Hardening components

Abstract

The present invention provides a masking material that has excellent shape retention, excellent freedom in coating shape, can be rapidly formed into a film, and is economical. Also, the present invention provides a masking material that has excellent physical properties (e.g., tear strength) after curing, and solves the problem of the masking material tearing when peeled off after curing. [Solution] (Formula 1): (CH2=C(R 1 )-CO-OR 2 -O-CO-NH-R 3 -NH-CO) n -R 4 [In the formula, R 1 each independently represents a hydrogen atom or a methyl group; R 2 each independently represents an aliphatic group having 1 to 8 carbon atoms; R 3 each independently represents an aromatic group or an aliphatic group having 1 to 30 carbon atoms; R 4 is an aromatic or aliphatic group having a polycarbonate skeleton and / or a polyester skeleton and a number average molecular weight of 500 or more, n is an integer from 2 to 4. A prepolymer (A1) represented by the formula: (Formula 2): (CH2=C(R 5 )-CO-OR 6 -O-CO-NH) m -R 7 [In the formula, R 5 each independently represents a hydrogen atom or a methyl group; R 6 each independently represents an aliphatic group having 1 to 8 carbon atoms; R 7 Each of these independently represents an aromatic group or an aliphatic group having 1 to 30 carbon atoms. m is an integer from 2 to 4. A curable composition comprising a non-polymer (A2) represented by the formula:

Description

Technical Field

[0001] The present invention relates to a curable composition, a curable masking material containing the curable composition, and a method for producing a conjugate using the curable composition.

Background Art

[0002] When performing painting on various products, masking is performed to protect a part of the base material so that painting is applied only to a predetermined portion. Conventionally, masking has been performed by attaching a film-like article such as a tape. However, from the viewpoint of handleability, this method is not easily automated. Instead of a film-like article such as a tape, it is known to apply a masking material obtained by dispersing or dissolving a resin in a solvent to a base material (Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, conventional solvent-based masking materials have poor shape retention, resulting in low freedom in coating shape and problems with handleability. In particular, this becomes a problem when automating the coating process using a robot or the like. In addition, conventional solvent-based masking materials require the installation of a drying furnace to improve the peelability of the masking material, which is not economical. An object of the present invention is to provide a masking material that has excellent shape retention, excellent freedom in coating shape, can be quickly coated, or has excellent economy. Another object of the present invention is to provide a masking material that has excellent physical properties (for example, tear strength) after curing and solves the problem that the masking material tears during peeling after curing.

Means for Solving the Problem

[0005] One embodiment of the present invention is as follows. [Item 1] (Formula 1): (CH2=C(R 5 )-CO-O-R 2 -O-CO-NH-R 3 -NH-CO) n -R 4 [In the formula, Each of R 1 is independently a hydrogen atom or a methyl group, Each of R 2 is independently an aliphatic group having 1 to 8 carbon atoms, Each of R 3 is independently an aromatic group or an aliphatic group having 1 to 30 carbon atoms, R 4 is an aromatic group or an aliphatic group having a number average molecular weight of 500 or more and having a polycarbonate skeleton and / or a polyester skeleton, n is an integer of 2 to 4.] The prepolymer (A1) represented by, and (Formula 2): (CH2=C(R 5 )-CO-O-R 6 -O-CO-NH) m -R 7 [In the formula, Each of R 5 is independently a hydrogen atom or a methyl group, Each of R 6 is independently an aliphatic group having 1 to 8 carbon atoms, Each of R 7 is independently an aromatic group or an aliphatic group having 1 to 30 carbon atoms. m is an integer of 2 to 4.] The non-polymer (A2) represented by A curable composition containing. [Item 2] The curable composition according to item 1, wherein the number average molecular weight of the prepolymer (A1) is 1000 or more and 5000 or less, and the number average molecular weight of the nonpolymer (A2) is 750 or less. [Section 3] The curable composition according to item 1, comprising 15% by weight or more of the prepolymer (A1) and 15% by weight or more of the nonpolymer (A2). [Section 4] The curable composition according to item 1, wherein the tanδ at 10°C to 30°C after curing is 0.07 or higher. [Section 5] The curable composition according to claim 1, further comprising other acrylic monomers (A3). [Section 6] The curable composition according to item 1, comprising 10% by weight or more of solid particles (B). [Section 7] A curable composition according to item 1, comprising a phosphorus-containing initiator. [Section 8] A curable masking material comprising the curable composition described in item 1. [Section 9] A masking step comprising providing a masking member that masks at least a portion of the surface of a substrate using the curable masking material described in item 8; A curing step including curing the masking member; An exposure step, which includes peeling off the masking member to expose a portion of the substrate surface; and A bonding step including bonding other members to the exposed portion of the surface of the substrate; A method for producing a compound, including the compound. [Section 10] moreover, A painting process including applying paint to the substrate. A method for producing the compound according to item 9, including the method described in item 9. [Section 11] The method for producing a composite according to claim 9, comprising, in the masking step, applying the curable masking material to a thickness of 0.1 mm or more to mask at least a portion of the surface of the substrate. [Section 12] The method for producing a composite according to claim 9, comprising, in the masking step, applying the curable masking material in a width of 5 mm or more to mask at least a portion of the surface of the substrate. [Section 13] The method for producing the compound according to item 9, wherein the substrate is a resin. [Section 14] A method for manufacturing the composite according to item 9, using a robot. [Effects of the Invention]

