CN110643270A - Heat-curable coating agent, cured product, and film - Google Patents

Heat-curable coating agent, cured product, and film Download PDF

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Publication number
CN110643270A
CN110643270A CN201910554334.6A CN201910554334A CN110643270A CN 110643270 A CN110643270 A CN 110643270A CN 201910554334 A CN201910554334 A CN 201910554334A CN 110643270 A CN110643270 A CN 110643270A
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meth
component
coating agent
hydroxyl group
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CN110643270B (en
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久米启太
桥本祐希
山崎彰宽
东本徹
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Arakawa Chemical Industries Ltd
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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
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/48—Polyethers
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
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    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
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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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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract

[ problem ] to provide a heat-curable coating agent, a cured product, and a film. [ solution ] the present disclosure provides a heat-curable coating agent containing (A) a hydroxyl group-containing (meth) acrylic resin having a glass transition temperature of less than-20 ℃, (B) a hydroxyl group-containing organically modified silicone, and (C) an allophanate form and/or a biuret form of a polyisocyanate, a cured product thereof, and a film containing the cured product. In one embodiment, the thermosetting coating agent contains a diol having a hydroxyl value of 200mgKOH/g or more and a molecular weight of 500 or less.

Description

Heat-curable coating agent, cured product, and film
Technical Field
The present disclosure relates to a heat-curable coating agent, a cured product, and a film.
Background
Plastic substrates such as ABS and polycarbonate are used for various industrial products such as electronic devices and automobile parts. In order to protect such plastic substrates, surface treatment is carried out by a coating agent.
When surface protection is performed using a hard coating agent (ハ ー ド コ ー テ ィ ン グ), there is a technical problem that cracks (ひ) are generated in the crotch region れ, which is not suitable for surface protection.
On the other hand, when surface protection is performed using a self-healing coating agent, a coating film that can be restored to its original shape even if deformed by an external force can be formed; further, since flexibility is high, cracks are not easily generated.
Patent document 1 describes a coating agent containing inorganic fine particles and a copolymer of a3 to 6 functional acrylate monomer and a multifunctional acrylate compound containing a caprolactone group.
Patent document 2 describes a urethane acrylate using a polyvalent isocyanate compound containing 2 or more allophanate groups.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 6114413
Patent document 2: japanese patent laid-open publication No. 2015-124265
Disclosure of Invention
Technical problem to be solved by the invention
However, in the case of patent document 1, in order to exhibit self-repairability, the film thickness after curing needs to be about 50 μm to 150 μm, and the amount of the coating agent needed is large; as a result, the energy required for curing increases, and thus productivity is poor. Further, the photopolymerizable coating agent and the coating agent containing inorganic particles of patent document 1 have a problem that cracks are easily generated in the coating film.
Further, in the case of patent document 2, there is a problem that it takes heat and a long time to deform to return to an original shape by receiving an external force.
The invention aims to provide a coating agent which enables a cured product to have good self-repairability, wear resistance, antifouling property and tensile property (characteristics of primer ).
Means for solving the problems
The present inventors have conducted extensive studies and, as a result, have found that the above-mentioned problems can be solved by a coating agent containing a specific component.
The following items are provided in accordance with the present disclosure.
(item 1)
A heat-curable coating agent containing:
(A) a hydroxyl group-containing (meth) acrylic resin having a glass transition temperature of less than-20 ℃;
(B) an organically modified silicone containing a hydroxyl group (having an anchor シ リ コ ー ン); and
(C) allophanate form and/or biuret form of the polyisocyanate.
(item 2)
The heat-curable coating agent as described in the above item, which contains (D) a diol having a hydroxyl value of 200mgKOH/g or more and a molecular weight of 500 or less.
(item 3)
The heat-curable coating agent according to any one of the above items, which contains (E) a curing catalyst.
(item 4)
The heat-curable coating agent according to any one of the above items, which contains (F) an organic solvent.
(item 5)
The heat-curable coating agent according to any one of the above items, which is a self-repairable coating agent.
(item 6)
A cured product of the heat-curable coating agent according to any one of the above items.
(item 7)
A film comprising the cured product as described above.
In the present disclosure, one or more of the features described above may be provided in further combination, in addition to the combinations explicitly described.
Advantageous effects
The cured product of the thermosetting coating agent of the present invention is excellent in self-repairability, abrasion resistance, antifouling property and tensile properties. Therefore, by using the heat-curable coating agent of the present invention, a film having good self-repairability, abrasion resistance, stain resistance and tensile properties can be produced. Further, the present invention can be applied to coating of a decorative film and the like.
Detailed Description
Throughout the present disclosure, the ranges of the numerical values such as the physical property values and the contents may be appropriately set (for example, selected from the upper and lower limits described in the following items). Specifically, the numerical value α is, for example, a1, a2, A3, etc. at the upper limit of the numerical value α, and B1, B2, B3, etc. at the lower limit thereof, the ranges of the numerical value α are, for example, a1 or less, a2 or less, A3 or less, B1 or more, B2 or more, B3 or more, B1 to a1, B2 to a1, B3 to a1, B1 to a2, B2 to a2, B3 to a2, B1 to A3, B2 to A3, B3 to A3, etc.
[ heat-curable coating agent: also referred to as coating agent ]
The present disclosure provides a heat-curable coating agent containing: (A) a hydroxyl group-containing (meth) acrylic resin having a glass transition temperature of less than-20 ℃, (B) a hydroxyl group-containing organomodified silicone, and (C) an allophanate form and/or a biuret form of a polyisocyanate.
< component (A): hydroxyl group-containing (meth) acrylic resin >
(A) The components: examples of the hydroxyl group-containing (meth) acrylic resin include a copolymer containing a structural unit derived from a hydroxyl group-free alkyl (meth) acrylate and a structural unit derived from a hydroxyl group-containing alkyl (meth) acrylate. The hydroxyl group-containing (meth) acrylic resin may be used alone or in combination of 2 or more.
In the present disclosure, "(meth) acrylic acid" ("(メ タ) ア ク リ ル") means "at least one selected from the group consisting of acrylic acid and methacrylic acid". Similarly, "(meth) acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". Further, "(meth) acryloyl group" means "at least one selected from the group consisting of acryloyl group and methacryloyl group".
(alkyl (meth) acrylate having no hydroxyl group)
The hydroxyl group-free alkyl (meth) acrylate is represented by the following formula:
[ solution 1]
Figure BDA0002106455390000041
(in the formula, Ra1Is a hydrogen atom or a methyl group, Ra2Is an alkyl group. ) The alkyl (meth) acrylate having no hydroxyl group may be used alone or in combination of 2 or more.
Alkyl groups are exemplified by straight chain alkyl groups, branched chain alkyl groups, cyclic alkyl groups, and the like.
Straight chain alkyl is represented by the formula-CnH2n+1(n is an integer of 1 or more). The straight-chain alkyl group is exemplified by methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl (n- デ カ メ チ ル -yl) group and the like.
