, 85 mass %, 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 %, and 0 mass %. In one embodiment, the content is preferably 0 mass % to 99 mass %.

[0200] <Additives> The release coating agent may optionally contain an agent (additive) that does not belong to any of the above.

[0201] Examples of additives include urethane resins, polyester resins, epoxy resins, defoaming agents, anti-slip agents, preservatives, rust inhibitors, pH adjusters, antioxidants, pigments, dyes, lubricants, leveling agents, conductive agents, polybutadiene, polyisoprene, polychloroprene, polypentene, polybutylene, polyisobutylene, polystyrene, isoprene-butadiene copolymers, styrene-isoprene copolymers, polyolefins and derivatives thereof, silicone resins, epoxy-containing compounds, amines, carboxylic anhydrides, and long-chain alkyl-containing alcohols.

[0202] In one embodiment, the content (additive / release coating agent) in parts by mass is preferably less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, or 0 part by mass.

[0203] In one embodiment, the content in parts by mass (additive / block polymer), the content in parts by mass (additive / cross-linking agent), the content in parts by mass (additive / curing catalyst), and the content in parts by mass (additive / organic solvent) are preferably less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc.

[0204] The release coating agent can be produced by dispersing and mixing the above-mentioned reagents.

[0205] Examples of the dispersing and mixing means include a stirrer, an emulsifying disperser, and an ultrasonic disperser.

[0206] Examples of applications (release coating agents) include thermosetting release coating agents, non-silicone release coating agents, thermosetting release coating agents for sheet molding, thermosetting release coating agents for green sheet production, and thermosetting release coating agents for adhesion.

[0207] [cured material] The present disclosure relates to a cured product of the release coating agent.

[0208] In one embodiment, the cured product includes, for example, a thermally cured product, etc. Curing conditions include, for example, the conditions described below.

[0209] [Laminate] The present disclosure relates to a laminate comprising the cured product.

[0210] In one embodiment, the laminate has a cured product of the coating agent on one or both sides of the substrate.

[0211] The amount of the cured product in the laminate is preferably 0.01 g / m 2 ~10g / m 2 More preferably, 0.05 g / m 2 ~5g / m 2 .

[0212] <Base material> Examples of the substrate include polyester, polycarbonate, polystyrene, polyimide, polyolefin, polyepoxy resin, triacetyl cellulose resin, acrylonitrile butadiene styrene (ABS) resin, acrylonitrile styrene (AS) resin, norbornene-based resin, polyester laminated paper, polyethylene laminated paper, and paper.

[0213] Examples of polyester include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.

[0214] Examples of the coating method include spraying, roll coater, reverse roll coater, gravure coater, knife coater, bar coater, and spot coater.

[0215] Examples of the curing method include heating.

[0216] Examples of the heating method include a circulating air dryer, etc. Examples of the drying (curing) temperature include 90° C. to 170° C., etc. Examples of the drying time include 30 seconds to 2 minutes, etc. [Example]

[0217] The present invention is described in detail below using examples and comparative examples. However, the above description and the following examples are not intended to limit the present invention. The present invention is limited only to the scope of the claims. Unless otherwise specified, all values ​​such as parts and % are by mass.

[0218] Preparation Example 1: Block Polymer (Phase 1) In a 300 mL flask equipped with a cooling tube and a nitrogen line, methyl ethyl ketone (57.58 g, 799 mmol), lauryl acrylate (60.10 g, 250 mmol), and RAFT-009 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2-cyano-2-[(dodecylthiocarbonylthio)thio]propane, 1.73 g, 5.00 mmol) were placed. The temperature in the reactor was raised to 80°C, 2,2'-azobis(2-methylbutyronitrile) (0.27 g, 1.65 mmol) was added, and polymerization was carried out for 2 hours while maintaining the liquid temperature at 80°C±2°C to obtain a first-stage product (macro RAFT agent) (Mn: 8500, Mw: 10000). (Phase 2) Methyl ethyl ketone (29.03 g, 403 mmol) and 2-hydroxyethyl acrylate (29.03 g, 250 mmol) were placed in the first-stage reactor, and polymerization was carried out for 5 hours while maintaining the liquid temperature at 80°C ± 2°C. The polymerization was terminated by ice bath to obtain a block polymer (Mn: 15,000, Mw: 18,000).