[0006] The curable masking material containing the curable composition of the embodiment of the present invention has excellent shape retention, allowing it to be applied only to the desired area and offering excellent freedom in application shape. Furthermore, it can form a film quickly, is economical, and has excellent peelability. Thus, the curable composition of the embodiment of the present invention has excellent handling properties, making it easy to automate with robots, etc., and improving work efficiency. Moreover, the curable composition of the embodiment of the present invention causes less contamination of the substrate and is less likely to adversely affect subsequent processes. Furthermore, the present invention provides a masking material that has excellent physical properties after curing and can be peeled off smoothly. [Modes for carrying out the invention]

[0007] <Curable composition> A curable composition in an embodiment of the present invention, (Formula 1): (CH2=C(R 1 )-CO-OR 2 -O-CO-NH-R 3 -NH-CO) n -R 4 [In the formula, R 1 Each of them is independently a hydrogen atom or a methyl group, R 2 Each of these is an aliphatic group with 1 to 8 carbon atoms, R 3 Each of these is independently an aromatic group or aliphatic group having 1 to 30 carbon atoms. R 4This is an aromatic group or aliphatic group with a molecular weight of 500 or more having a polycarbonate backbone and / or polyester backbone. n is between 2 and 4. A prepolymer (A1) represented by, and (Formula 2): (CH2=C(R 5 )-CO-OR 6 -O-CO-NH) m -R 7 [In the formula, R 5 Each of them is independently a hydrogen atom or a methyl group, R 6 Each of these is an aliphatic group with 1 to 8 carbon atoms, R 7 Each of these is independently an aromatic or aliphatic group having 1 to 30 carbon atoms. m is between 2 and 4. Nonpolymer (A2) represented by Includes.

[0008] [Prepolymer (A1)] A curable composition in an embodiment of the present invention, (CH2=C(R 1 )-CO-OR 2 -O-CO-NH-R 3 -NH-CO) n -R 4 (Formula 1) [In the formula, R 1 Each of them is independently a hydrogen atom or a methyl group, R 2 Each of these is an aliphatic group with 1 to 8 carbon atoms, R 3 Each of these is independently an aromatic group or aliphatic group having 1 to 30 carbon atoms. R 4 This is an aromatic group or aliphatic group with a molecular weight of 500 or more having a polycarbonate backbone and / or polyester backbone. n is between 2 and 4. It contains a prepolymer (A1) represented by [formula].

[0009] R1 Each of these is independently either a hydrogen atom or a methyl group.

[0010] R 2 This is an aliphatic group, which may be an aliphatic hydrocarbon group, and is preferably an alkylene group.