Branched alkyl is a group in which at least one hydrogen of a linear alkyl group is substituted with an alkyl group. Examples of the branched alkyl group include isobutyl, sec-butyl, tert-butyl, diethylpentyl, trimethylbutyl, trimethylpentyl, trimethylhexyl and the like.
Cycloalkyl groups are exemplified by monocyclic cycloalkyl, bridged cycloalkyl, fused cyclic cycloalkyl, and the like.
Monocyclic cycloalkyl groups are exemplified by cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, 3,5, 5-trimethylcyclohexyl, and the like.
Examples of bridged cycloalkyl groups include tricyclodecyl (ト リ シ ク ロ デ シ ル -yl), adamantyl, norbornyl (ノ ル ボ ル ニ ル -yl), and the like.
The condensed ring cycloalkyl group is exemplified by bicyclodecyl (ビ シ ク ロ デ シ ル yl) and the like.
Examples of the alkyl (meth) acrylate having no hydroxyl group include a straight-chain alkyl (meth) acrylate having no hydroxyl group, a branched alkyl (meth) acrylate having no hydroxyl group, a cycloalkyl (meth) acrylate having no hydroxyl group, and the like.
Examples of the linear alkyl (meth) acrylate having no hydroxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, hexadecyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate ((メ タ) ア ク リ ル acid イ コ シ ル), and docosyl (meth) acrylate.
Examples of the branched alkyl (meth) acrylate having no hydroxyl group include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
Examples of the cycloalkyl (meth) acrylate having no hydroxyl group include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate ((メ タ) ア ク リ ル acid ジ シ ク ロ ペ ン タ ニ ル), isobornyl (meth) acrylate, and the like.
Among them, in order to impart abrasion resistance, leveling property (レ ベ リ ン グ property), and adhesion to the coating agent, a hydroxyl group-free alkyl (meth) acrylate having an alkyl group with about 1 to 20 carbon atoms is preferable. Further, by using a combination of alkyl (meth) acrylates having different alkyl groups and no hydroxyl group, physical properties such as the glass transition temperature of the hydroxyl group-containing (meth) acrylic resin can be adjusted.
(A) The upper limit of the content of the structural unit derived from the hydroxyl group-free alkyl (meth) acrylate in the component (a) is 98 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, etc., based on 100 mol% of the total structural units, and the lower limit is 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 62 mol%, etc. In one embodiment, the content of the structural unit derived from the alkyl (meth) acrylate containing no hydroxyl group in the component (a) is preferably in a range of about 62 mol% to 98 mol% based on 100 mol% of the total structural units, from the viewpoint of self-repairability and abrasion resistance.
(A) The upper limit of the content of the structural unit derived from the hydroxyl group-free alkyl (meth) acrylate in the component (a) is 98 mass%, 95 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, etc. in 100 mass% of the total structural units, and the lower limit is 95 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, etc. in this case, the content is not limited to the above-mentioned content. In one embodiment, the content of the structural unit derived from the alkyl (meth) acrylate containing no hydroxyl group in the component (a) is preferably about 65 to 98 mass% based on 100 mass% of the total structural units, from the viewpoints of self-repairability and wear resistance.
(hydroxyl group-containing alkyl (meth) acrylate)
The hydroxyl group-containing alkyl (meth) acrylate is represented by the following structural formula:
[ solution 2]
Figure BDA0002106455390000061
(in the formula, Ra3Is a hydrogen atom or a methyl group, Ra4Is a linear alkylene, branched alkylene or cycloalkylene group. ) The hydroxyl group-containing alkyl (meth) acrylate may be used alone or in combination of 2 or more. Examples of the linear alkylene group, the branched alkylene group and the cycloalkylene group include the groups described later.
Examples of the hydroxyl group-containing alkyl (meth) acrylate include hydroxyl group-containing linear alkyl (meth) acrylate, hydroxyl group-containing branched alkyl (meth) acrylate, hydroxyl group-containing cycloalkyl (meth) acrylate, and the like.
Examples of the hydroxyl group-containing linear alkyl (meth) acrylate include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the branched alkyl (meth) acrylate containing a hydroxyl group include 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) acrylate.
Examples of the cycloalkyl (meth) acrylate containing a hydroxyl group include hydroxycyclohexyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl (meth) acrylate, and the like.
The hydroxyl group-containing alkyl (meth) acrylate preferably has a hydroxyalkyl group having about 1 to 4 carbon atoms from the viewpoints of curability of the coating agent, pot life (ポ ッ ト ラ イ フ), and the like.
(A) The upper limit of the content of the structural unit derived from the hydroxyl group-containing alkyl (meth) acrylate in the component (a) is, for example, 38 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 2.5 mol% or the like based on 100 mol% of the total structural units, and the lower limit is, for example, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 2.5 mol%, 1.5 mol% or the like. In one embodiment, the content of the structural unit derived from the hydroxyl group-containing alkyl (meth) acrylate in the component (a) is preferably in a range of about 1.5 mol% to 38 mol% based on 100 mol% of the total structural units, from the viewpoints of self-repairability, abrasion resistance, coating film appearance, and pot life.
(A) The upper limit of the content of the structural unit derived from the hydroxyl group-containing alkyl (meth) acrylate in the component (a) is 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 2.5 mass%, etc., in 100 mass% of the total structural units, and the lower limit is 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 2.5 mass%, 2 mass%, etc., for example. In one embodiment, the content of the structural unit derived from the hydroxyl group-containing alkyl (meth) acrylate in the component (a) is preferably about 2 to 35% by mass based on 100% by mass of the total structural units, from the viewpoints of self-repairability, abrasion resistance, coating film appearance, and pot life.
(A) The amount ratio of the substance derived from the structural unit derived from the hydroxyl group-free alkyl (meth) acrylate to the substance derived from the structural unit derived from the hydroxyl group-containing alkyl (meth) acrylate in the component (hydroxyl group-free alkyl (meth) acrylate)molHydroxyl group-containing alkyl (meth) acrylatemol) The upper limit of (b) is shown by way of example as 65, 60, 50, 40, 30, 20, 10, 5, 2, etc., and the lower limit is shown by way of example as 60, 50, 40, 30, 20, 10, 5, 2, 1.6, etc. In one embodiment, the amount of the substance derived from the structural unit derived from the hydroxyl group-free alkyl (meth) acrylate and the structural unit derived from the hydroxyl group-containing alkyl (meth) acrylate in the component (a) is in a ratio to the amount of the substance derived from the hydroxyl group-free alkyl (meth) acrylate in terms of self-repairability, abrasion resistance, coating film appearance, and pot lifemolHydroxyl group-containing alkyl (meth) acrylatemol) Preferably about 1.6 to 65.