[0219] Unless otherwise specified, other examples were carried out in the same manner as described above except for changes as shown in the following table.

[0220] [Table 1] LA: Lauryl acrylate BA: Butyl acrylate HEA: Hydroxyethyl acrylate HEMA: Hydroxyethyl Methacrylate 4HBA: 4-Hydroxybutyl acrylate FA2D: Placcel FA2D, 2 mol caprolactone addition monomer of 2-hydroxyethyl acrylate (manufactured by Daicel Corporation)

[0221] Comparative Manufacturing Example 1 In a 300 mL flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, 67 parts of lauryl acrylate, 33 parts of 2-hydroxyethyl acrylate, 2 parts of 2,2'-azobis(2-methylbutyronitrile) as an initiator, and 153 parts of methyl ethyl ketone as a solvent were added. The temperature was gradually raised to 80°C, and the reaction was carried out for 9 hours to obtain a polymer solution with a solid content concentration of 40%.

[0222] Unless otherwise specified, other examples were carried out in the same manner as described above except for changes as shown in the following table.

[0223] [Table 2] LA HEA BA Comparative Manufacturing Example 1 67 33 Comparative Manufacturing Example 2 50 24 26 Comparative Manufacturing Example 3 90 10 Comparative Manufacturing Example 4 99 1

[0224] Example 1 The substances described in the following table were mixed as non-volatile components, and then diluted with toluene to obtain a release coating agent (non-volatile content 10%).

[0225] Unless otherwise specified, other examples were carried out in the same manner as described above except for changes as shown in the following table.

[0226] [Table 3] Methylated melamine resin: Product name: "Saimel 303LF", a fully ether-type methylated melamine resin, manufactured by Ornex Japan Co., Ltd. Hydrogenated dimer diol: Product name "Pripol 2033-LQ", manufactured by Cargill Japan Co., Ltd., number average molecular weight 540 Cyclohexanedimethanol: Product name "CHDM-D", manufactured by Eastman Chemical Company

[0227] (Peel force) A polyester adhesive tape (31B tape manufactured by Nitto Denko Corporation: 25 mm wide) was pressed against the release film using a 2 kg roller and then stored at 23°C for 1 hour. The tape was then stretched at an angle of 180° and a peeling rate of 0.3 m / min, and the force required for peeling (N / 25 mm) was measured.

[0228] (Peel strength after heating) A polyester adhesive tape (31B tape manufactured by Nitto Denko Corporation: 25 mm wide) was pressed against the release film using a 2 kg roller and then stored at 70°C for 20 hours. The tape was then stretched at an angle of 180° and a peeling rate of 0.3 m / min, and the force required for peeling (N / 25 mm) was measured.

[0229] (Low metastasis) A PET film (Lumira T60 manufactured by Toray Industries, Ltd.) was laminated to a release film and subjected to a pressure of 2 kg / cm2 at 40°C. 2After standing for 72 hours, the PET film was peeled off from the release film. A polyester adhesive tape (31B tape manufactured by Nitto Denko Co., Ltd.: 25 mm wide) was pressed onto the contact surface of the peeled PET film with the release film using a 2 kg roller, and the film was laminated at the same time. The film was then stored at 23°C for 1 hour. Next, the tape was stretched at an angle of 180° and a peeling speed of 0.3 m / min, and the force X (N / 25 mm) required for peeling was measured. The force Y required for peeling the PET film not laminated to the release film was measured, and the ratio Z% of X to Y was calculated (=(X / Y)×100%). (◎: 80<Z, ○: 65<Z≤80, △: 50<Z≤65, ×: Z≤50).

Claims

1. A release coating agent comprising: a block polymer, The block polymer comprises a long chain block and a hydroxyl-containing block, The long chain block comprises a (meth)acrylate unit containing a C10-28 alkyl group, The hydroxyl group-containing block includes a hydroxyl group-containing alkyl (meth)acrylate unit. 2 . The release coating agent according to claim 1 , wherein the block polymer comprises a (meth)acrylate unit containing a C 1 to 9 alkyl group.

3. A cured product of the release coating agent according to claim 1 or 2. A laminate comprising the cured product according to claim 3 .

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