[0011] R 2 The number of carbon atoms is 1 to 8, and may be 1 or more, 2 or more, or 3 or more, and may be 8 or less, 7 or less, or 6 or less.

[0012] R 2 Specific examples include ethylene groups, propylene groups, trimethylene groups, and butylene groups.

[0013] R 3 is an aromatic group or an aliphatic group, and may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

[0014] R 3 The number of carbon atoms is 1 to 30, and may be 2 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 28 or less, 24 or less, 20 or less, or 16 or less.

[0015] R 3 The group may be derived from a diisocyanate compound. That is, the group may be obtained by removing two -NCO groups from a diisocyanate compound. The diisocyanate compound may be an aliphatic diisocyanate or an aromatic diisocyanate, and from the viewpoint of physical properties after curing, an aliphatic diisocyanate is preferred. The alicyclic diisocyanate may be a monocyclic alicyclic diisocyanate or a polycyclic alicyclic diisocyanate (e.g., a bicyclic alicyclic diisocyanate, a tricyclic alicyclic diisocyanate, a bridged alicyclic diisocyanate, etc.).

[0016] Examples of diisocyanate compounds include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate. Acyclic aliphatic diisocyanates such as methyl caproate, lysine diisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate; 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IP DI), methylenebis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate) or mixtures thereof) (hydrogenated MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanate methyl)cyclohexane (1,3- or 1,4-bis(isocyanate methyl)cyclohexane or mixtures thereof) (hydrogenated XDI), DI Monocyclic alicyclic diisocyanates such as diisocyanate mer acid, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI); polycyclic (e.g., bridged ring) alicyclic diisocyanates such as norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanate methylbicycloheptane, and di(diisocyanate methyl)tricyclodecane;Tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or mixture thereof) (TDI), phenylene diisocyanate (m-,p-phenylene diisocyanate or mixture thereof, 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixture thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixture thereof) (XDI), Examples include tranmethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or a mixture thereof) (NDI), nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and aromatic diisocyanates such as 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

[0017] R 4 This is an aromatic group or aliphatic group with a molecular weight of 500 or more, having a polycarbonate backbone and / or polyester backbone.

[0018] R 4 It is an n-valence function, where n is an integer between 2 and 4, preferably 2.

[0019] A polycarbonate skeleton is, (Formula 21): -[-R 41 -OC(=O)-O-] q - (In the formula, R 41 (where is a divalent hydrocarbon group and q is an integer.) The skeleton shown is acceptable.

[0020] R 41 R may be aromatic or aliphatic, preferably a linear, branched, or cyclic alkylene group, and more preferably a linear alkylene group. 41 The number of carbon atoms may be 1 to 15, for example 2 to 10, preferably 3 to 7. 41 Specific examples include trimethylene groups, propylene groups, tetramethylene groups, pentamethylene groups, hexamethylene groups, heptamethylene groups, etc. In the polycarbonate skeleton, each R 41 They may be the same or different.

[0021] q may be 3 or greater, for example, 5 or greater, preferably 10 or greater.

[0022] Polyester skeleton is, (Formula 22): -[C(=O)-R 42 -O-] r - (In the formula, R 42 (where r is a divalent hydrocarbon group, and r is an integer.) The skeleton shown is acceptable.

[0023] R 42 R may be a linear, branched, or cyclic alkylene group, and is preferably a linear alkylene group. 42 The number of carbon atoms may be 1 to 15, for example 2 to 10, preferably 2 to 7. 42 A concrete example is R 42 Specific examples include methylene groups, ethylene groups, trimethylene groups, propylene groups, tetramethylene groups, pentamethylene groups, hexamethylene groups, heptamethylene groups, etc. In the polycarbonate skeleton, each R 42 They may be the same or different.

[0024] r may be 3 or greater, for example, 5 or greater, preferably 10 or greater.