(A) The mass ratio of the structural unit derived from the hydroxyl group-free alkyl (meth) acrylate to the structural unit derived from the hydroxyl group-containing alkyl (meth) acrylate in the component (the hydroxyl group-free alkyl (meth) acrylate)massHydroxyl group-containing alkyl (meth) acrylatemass) The upper limits of (b) show, for example, 49, 40, 30, 20, 10, 5, 2, etc., and the lower limits show, for example, 45, 40, 30, 20, 10, 5, 2, 1.8, etc. In one embodiment, the mass ratio of the structural unit derived from the alkyl (meth) acrylate having no hydroxyl group to the structural unit derived from the alkyl (meth) acrylate having a hydroxyl group in the component (a) is (the alkyl (meth) acrylate having no hydroxyl group) in terms of self-repairability, abrasion resistance, coating film appearance, and pot lifemassHydroxyl group-containing alkyl (meth) acrylatemass) Preferably about 1.8 to 49.
(monomers which are neither hydroxyl group-free alkyl (meth) acrylates nor hydroxyl group-containing alkyl (meth) acrylates: also referred to as other monomers)
In the production of the hydroxyl group-containing (meth) acrylic resin, a monomer not corresponding to either of the hydroxyl group-free alkyl (meth) acrylate and the hydroxyl group-containing alkyl (meth) acrylate may be used. The other monomers may be used alone or in combination of 2 or more.
Other monomers show by way of example (meth) acrylic acid; an α, β -unsaturated carboxylic acid; styrenes; an alpha-olefin; unsaturated alcohols and salts thereof; dialkylaminoalkyl (meth) acrylamides and salts thereof; a chain transfer monomer; (meth) acrylonitrile; (meth) acrylamides; a vinylamine; bis (meth) acrylamide; di (meth) acrylates; a divinyl ester; difunctional monomers, trifunctional monomers, tetrafunctional monomers and the like other than the above.
(A) The upper limit of the content of the structural unit derived from another monomer in the component (a) is 13 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 1 mol% or the like based on 100 mol% of the total structural units, and the lower limit is 12 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 1 mol%, 0 mol% or the like. In one embodiment, the content of the structural unit derived from another monomer in the component (a) is preferably in a range of about 0 mol% to 13 mol% based on 100 mol% of the total structural units, from the viewpoint of self-repairability and abrasion resistance.
(A) The upper limit of the content of the constituent unit derived from another monomer in the component (a) is 10 mass%, 9 mass%, 5 mass%, 4 mass%, 1 mass%, etc., with respect to 100 mass% of all the constituent units, and the lower limit is 9 mass%, 5 mass%, 4 mass%, 1 mass%, 0 mass%, etc., with respect to the total constituent units. In one embodiment, the content of the structural unit derived from another monomer in the component (a) is preferably in a range of about 0 to 10% by mass based on 100% by mass of the total structural units, from the viewpoint of self-repairability and wear resistance.
(A) The amount ratio of the constituent unit derived from another monomer to the constituent unit derived from the hydroxyl group-free alkyl (meth) acrylate in the component (other monomer)molAlkyl (meth) acrylates containing no hydroxyl groupmol) Examples of the upper limit of (B) are 0.22, 0.20, 0.150.10, 0.05, etc., with lower limits of 0.20, 0.15, 0.10, 0.05, 0, etc., as examples. In one embodiment, the amount ratio of the constituent unit derived from another monomer to the constituent unit derived from the hydroxyl group-free alkyl (meth) acrylate in the component (a) is (the other monomer) from the viewpoint of self-repairability and abrasion resistancemolAlkyl (meth) acrylates containing no hydroxyl groupmol) Preferably about 0 to 0.22.
(A) The mass ratio of the structural unit derived from another monomer to the structural unit derived from the hydroxyl group-free alkyl (meth) acrylate in the component (other monomer)massAlkyl (meth) acrylates containing no hydroxyl groupmass) The upper limit of (b) is exemplified by 0.19, 0.15, 0.10, 0.05, etc., and the lower limit is exemplified by 0.15, 0.10, 0.05, 0, etc. In one embodiment, the mass ratio of the structural unit derived from another monomer to the structural unit derived from the alkyl (meth) acrylate having no hydroxyl group in the component (a) (the other monomer) is from the viewpoint of self-repairability and abrasion resistancemassAlkyl (meth) acrylates containing no hydroxyl groupmass) Preferably about 0 to 0.19.
(A) The amount ratio of the substance derived from the structural unit derived from another monomer to the substance derived from the structural unit derived from the hydroxyl group-containing alkyl (meth) acrylate in the component (other monomer)molHydroxyl group-containing alkyl (meth) acrylatemol) The upper limits of (b) are exemplified by 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.0, 0.5, etc., and the lower limits are exemplified by 7.5, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.0, 0.5, 0, etc. In one embodiment, the amount ratio of the substance derived from the structural unit derived from another monomer to the structural unit derived from the hydroxyl group-containing alkyl (meth) acrylate in the component (a) (the other monomer) is from the viewpoint of self-repairability and abrasion resistancemolHydroxyl group-containing alkyl (meth) acrylatemol) Preferably about 0 to 8.0.
(A) The mass ratio of the structural unit derived from another monomer to the structural unit derived from the hydroxyl group-containing alkyl (meth) acrylate in the component (other monomer)massHydroxyl group-containing alkyl (meth) acrylatemass) Examples of the upper limit of (b) are 5.0, 4.0, 3.0, 2.0. 1.0, 0.5, etc., with the lower limits being exemplified by 4.5, 4.0, 3.0, 2.0, 1.0, 0.5, 0, etc. In one embodiment, the mass ratio of the structural unit derived from another monomer to the structural unit derived from the hydroxyl group-containing alkyl (meth) acrylate in the component (a) (the other monomer) is from the viewpoint of self-repairability and abrasion resistancemassHydroxyl group-containing alkyl (meth) acrylatemass) Preferably about 0 to 5.0.
< physical Properties of hydroxyl group-containing (meth) acrylic resin, etc. >
(A) Examples of the upper limit of the glass transition temperature of the components include-20 ℃, -20.1 ℃, -21 ℃, -23 ℃, -25 ℃, -30 ℃, -31 ℃, -35 ℃, -39 ℃, and examples of the lower limit thereof include-20.1 ℃, -21 ℃, -23 ℃, -25 ℃, -30 ℃, -31 ℃, -35 ℃, -39 ℃, -40 ℃. In one embodiment, the glass transition temperature of the component (a) is preferably lower than-20 ℃, more preferably higher than-40 ℃ and lower than-20 ℃ from the viewpoint of self-repairability, abrasion resistance and tensile characteristics.
The glass transition temperature is calculated from the Fox equation.