[0025] Alternatively, a polyester skeleton is, Formula (23): -[-C(=O)-R 43 -C(=O)OR 44 -O-] s - (In the formula, R 43 and R 44 (Each of these is an independent divalent hydrocarbon, and s is an integer.) The skeleton shown may also be used.

[0026] For example, R 43 R may be a divalent aromatic group having 6 to 10 carbon atoms (e.g., a phenylene group (p-phenylene group)) or an alkylene group having 1 to 15 carbon atoms (e.g., an alkylene group having 2 to 10 carbon atoms), and preferably an alkylene group having 2 to 7 carbon atoms. 44 This may be an alkylene group having 1 to 15 carbon atoms, for example, an alkylene group having 2 to 10 carbon atoms, and preferably an alkylene group having 2 to 8 carbon atoms.

[0027] s may be 3 or greater, for example, 5 or greater, preferably 10 or greater.

[0028] R 4 The number-average molecular weight is 500 or more, and may be 750 or more, 1000 or more, 1250 or more, 1500 or more, or 2500 or more, preferably 750 or more. 4 The number-average molecular weight may be 10,000 or less, 7,500 or less, 5,000 or less, 4,000 or less, 3,000 or less, or 2,500 or less, preferably 4,000 or less. Here, the number-average molecular weight is the polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0029] The number-average molecular weight of prepolymer (A1) may be 750 or more, 1000 or more, 1500 or more, 2000 or more, 2500 or more, or 3000 or more, preferably 1000 or more. The number-average molecular weight of prepolymer (A1) may be 10000 or less, 7500 or less, 5000 or less, 4000 or less, 3000 or less, or 2500 or less, preferably 5000 or less. A molecular weight within the above range is advantageous in terms of physical properties and viscosity after curing. Note that the number-average molecular weight is the polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0030] The viscosity of the prepolymer (A1) at 40°C may be 1 Pa·s or more, for example 10 Pa·s or more, and preferably 20 Pa·s or more. The viscosity of the prepolymer (A1) at 40°C may be 200 Pa·s or less, for example 150 Pa·s or less, and preferably 100 Pa·s or less. When the viscosity of the prepolymer (A1) at 40°C is within the above range, the coatability and peelability are more favorable. The test is performed using a rheometer (DHR-3, manufactured by TA instruments) equipped with a 20 mm plate, at a rotation speed of 0.42 rpm and 40°C.

[0031] [Nonpolymer (A2)] A curable composition in an embodiment of the present invention, Formula (2): (CH2=C(R 5 )-CO-OR 6 -O-CO-NH) m -R 7 [In the formula, R 5 Each of them is independently a hydrogen atom or a methyl group, R 6 Each of these is an aliphatic group with 1 to 8 carbon atoms, R 7 These are independently aromatic or aliphatic groups having 1 to 30 carbon atoms. m is between 2 and 4. It contains a nonpolymer (A2) represented by [formula].

[0032] R 5 Each of these is independently either a hydrogen atom or a methyl group.

[0033] R 6 This is an aliphatic group, which may be an aliphatic hydrocarbon group, and is preferably an alkylene group.

[0034] R 7 The number of carbon atoms is 1 to 8, and may be 1 or more, 2 or more, 3 or more, and may be 8 or less, 7 or less, or 6 or less.

[0035] R 7 Specific examples include ethylene groups, propylene groups, trimethylene groups, and butylene groups.

[0036] R 7 is an aromatic group or an aliphatic group, and may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

[0037] R 7 The number of carbon atoms is between 1 and 30, and may be 2 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 28 or less, 24 or less, 20 or less, or 16 or less.

[0038] R 7 The group may be derived from a polyisocyanate compound. That is, it may be a group obtained by removing m -NCO groups from a polyisocyanate compound. m may be an integer from 2 to 4, preferably 2. The polyisocyanate compound may be an aliphatic polyisocyanate or an aromatic polyisocyanate, and from the viewpoint of physical properties after curing, an aliphatic polyisocyanate is preferred. The alicyclic isocyanate may be a monocyclic alicyclic polyisocyanate or a polycyclic alicyclic polyisocyanate (e.g., a bicyclic alicyclic polyisocyanate, a tricyclic alicyclic polyisocyanate, a bridged alicyclic polyisocyanate, etc.).

[0039] Examples of polyisocyanate compounds include the above R 3In addition to the diisocyanate compounds mentioned in the description, other examples include triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, and 1,3,6-hexamethylene triisocyanate.

[0040] The number-average molecular weight of the nonpolymer (A2) may be 100 or more, 200 or more, 300 or more, 400 or more, or 500 or more. The number-average molecular weight of the nonpolymer (A2) may be 750 or less, 700 or less, 650 or less, 600 or less, 550 or less, or 500 or less. A molecular weight within the above range is advantageous in terms of physical properties and viscosity after curing. The number-average molecular weight may be a polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0041] [Other acrylic monomers (A3)] The curable composition may contain other acrylic monomers (A3). The inclusion of other acrylic monomers (A3) is advantageous in terms of the physical properties after curing.

[0042] The number of acrylic polymerization groups (acrylate groups, acrylamide groups, etc.) in the other acrylic monomer (A3) may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less, for example, 1, 2, or 3.

[0043] The other acrylic monomer (A3) may or may not have a urethane group and / or a urea group, but it is preferable that it does not have one.

[0044] The number-average molecular weight of the other acrylic monomer (A3) may be 100 or more, 200 or more, 300 or more, 400 or more, or 500 or more. The number-average molecular weight of the other acrylic monomer (A3) may be 1000 or less, 750 or less, 700 or less, 650 or less, 600 or less, 550 or less, or 500 or less. The number-average molecular weight may be the polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0045] Other examples of acrylic monomers (A3) include alkyl(meth)acrylates such as methyl(meth)acrylate, butyl(meth)acrylate, hexyl(meth)acrylate, isodecyl(meth)acrylate, stearyl(meth)acrylate, isobornyl(meth)acrylate, etc. (wherein the alkyl group has 1 or more carbon atoms, 3 or more, 5 or more, 7 or more, 10 or more, 12 or more, and 30 or less, 27 or less, 24 or less, 20 or less, or 16 or less); hydroxyl group-containing(meth)acrylates such as hydroxymethyl(meth)acrylate and hydroxyethyl(meth)acrylate; (poly)alkylene(meth)acrylates such as diethylene glycol monoethyl ether acrylate, dipropylene glycol monoethyl ether acrylate, polyethylene glycol monoethyl ether acrylate, and polypropylene glycol monoethyl ether acrylate. Examples include chol group-containing (meth)acrylates; epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate and (3,4-epoxycyclohexyl)methyl (meth)acrylate; aromatic group-containing monomers such as styrene and 2-hydroxy-3-phenoxypropyl acrylate; isocyanate group-containing monomers such as 2-isocyanatoethyl (meth)acrylate; Si group-containing monomers such as trimethylsilyl acrylate and trialkoxysilyl acrylate; acidic functional group-containing monomers such as (meth)acrylic acid and 3-(acryloyloxy)propane-1-sulfonic acid and their salts; cyclic group-containing monomers such as adamantyl acrylate and cyclohexyl acrylate; fluorine-containing monomers such as 1H,1H,2H,2H-tridecafluoro-n-octyl (meth)acrylate; and amide monomers such as acrylamide and N-alkylacrylamide.

[0046] [Solid particles (B)] The curable composition of the embodiment of the present invention comprises solid particles (B). The solid particles (B) are particles that are solid at room temperature and are not particularly limited as long as the curable composition for which the present invention is aimed can be obtained. Examples of solid particles (B) include alkali metal or alkaline earth metal carbonates, oxides, or hydroxides such as calcium carbonate, calcium hydroxide, calcium oxide, and magnesium hydroxide; silica such as fumed silica and precipitated silica; carbon such as carbon black and graphite; mineral fillers such as alumina, talc, mica, and clay; glass beads; balloons such as shirasu balloons, glass balloons, silica balloons, and plastic balloons; inorganic fibers such as glass fibers and metal fibers; organic fibers such as polyethylene fibers and polypropylene fibers; ceramic fillers such as aluminum borate, silicon carbide, silicon nitride, potassium titanate, magnesium borate, and titanium diboride; and needle-shaped crystalline fillers such as chrysotile and wollastonite. The solid particles (B) may also be surface-treated particles (e.g., fatty acid treatment).