Fox formula: 1/Tg ═ Wa/Tga) + (Wb/Tgb) + … + (Wn/Tgn)
Tg: glass transition temperature (K) of the copolymer
Wa: mass% of monomer A%
Tga: glass transition temperature (K) of homopolymer of monomer A
Wb: mass% of monomer B
Tgb: glass transition temperature (K) of homopolymer of monomer B
Wn: mass% of monomer N
Tgn: glass transition temperature (K) of homopolymer of monomer N
(A) The upper limit of the hydroxyl equivalent weight of the component (A) is, for example, 2.7meq/g, 2.5meq/g, 2.0meq/g, 1.8meq/g, 1.5meq/g, 1.0meq/g, 0.5meq/g, 0.25meq/g or the like, and the lower limit is, for example, 2.5meq/g, 2.0meq/g, 1.8meq/g, 1.5meq/g, 1.0meq/g, 0.5meq/g, 0.25meq/g, 0.17meq/g or the like. In one embodiment, the hydroxyl group equivalent of the component (A) is preferably about 0.17meq/g to 2.7meq/g, more preferably about 0.5meq/g to 1.8meq/g, from the viewpoints of self-repairability, abrasion resistance, coating film appearance, and pot life.
In this disclosure, the hydroxyl equivalent is the amount of material of hydroxyl groups present in 1g of solid.
(A) The upper limit of the hydroxyl value of the component (converted to a solid component) is, for example, 150mgKOH/g, 140mgKOH/g, 130mgKOH/g, 120mgKOH/g, 110mgKOH/g, 100mgKOH/g, 90mgKOH/g, 80mgKOH/g, 70mgKOH/g, 60mgKOH/g, 50mgKOH/g, 40mgKOH/g, 30mgKOH/g, 20mgKOH/g, 15mgKOH/g, etc., and the lower limit is, for example, 140mgKOH/g, 130mgKOH/g, 120mgKOH/g, 110mgKOH/g, 100mgKOH/g, 90mgKOH/g, 80mgKOH/g, 70mgKOH/g, 60mgKOH/g, 50mgKOH/g, 40mgKOH/g, 30mgKOH/g, 20mgKOH/g, 15mgKOH/g, 10mgKOH/g, etc. In one embodiment, the hydroxyl value (in terms of solid content) of the component (A) is preferably about 10 to 150mgKOH/g from the viewpoints of self-repairability, abrasion resistance, coating film appearance, and pot life.
The hydroxyl value was measured by a method (acetylation method) according to JIS K1557-1.
(A) The upper limit of the acid value of the component is, for example, 10mgKOH/g, 5mgKOH/g, 1mgKOH/g, 0.1mgKOH/g, etc., and the lower limit is, for example, 5mgKOH/g, 1mgKOH/g, 0.1mgKOH/g, 0mgKOH/g, etc. In one embodiment, the acid value of the component (A) is preferably about 0 to 10mgKOH/g, more preferably about 0 to 1mgKOH/g, in view of curability.
The acid value was measured by a method based on JIS K0070.
(A) Examples of the upper limit of the weight average molecular weight (Mw) of the component (B) include 300000, 200000, 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, and examples of the lower limit include 200000, 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000. In one embodiment, the weight average molecular weight (Mw) of the component (a) is preferably 10000 to 300000, more preferably 50000 to 300000, from the viewpoint of self-repairability, wear resistance, tensile properties, and antifouling properties of the coating agent.
(A) The upper limit of the number average molecular weight (Mn) of the component (B) is 100000, 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, etc., and the lower limit is 90000, 80000, 70000, 60000, 50000, 40000, 30000, 20000, 10000, 5000, etc., as examples. In one embodiment, the number average molecular weight (Mn) of the component (a) is preferably about 5000 to 100000, more preferably about 10000 to 100000, from the viewpoint of self-repairability, abrasion resistance, tensile properties, and antifouling property of the coating agent.
(A) The upper limits of the molecular weight distribution (Mw/Mn) of the component (B) are, for example, 10, 7.5, 5, 2.5, 2, etc., and the lower limits are, for example, 9.5, 7.5, 5, 2.5, 2, 1.5, etc. In one embodiment, the molecular weight distribution (Mw/Mn) of the component (a) is preferably about 1.5 to 10 from the viewpoints of self-repairability, wear resistance, tensile properties, and antifouling properties.
(A) The component (b) can be produced by various known methods. The method for producing the hydroxyl group-containing (meth) acrylic resin is exemplified by: a method of copolymerizing a hydroxyl group-free alkyl (meth) acrylate, a hydroxyl group-containing alkyl (meth) acrylate, and other monomers as needed at about 70 to 180 ℃ for about 1 to 10 hours in the absence of a solvent or in an organic solvent, usually in the presence of a polymerization initiator. The organic solvent used in the production of the hydroxyl group-containing (meth) acrylic resin is exemplified by the organic solvent described later. Examples of the polymerization initiator include azo initiators such as Azobisisobutyronitrile (AIBN).
The upper limit of the content (in terms of solid content) of the component (a) in the coating agent is, for example, 90 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, etc., and the lower limit is, for example, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, etc. In one embodiment, the content (in terms of solid content) of the component (a) in the coating agent is preferably 10 to 90% by mass from the viewpoints of self-repairability, wear resistance, tensile properties, and antifouling properties.
< component (B): hydroxyl group-containing organic-modified Silicone >
In the present disclosure, "hydroxyl group-containing organomodified silicone" means, for example, a silicone having a hydroxyl group-containing organic group. (B) The components: the hydroxyl group-containing organic modified silicone may be used alone or in combination of 2 or more. Since the hydroxyl group-containing compound is fixed to the cured product by reaction with the polyisocyanate, the antifouling property is maintained for a long period of time. (B) The component (a) is exemplified by hydroxyl group-containing organic modified silicone modified with an acrylic polymer, hydroxyl group-containing organic modified silicone modified with a polyester, hydroxyl group-containing organic modified silicone modified with a polyether, hydroxyl group-containing organic modified silicone modified with methanol (カ ル ビ ノ ー ル -modified), and the like. The modified site may be introduced into any one of one end, both ends and a side chain of a silicone chain.
Commercially available products of hydroxyl group-containing organically modified silicone modified with an acrylic polymer include, for example, ZX-028-G (manufactured by T & K TOKA, Inc.), BYK-SILCLEAN3700 (manufactured by ビ ッ ク ケ ミ ー & ジ ャ パ ン, Inc.), サ イ マ ッ ク US-270 (manufactured by Toyo Seisaku Co., Ltd.), and the like.
Commercially available products of polyether-modified hydroxyl group-containing organomodified silicone or polyester-modified hydroxyl group-containing organomodified silicone include, for example, BYK-370, BYK-375, BYK-377, BYK-SILCLEAN3720 (manufactured by ビ ッ ク ケ ミ ー & ジ ャ パ ン); x-22-4952, KF-6123 (manufactured by shin-Etsu chemical Co., Ltd.), and the like.