[0047] The central particle size of the solid particle (B) may be 0.003 μm or larger, for example, 0.5 μm or larger. Furthermore, the central particle size of the solid particle (B) is preferably 20 μm or smaller, more preferably 10 μm or smaller, and even more preferably 5 μm or smaller. The central particle size is defined as the 50% diameter of the weight-cumulative particle size distribution measured by a laser diffraction / scattering particle size distribution analyzer.

[0048] The solid particles (B) may be alkali metal or alkaline earth metal carbonates, oxides or hydroxides, silica, or alumina, etc., from the viewpoint of improving coatability and peelability, and among these, carbonates, particularly calcium carbonate, are preferred.

[0049] [Polymerization initiator (C)] The curable compositions of embodiments of the present invention may contain a polymerization initiator. The polymerization initiator may be, for example, a photoinitiator and / or a thermal initiator, and is not particularly limited as long as the curable composition for which the present invention is aimed is obtained. When using a curable composition for photomasking, a photoinitiator is usually used. Examples of polymerization initiators include benzoin-based initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-allylbenzoin, and 2-chlorbenzoin; acetophenone-based initiators such as 1-hydroxycyclohexyl phenyl ketone, diethoxyacetophenone, hydroxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, α-aminoacetophenone, and 2,2-dimethoxy-1,2-diphenylethane-1-one; benzophenone-based initiators such as benzophenone, 4-methylbenzophenone, 4-chlorbenzophenone, and 4-chlorbenzophenone; thioxanthone-based initiators such as 2-methylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothiooxanthonone; and azo-based initiators such as azobisisobutyronitrile. Examples include peroxide-based initiators such as benzoyl peroxide; quinone-based initiators such as anthraquinone, 2-chloranthraquinone, and phenanthrene; phosphorus-containing initiators including phosphine oxide-based initiators such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and phosphinate-based initiators such as ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate.

[0050] The polymerization initiator may include a phosphorus-containing initiator, particularly a phosphorus-containing aromatic initiator (e.g., an aromatic phosphinate). When the curable composition is applied thickly (e.g., 0.2 mm or more, particularly 0.5 mm or more), the light transmittance decreases exponentially, which can be problematic as the entire curable composition becomes difficult to cure. In the curable composition of the embodiment of the present invention, by combining a prepolymer (A), solid particles (B), and a phosphorus-containing initiator, both deeper curing and rapid curing can be achieved. This is particularly effective when the curable composition is applied thickly. After sufficient curing, subsequent processes such as baking paint can be performed to improve peelability.

[0051] [Other ingredients] The curable composition of the embodiment of the present invention may contain other components, and the other components are not particularly limited as long as the curable composition for which the present invention is sought is obtained.

[0052] The curable composition may also contain, as one of its other components, a prepolymer (A1), a nonpolymer (A2), or other monomers or polymers other than acrylic monomers (A3).

[0053] The curable composition may also contain an antioxidant as one of its other components. Examples of antioxidants include phenolic antioxidants (e.g., hindered phenols), aromatic amine antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. The inclusion of an antioxidant ensures good release properties of the masking material even after high-temperature heating.

[0054] The curable composition may contain, in appropriate amounts, other components such as colorants (e.g., iron oxide, titanium dioxide, other coloring pigments, dyes, etc.), solvents (e.g., water, polar organic solvents, non-polar organic solvents, etc.), silane compounds (silane compounds having functional groups such as amino groups, mercapto groups, epoxy groups, (meth)acrylic groups, vinyl groups, etc.), epoxy compounds which may have polyoxyalkylene groups, plasticizers, ultraviolet absorbers / light stabilizers (e.g., benzotriazoles, hindered amines, etc.), thixotropes (e.g., colloidal silica, organic bentonite, fatty acid amides, hydrogenated castor oil, etc.), viscosity modifiers, sensitizers, polymerization inhibitors, etc.