Commercially available products of methanol-modified hydroxyl group-containing organomodified silicones include, for example, X-22-4039, X-22-4015, X-22-4952, X-22-4272, X-22-170BX, X-22-170DX, KF-6000, KF-6001, KF-6002, KF-6003, KF-6123 and X-22-176F (manufactured by shin-Etsu chemical Co., Ltd.); サ イ ラ プ レ ー ン FM-4411, サ イ ラ プ レ ー ン FM-4421, サ イ ラ プ レ ー ン FM-4425, サ イ ラ プ レ ー ン FM-0411, サ イ ラ プ レ ー ン FM-0421, サ イ ラ プ レ ー ン FM-DA11, サ イ ラ プ レ ー ン FM-DA21, サ イ ラ プ レ ー ン FM-DA26 (manufactured by JNC Co., Ltd.), and the like.
The upper limit of the content (in terms of solid content) of the component (B) in the coating agent is, for example, 5 mass%, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.9 mass%, 0.5 mass%, 0.2 mass%, etc., and the lower limit is, for example, 4 mass%, 3 mass%, 2 mass%, 1 mass%, 0.9 mass%, 0.5 mass%, 0.2 mass%, 0.1 mass%, etc. In one embodiment, the content (in terms of solid content) of the component (B) in the coating agent is preferably 0.1 to 5.0 mass% from the viewpoint of antifouling property.
< component (C): allophanate form and/or biuret form of polyisocyanate >
(C) The components: the allophanate form and/or biuret form of the polyisocyanate may be used alone or in 2 or more kinds. In the present disclosure, a "polyisocyanate" is a compound having 2 or more isocyanate groups (-N ═ C ═ O). In the production of the allophanate form or the biuret form of the polyisocyanate, the polyisocyanate may be used alone or in 2 or more kinds.
Examples of the polyisocyanate include aliphatic polyisocyanates, aromatic polyisocyanates, and the like.
Examples of the aliphatic polyisocyanate include a straight-chain aliphatic polyisocyanate, a branched-chain aliphatic polyisocyanate, and an alicyclic polyisocyanate.
Examples of the linear aliphatic group include a linear alkylene group and the like. The linear alkylene group may be represented by the formula- (CH)2)nThe term- (n is an integer of 1 or more) represents, for example, methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decamethylene (group n- デ カ メ チ レ ン), etc.
The linear aliphatic polyisocyanate is exemplified by methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, and the like.
Examples of the branched aliphatic group include a branched alkylene group and the like. The branched alkylene group is a group in which at least 1 hydrogen of the linear alkylene group is substituted with an alkyl group, and specific examples thereof include diethylpentylene, trimethylbutylene, trimethylpentylene, trimethylhexylene (trimethylhexamethylene), and the like.
Examples of the branched aliphatic polyisocyanate include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, trimethylhexamethylene diisocyanate, and the like.
The alicyclic group is exemplified by monocyclic alicyclic group, bridged alicyclic group, fused alicyclic group, and the like. Further, 1 or more hydrogens of the cycloalkylene group may be substituted with a linear or branched alkyl group.
In the present disclosure, monocyclic means a cyclic structure formed by covalent bonds of carbon and having no bridging structure inside. Further, a condensed ring means a cyclic structure in which 2 or more monocyclic rings share 2 atoms (i.e., only one side of each ring is shared (condensed) with each other). Bridged ring means a cyclic structure in which 2 or more monocyclic rings have 3 or more atoms in total.
Monocyclic alicyclic groups are exemplified by cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, 3,5, 5-trimethylcyclohexylene, and the like.
Examples of bridged cycloaliphatic radicals are tricyclodecaneidenyl, adamantyl (ア ダ マ ン チ レ ン radical), norbornyl (ノ ル ボ ル ニ レ ン radical), and the like.
Examples of the fused-ring alicyclic group include bicyclodecylidene (ビ シ ク ロ デ シ レ ン group) and the like.
Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, bridged alicyclic polyisocyanate, and condensed alicyclic polyisocyanate.
The monocyclic alicyclic polyisocyanate is exemplified by hydrogenated xylylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5, 5-trimethylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate and the like.
Examples of the bridged alicyclic polyisocyanate include tricyclodecylidene diisocyanate, adamantyl diisocyanate, norbornene diisocyanate, and the like.
Examples of the fused-ring alicyclic polyisocyanate include dicyclodeecylene diisocyanate and the like.
The number of carbon atoms of the aliphatic group is not particularly limited, and the upper limit thereof is 30, 29, 25, 20, 16, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc., and the lower limit thereof is 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc., for example. In one embodiment, the aliphatic group has preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms from the viewpoint of self-repairability, wear resistance, and tensile properties.
The aromatic group is exemplified by phenylene, naphthylene, etc.
Examples of the aromatic polyisocyanate include xylylene diisocyanate and the like.
The allophanate form of the polyisocyanate is exemplified by the compounds represented by the following structural formula:
[ solution 3]
Figure BDA0002106455390000141
{ wherein n is an integer of 0 or more, RAIs alkyl or aryl, RB～RGEach independently being alkylene or arylene, Rα～RγEach independently is an isocyanate group or
[ solution 4]
Figure BDA0002106455390000151
(n1 is an integer of 0 or more, R1～R6Each independently alkylene or arylene, each R 'to R' "independently is an isocyanate group or Rα～RγA group of itself. For each structural unit, R1～R4The groups R' to R "may also be different. ) For each structural unit, RB～RE、Rα～RβThe groups of (a) may also be different. }
Commercially available products of allophanate form of polyisocyanate are exemplified by CORONATE (コ ロ ネ ー ト)2793 (manufactured by DONG ソ ー Co., Ltd.), TAKENATE (タ ケ ネ ー ト) D-178N (manufactured by Mitsui chemical Co., Ltd.), and the like.
The biuret form of the polyisocyanate exemplifies compounds represented by the following structural formula, and the like:
[ solution 5]
Figure BDA0002106455390000152
{ in the formula (I) { wherein,
nbis an integer of 1 or more, and is,
RbA～RbEeach independently being an alkylene or arylene group,
Rbα～Rbβeach independently is an isocyanate group or
[ solution 6]
Figure BDA0002106455390000153
(nb1Is an integer of 0 or more, and,
Rb1～Rb5each independently being an alkylene or arylene group,
Rb’～Rb"are each independently an isocyanate group or Rbα～RbβA group of itself.
For each structural unit, Rb4～Rb5、RbThe "groups may also be different. )
For each structural unit, RbD～RbE、RbβThe groups of (a) may also be different. }
The biuret forms of the polyisocyanates are exemplified by DURANATE (デ ュ ラ ネ ー ト)24A-100, DURANATE 22A-75P, DURANATE 21S-75E (manufactured by Asahi Kasei corporation, supra); デ ス モ ジ ュ ー ル N3200A (biuret form of hexamethylene diisocyanate) (manufactured by Sumitomo バ イ エ ル ウ レ タ ン, Inc.) and the like.
(C) Examples of the upper limit of the NCO content of the component (NCO% in the solid content) include 30% by mass, 25% by mass, 20% by mass, and 15% by mass, and examples of the lower limit include 25% by mass, 20% by mass, 15% by mass, and 10% by mass. In one embodiment, the NCO content (NCO% in solid content) of the component (C) is preferably 10% by mass to 30% by mass from the viewpoints of self-repairability, abrasion resistance and tensile properties.
The upper limit of the content (in terms of solid content) of the component (C) in the coating agent is, for example, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 15 mass%, etc., and the lower limit is, for example, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 15 mass%, 10 mass%, etc. In one embodiment, the content (in terms of solid content) of the component (C) in the coating agent is preferably 10 to 80% by mass from the viewpoints of self-repairability, wear resistance, and tensile properties.
The mass ratio of the component (a) to the component (C) in the coating agent (the upper limit of (component (a)/component (C)) is, for example, 5, 4, 3, 2, 1, 0.9, 0.5, 0.3, etc., and the lower limit thereof is, for example, 4, 3, 2, 1, 0.9, 0.5, 0.3, 0.2, etc. In one embodiment, the mass ratio of the component (a) to the component (C) in the coating agent ((a) component/(C) component) is preferably 0.2 to 5.0 from the viewpoints of self-repairability, wear resistance, and tensile properties.
< component (D): diol having a hydroxyl value of 200mgKOH/g or more and a molecular weight of 500 or less >
In one embodiment, the coating agent may contain (D) a diol having a hydroxyl value of 200mgKOH/g or more and a molecular weight of 500 or less. By containing the component (D), the self-repairability, wear resistance and tensile properties are improved. (D) The components can be used alone or in combination of 2 or more.
In the present disclosure, when only "molecular weight" is recited, it means one of formula weight or number average molecular weight. When the structure of a compound can be uniquely represented by a specific chemical formula (i.e., molecular weight distribution of 1), the above molecular weight means the formula weight. On the other hand, when the structure of the compound cannot be uniquely represented by a specific chemical formula (i.e., molecular weight distribution is more than 1), the above molecular weight means a number average molecular weight.
(D) The component (A) is exemplified by alkylene glycol, polyether glycol, etc. The alkylene glycol is exemplified by a straight chain alkylene glycol, a branched chain alkylene glycol, a cyclic alkylene glycol, and the like.
Examples of the straight chain alkylene glycol include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, and the like.
Examples of the branched alkylene glycol include neopentyl glycol, 2, 4-diethyl-1, 5-pentanediol, 2, 4-dibutyl-1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1-methyl glycol, 1-ethyl glycol, and the like.
Examples of the cycloalkylene glycol include monocyclic cycloalkylene glycol, bridged cycloalkylene glycol and the like.
Examples of monocyclic cycloalkylene glycol include 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, 2' -bis (4-hydroxycyclohexyl) propane and the like.
Examples of the bridged cycloalkylene glycol include tricyclodecanedimethanol and the like.
Examples of the polyether glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polytetramethylene ether glycol, and the like.
The upper limit of the content (in terms of solid content) of the component (D) in the coating agent is, for example, 20 mass%, 19 mass%, 15 mass%, 10 mass%, 9 mass%, 5 mass%, 3 mass%, 1 mass%, etc., and the lower limit is, for example, 19 mass%, 15 mass%, 10 mass%, 9 mass%, 5 mass%, 3 mass%, 1 mass%, 0 mass%, etc. In one embodiment, the content (in terms of solid content) of the component (D) in the coating agent is preferably 0 to 20% by mass.
The upper limit of the mass ratio of the component (D) to the component (a) (component (D)/component (a)) in the coating agent is, for example, 1.0, 0.9, 0.7, 0.5, 0.4, 0.2, 0.1, and the lower limit is, for example, 0.9, 0.7, 0.5, 0.4, 0.2, 0.1, 0, and the like. In one embodiment, the mass ratio of the component (D) to the component (a) ((D) component/(a) component) in the coating agent is preferably 0 to 1.0 from the viewpoints of self-repairability, wear resistance, and leveling property.
The mass ratio of the component (D) to the component (C) in the coating agent (component (D)/(component (C)) has upper limits of 0.5, 0.4, 0.2, 0.1, and lower limits of 0.4, 0.2, 0.1, and 0, respectively. In one embodiment, the mass ratio of the component (D) to the component (C) in the coating agent ((D)/C) component) is preferably 0 to 0.5.
(C) The upper limit of the molar ratio (NCO/OH) of the isocyanate group of the component (a) to the hydroxyl groups of the component (B), the component (D) and other components (NCO) is, for example, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1.5, 1, 0.8, 0.6, 0.4, 0.1, etc., and the lower limit thereof is, for example, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, etc. The range of the above molar ratio (NCO/OH) can be appropriately set (for example, selected from the above upper and lower limits). In one embodiment, the molar ratio (NCO/OH) of the isocyanate group of the component (C) to the hydroxyl groups of the component (a), the component (B), the component (D) and other components is preferably about 0.05 to 10 from the viewpoints of self-repairability, abrasion resistance, stain resistance and tensile properties.
(D) Examples of the upper limit of the hydroxyl value of the component include 1600mgKOH/g, 1500mgKOH/g, 1250mgKOH/g, 1100mgKOH/g, 1090mgKOH/g, 1080mgKOH/g, 1070mgKOH/g, 1060mgKOH/g, 1050mgKOH/g, 1000mgKOH/g, 990mgKOH/g, 975mgKOH/g, 950mgKOH/g, 900mgKOH/g, 750mgKOH/g, 500mgKOH/g, 250mgKOH/g, and the like, the lower limits are, for example, 1500mgKOH/g, 1250mgKOH/g, 1100mgKOH/g, 1090mgKOH/g, 1080mgKOH/g, 1070mgKOH/g, 1060mgKOH/g, 1050mgKOH/g, 1000mgKOH/g, 990mgKOH/g, 975mgKOH/g, 950mgKOH/g, 900mgKOH/g, 750mgKOH/g, 500mgKOH/g, 250mgKOH/g, 200mgKOH/g, etc. In one embodiment, the hydroxyl value of the component (D) is preferably from 200mgKOH/g to 1600 mgKOH/g.
(D) The upper limit of the molecular weight of the component (a) is 500, 490, 450, 400, 350, 300, 250, 200, 150, 120, 119, 115, 110, 109, 105, 100, 75, etc., and the lower limit is 490, 450, 400, 350, 300, 250, 200, 150, 120, 119, 115, 110, 109, 105, 100, 75, 50, etc., as examples. In one embodiment, the molecular weight of the component (D) is preferably 50 to 500.
< (E) component: curing catalyst >
In one embodiment, the above coating agent may contain (E) the component (a): a curing catalyst. (E) The components can be used alone or in combination of 2 or more.
(E) The components include, for example, organometallic catalysts and organic amine catalysts.