[0055] [Composition of curable composition] The amount of prepolymer (A1) may be 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 30% by weight or more, or 40% by weight or more, relative to the curable composition, and preferably 10% by weight or more. The amount of prepolymer (A) may be 90% by weight or less, 75% by weight or less, 60% by weight or less, 45% by weight or less, or 30% by weight or less, relative to the curable composition, and preferably 60% by weight or less.

[0056] The amount of nonpolymer (A2) may be 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 30% by weight or more, or 40% by weight or more, relative to the curable composition, preferably 10% by weight or more. The amount of nonpolymer (A2) may be 90% by weight or less, 75% by weight or less, 60% by weight or less, 45% by weight or less, or 30% by weight or less, relative to the curable composition, preferably 60% by weight or less.

[0057] The amount of monomer (A3) may be 30% by weight or less, 25% by weight or less, 20% by weight or less, 15% by weight or less, or 10% by weight or less, relative to the curable composition. When the amount of monomer (A3) in the curable composition is within the above range, unreacted material is less likely to remain in the cured product, and the substrate is less likely to be contaminated when the masking material is removed.

[0058] The amount of solid particles (B) may be 0%, 1% or more by weight, 5% or more by weight, 10% or more by weight, 15% or more by weight, or 25% or more by weight, relative to the curable composition. The amount of solid particles (B) may be 65% or less by weight, 50% or less by weight, 35% or less by weight, or 15% or less by weight, relative to the curable composition.

[0059] The amount of polymerization initiator (C) may be 0.01% by weight or more, 0.05% by weight or more, 0.1% by weight or more, or 0.5% by weight or less, relative to the curable composition. The amount of polymerization initiator (C) may be 5% by weight or less, 4% by weight or less, 3% by weight or less, 2.5% by weight or less, or 2% by weight or less, relative to the curable composition.

[0060] The amount of other components may be 0.1% by weight or more relative to the curable composition, for example, 1% by weight or more. The amount of other components may be 25% by weight or less relative to the curable composition, for example, 10% by weight or less. Note that the weight percentage may be based on the portion excluding the solvent.

[0061] The antioxidant content in the curable composition may be 0.01% by weight or more, 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, or 1% by weight or more. The antioxidant content may be 7.5% by weight or less, 5% by weight or less, 3.5% by weight or less, 1.5% by weight or less, or 1% by weight or less.

[0062] [Viscosity of curable compositions] The viscosity of the curable composition at 40°C may be 10 Pa·s or more, 20 Pa·s or more, or 30 Pa·s or more, for example, 50 Pa·s or more, preferably 100 Pa·s or more. The viscosity of the curable composition at 40°C may also be 300 Pa·s or less, 250 Pa·s or less, or 200 Pa·s or less, preferably 180 Pa·s or less. The TI (thixotropy index) value of the curable composition at 40°C may be 0.3 or more, 0.6 or more, or 0.8 or more, for example, 1 or more. The TI value of the curable composition at 40°C may also be 3 or less, 2.5 or less, or 2 or less, preferably 1.8 or less. The curable composition of the embodiment of the present invention may be in the form of a fluid exhibiting the above viscosity or TI value. Having the viscosity or TI value of the curable composition within the above range results in more favorable coatability and peelability. The TI value is calculated from the ratio of the viscosity at 0.42 rpm to the viscosity at 4.2 rpm.