Examples of the organometallic catalyst include an organic main group metal catalyst (typical metal catalyst), an organic transition metal catalyst, and the like.
Examples of the organic main group metal catalyst include an organotin catalyst, an organobismuth catalyst, and the like.
Examples of the organotin catalyst include dibutyltin dilaurate, dioctyltin dilaurate and the like.
The organic bismuth catalyst includes, for example, bismuth octoate.
Examples of the organic transition metal catalyst include an organic titanium catalyst, an organic zirconium catalyst, and an organic iron catalyst.
The organic titanium catalyst is exemplified by titanium ethyl acetoacetate (チ タ ン エ チ ル ア セ ト ア セ テ ー ト) and the like.
Examples of the organozirconium catalyst include zirconium tetraacetylacetonate (ジ ル コ ニ ウ ム テ ト ラ ア セ チ ル ア セ ト ネ ー ト) and the like.
Examples of the organic iron catalyst include iron acetylacetonate (iron ア セ チ ル ア セ ト ネ ー ト) and the like.
Examples of the organic amine catalyst include diazabicyclooctane, dimethylcyclohexylamine, tetramethylpropylenediamine, ethylmorpholine, dimethylethanolamine, triethylamine, triethylenediamine, and the like.
The upper limit of the content (converted into solid content) of the component (E) in the coating agent is, for example, 1 mass%, 0.9 mass%, 0.75 mass%, 0.5 mass%, 0.25 mass%, 0.1 mass%, 0.09 mass%, 0.05 mass%, 0.02 mass%, etc., and the lower limit is, for example, 0.9 mass%, 0.75 mass%, 0.5 mass%, 0.25 mass%, 0.1 mass%, 0.09 mass%, 0.05 mass%, 0.02 mass%, 0.01 mass%, 0 mass%, etc. In one embodiment, the content (in terms of solid content) of the component (E) in the coating agent is preferably about 0 to 1% by mass from the viewpoint of curability and pot life.
< component (F): organic solvent >
In one embodiment, the above coating agent may contain (F) component: an organic solvent. (F) The components can be used alone or in combination of 2 or more. (F) The components are exemplified by ketone solvents such as methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, and cyclohexanone; aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, and butanol; glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate; ester solvents such as ethyl acetate, butyl acetate, methyl cellosolve acetate, and cellosolve acetate; petroleum solvents such as solvasso (ソ ル ベ ッ ソ) #100 and solvasso #150 (both trade names, manufactured by エ ク ソ ン モ ー ビ ル); halogenated alkane solvents such as chloroform; amide solvents such as dimethylformamide, and the like. Among these, from the viewpoint of pot life of the coating agent of the present invention, a ketone solvent is preferable, and acetylacetone is preferable among the ketone solvents.
When the coating agent contains an organic solvent, the upper limit of the content of the component (F) in the coating agent is 90 mass%, 80 mass%, 70 mass%, 60 mass%, 55 mass%, etc., and the lower limit is 85 mass%, 80 mass%, 70 mass%, 60 mass%, 55 mass%, 50 mass%, etc., for example. In one embodiment, when the coating agent contains the component (F), the content of the component (F) in the coating agent is preferably about 50 to 90% by mass from the viewpoint of pot life. The component (F) contained in the coating agent may contain an organic solvent contained in the components (a), (B), (C) and (E).
< additives >
The thermosetting coating agent may contain, as additives, agents other than the component (a), the component (B), the component (C), the component (D), the component (E), and the component (F). Examples of the additives include triols, tetrols, polymerization inhibitors, antioxidants, light stabilizers, defoamers, surface conditioners, pigments, antistatic agents, metal oxide fine particle dispersions, organic fine particle dispersions, and the like. In one embodiment, the content of the additive is, for example, about 0.1 to 10% by mass, less than about 5% by mass, less than about 1% by mass, less than about 0.1% by mass, less than about 0.01% by mass, 0% by mass, or the like (in terms of solid content) of the coating agent.
The thermosetting coating agent can be obtained by a method including a step of mixing the component (a), the component (B), and the component (C) by various known means, and if necessary, the component (D), the component (E), the component (F), and/or additives.
The thermosetting coating agent can be used as a self-repairing thermosetting coating agent or a thermosetting coating agent for a decorative film.
[ cured product ]
The present disclosure provides a cured product of the above thermosetting coating agent. The conditions for producing the cured product are exemplified by the conditions described below.
[ film ]
The present disclosure provides a film containing the cured product.
The substrate may be any of various known substrates. Examples of the substrate include a polycarbonate film, an acrylic film (e.g., a polymethyl methacrylate film), a polystyrene film, a polyester film, a polyolefin film, an epoxy resin film, a melamine resin film, a triacetyl cellulose film, an ABS film, an AS film, a norbornene resin film, a cycloolefin film, a polyvinyl alcohol film, and a thermoplastic polyurethane elastomer (TPU) film. The thickness of the substrate is not particularly limited, and is preferably about 20 μm to 300. mu.m. The thickness of the coating layer is not particularly limited, but is preferably about 2 μm to 30 μm.
The above-mentioned film can be produced by various known methods. In one embodiment, a method of making a membrane includes: a step (coating step) of coating the coating agent on at least one surface of a base material; and a step of forming a coating agent cured layer by thermal curing (thermal curing step).
(coating Process)
Examples of the coating method include bar coater coating, wire bar coating (ワ イ ヤ ー バ ー coating), Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing (フ レ キ ソ printing), and screen printing.
The amount of coating is not particularly limited. The coating weight is preferably 0.1g/m in mass after drying2～30g/m2About, more preferably 1g/m2～20g/m2Left and right.
(Heat curing step)
Examples of the drying method include drying with a circulating air dryer. The drying conditions include, for example, standing at 120 ℃ for 1 minute and the like.
When the film is produced, the film is dried and then aged (エ ー ジ ン グ) as necessary. As an example, an aging treatment at 40 ℃ for 24 hours, etc. are exemplified.
Examples
The present invention is specifically illustrated by the following 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, nor to the examples specifically described in the present specification, but is limited only by the scope of the claims. Meanwhile, in each of examples and comparative examples, numerical values of parts,% and the like are based on mass unless otherwise specified.
< preparation of starting Material >
[ (meth) acrylic resin ]
[ resin A ]
24.0 parts by mass of methyl methacrylate (hereinafter, also referred to as MMA), 59.0 parts by mass of n-butyl acrylate (hereinafter, also referred to as BA), 17.0 parts by mass of 2-hydroxyethyl acrylate (hereinafter, also referred to as HEA) and 150 parts by mass of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube, and the reaction system was set to 80 ℃. Then, 0.5 part by mass of azobisisobutyronitrile was added thereto, and the mixture was kept at about 80 ℃ for 5 hours. Subsequently, 1.0 part by mass of azobisisobutyronitrile was added, and the reaction system was further kept at about the same temperature for 4 hours. Then, the reaction system was cooled to room temperature, thereby obtaining a solution (nonvolatile content 40%) of resin a having the physical properties shown in table 1.
[ resin B and resin C ]
The resin was prepared in the same manner as in the preparation of resin a, except that the raw materials were changed to those shown in table 1. The physical properties of the obtained resin B and resin C are shown in table 1. The acid values of resins A to C were all 0 mgKOH/g.
TABLE 1
Resin composition Tg(℃) Hydroxyl value (mgKOH/g) MMA (% by mass) BA (% by mass) HEA (mass%)
A －22 80 24 59 17
B －4 80 45 38 17
C 49 80 70 13 17
The glass transition temperatures (Tg) in the table are values calculated based on the Fox equation. Further, as for the resin A, when measured by Differential Scanning Calorimetry (DSC) at a temperature rising rate of 10 ℃ per minute under a nitrogen gas flow, the glass transition temperature was-23 ℃.
< preparation of Heat-curable coating agent >
Example 1
47.17 parts of resin A as component (A), 1.03 parts of BYK-SILCLEAN3700 (manufactured by ビ ッ ク ケ ミ ー, ジ ャ パ ン, Inc.), 1.03 parts of hydroxyl group-containing organic modified silicone modified with an acrylic polymer (having a solid content of 25%), 6.85 parts of CORONATE 2793 (manufactured by Bay ソ ー, Inc.) as component (C), 6.85 parts of dioctyltin dilaurate as component (E) (having a solid content of 100%, hereinafter referred to as DOTDL), 41.06 parts of methyl ethyl ketone (MEK, hereinafter referred to as "DOTDL") as component (F), and 3.86 parts of acetylacetone (hereinafter referred to as "AcAc") as component (B) were used. By thoroughly mixing the above components, a coating agent having a solid content concentration of 26% was prepared.
Examples 2 to 6 and comparative examples 1 to 9
The heat-curable coating agents of examples and comparative examples other than example 1 were prepared in the same manner as in example 1, except that the component compositions were changed as shown in the following table. The coating agent had a solid content concentration of 26%.
TABLE 2
Figure BDA0002106455390000241
DURANATE 24A-100: biuret form of hexamethylene diisocyanate (solid content: 100%) manufactured by Asahi Kasei corporation
TAKENATE D-140N: manufactured by Mitsui chemical Co., Ltd., adduct form of isophorone diisocyanate (solid content concentration 75%)
TAKENATE D-120N: manufactured by Mitsui chemical Co., Ltd., adduct form of hydrogenated xylylene diisocyanate (solid content concentration 75%)
TAKENATE D-110N: manufactured by Mitsui chemical Co., Ltd., adduct form of xylylene diisocyanate (solid content concentration 75%)
TAKENATE D-204 EA-1: isocyanurate form of toluene diisocyanate (solid content 50%)
CORONATE HX: manufactured by Chinese envoy ソ ー, an isocyanurate form of hexamethylene diisocyanate (solid content concentration: 100%)
TAKENATE D-160N: manufactured by Mitsui chemical Co., Ltd., adduct form of hexamethylene diisocyanate (solid content concentration 75%)
ADEKA (ア デ カ) polyether GM-30: ether triol having a hydroxyl value of 535mgKOH/g to 565mgKOH/g manufactured by ADEKA
< preparation of film >
The obtained heat-curable coating agent was applied to a commercially available polyethylene terephthalate film (trade name: コ ス モ シ ャ イ ン A4100, 100 μm thick) to give a coating film thickness of 10 μm after drying, and dried at 120 ℃ for 60 seconds, thereby heat-curing the coating agent.
< self-repairability of cured product >
The film surface was reciprocated 10 times by a brass brush (true ブ ラ シ), and the time until the scratch disappeared was measured.
Very good: recovery within 1 second
O: recovery within 1 minute
And (delta): recovery within 5 minutes
X: does not recover within 5 minutes
< abrasion resistance of cured product >
The haze value (ヘ イ ズ value) before and after the Taber (テ ー バ ー) abrasion test (color technical research institute on kamura, ltd., HM-150) according to the abrasion test method of JIS K7204 plastic-abrasion wheels was measured, and the difference (Δ H) between the haze values before and after the test was calculated. Taber abrasion test Using a Taber abrasion tester (AB-101 Taber abrasion tester manufactured by テ ス タ ー industries, Ltd.), the abrasion wheel CS-10F was rotated 100 times under the conditions of a load of 500g and a rotation speed of 60 rpm.
< antifouling Property of cured product >
The film surface was marked with a blot of an oily marker (manufactured by ZEBRA corporation, trade name マ ッ キ ー (red)), and the blot was wiped with a dry nonwoven fabric (manufactured by asahi chemical corporation, trade name ベ ン コ ッ ト M-3II) to evaluate the film surface. The evaluation criteria are as follows.
O: can be wiped off
X: without wiping off
< elongation at break of cured product >
The elongation at break of the cured product alone was measured under the test conditions of the test method for plastic-tensile properties according to JIS K7204. The cured product had a shape of 5mm in width, 10 μm in thickness and 25mm in length, and the test speed was 200 mm/min.
Elongation at break (%) (100X (L-25)/25)
L: length of cured product at break of cured product
TABLE 3
Self-repairing property Abrasion resistance Antifouling property Elongation at break
Example 1 ◎ 8.0 ○ 140
Example 2 ◎ 4.1 ○ 180
Example 3 ◎ 5.3 ○ 170
Example 4 ◎ 5.5 ○ 170
Example 5 ○ 9.2 ○ 160
Example 6 ◎ 7.9 ○ 160
Comparative example 1 × 24.7 ○ 100
Comparative example 2 × 23.2 ○ 140
Comparative example 3 × 19.0 ○ 140
Comparative example 4 × 23.0 ○ 60
Comparative example 5 △ 13.2 ○ 140
Comparative example 6 × 11.6 ○ 150
Comparative example 7 × 14.5 ○ 150
Comparative example 8 × 16.8 ○ 100
Comparative example 9 ◎ 12.4 × 140

Claims (7)

1. A heat-curable coating agent containing:
(A) a hydroxyl group-containing (meth) acrylic resin having a glass transition temperature of less than-20 ℃;
(B) a hydroxyl group-containing organically modified silicone; and
(C) allophanate form and/or biuret form of the polyisocyanate.
2. The heat-curable coating agent according to claim 1, which comprises
(D) A diol having a hydroxyl value of 200mgKOH/g or more and a molecular weight of 500 or less.
3. The heat-curable coating agent according to claim 1 or 2, which contains (E) a curing catalyst.
4. The heat-curable coating agent according to any one of claims 1 to 3, which contains (F) an organic solvent.
5. The heat-curable coating agent according to any one of claims 1 to 4, which is a self-healing coating agent.
6. A cured product of the heat-curable coating agent according to any one of claims 1 to 5.
7. A film comprising the cured product according to claim 6.
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