[0063] [Viscoelasticity of curable compositions after curing] The curable composition (cured product) after curing may have a tanδ of 0.07 or higher, 0.08 or higher, 0.09 or higher, 0.10 or higher, 0.11 or higher, 0.12 or higher, 0.13 or higher, or 0.14 or higher in the range of 10°C to 30°C, preferably 0.08 or higher, more preferably 0.10 or higher. The curable composition (cured product) after curing may have a tanδ of 0.50 or lower, 0.40 or lower, 0.30 or lower, 0.25 or lower, 0.20 or lower, or 0.18 or lower in the range of 10°C to 30°C, preferably 0.25 or lower, more preferably 0.20 or lower. By using the curable composition of the present invention, a cured product having the above-mentioned characteristic tanδ can be obtained, and good physical properties of the cured product can be exhibited. Tanδ is measured, for example, using a Perkin Elmer DMA 8000 at a rate of 1 Hz and 1°C / second.

[0064] <Curing Masking Material> The curable masking material in the embodiments of the present invention includes the above-mentioned curable composition and is not particularly limited as long as it can mask a portion of the substrate. By using the masking material to mask the surface of the substrate during painting, it is possible to prevent the masked surface of the substrate from being painted.

[0065] <Method for manufacturing the composite> The present invention further provides a novel method for manufacturing a composite, comprising a masking step, a curing step, an exposure step, and a bonding step. Furthermore, a painting step may be included after the masking step (preferably after the curing step) and before the exposure step.

[0066] In the method for manufacturing the composite according to the embodiment of the present invention, a drying step may be performed as necessary, but the coating can be formed by reducing the drying step or even without a drying step. From the viewpoint of workability, it is preferable to reduce the drying step, and more preferably to omit the drying step. Therefore, a drying oven may not be required.

[0067] [Masking process] The masking step includes providing a masking member that masks at least a portion of the substrate surface. The masking member is obtained by applying the above-mentioned curable masking material to the substrate surface.

[0068] The curable masking material may be applied in a wide, thick bead. The nozzle shape may be a round bead nozzle, a flat bead nozzle, a tapered bead nozzle, etc., and may be selected according to the purpose. When a certain degree of wide masking is required, a tapered bead nozzle or a fan nozzle is preferred. By adjusting the discharge speed, it is also possible to apply the material in a wider area using a shot nozzle or a slit nozzle, or by swirl application or spray application. For example, the curable composition may be supplied from a container to the substrate using a supply pump via a material supply hose. The application dispenser may be fixed to a robot and automatically applied to the desired area. To stabilize the amount of masking material supplied, a metering pump may be installed between the supply pump and the dispenser. A supply pump or dispenser with a metering device may also be used.

[0069] The coating thickness of the curable masking material may be 0.1 mm or more, 0.2 mm or more, 0.5 mm or more, 1 mm or more, 1.5 mm or more, 3 mm or more, or 5 mm or more. The coating thickness of the curable masking material may be 30 mm or less, 15 mm or less, or 10 mm or less. By having a coating thickness within the above range, the paint film and the cured masking material are less likely to become one after painting, making it easier to peel off only the cured masking material. For example, it becomes easier to automatically peel off the masking material using a gripping jig or peeling jig mounted on a robot.

[0070] The application width of the curable masking material may be 3 mm or more, 5 mm or more, or 10 mm or more. The application width of the curable masking material may be 75 mm or less, 50 mm or less, or 30 mm or less.

[0071] The above-mentioned coating thickness and coating width of the curable masking material may refer to the thickness and width after curing or painting.

[0072] The substrate is not limited and may be a metal, resin (e.g., acrylic resin, olefin resin, polyamide resin, polyimide resin, polycarbonate resin, etc.), glass, ceramic, or the like.

[0073] [Curing step] The curing step includes curing the masking member. The cured product of the embodiment of the present invention has appropriate flexibility and toughness that do not easily break even during peeling. Further, the curable masking member of the embodiment of the present invention is excellent in rapid curability.

[0074] The curing of the masking member in the embodiment of the present invention is performed by activating a polymerization initiator to advance the polymerization. The curing of the masking member may be performed by irradiating the curable composition with light or heating it. From the viewpoint of workability, it is preferable that the curing is performed by light irradiation (e.g., UV irradiation, visible light irradiation, etc.).

[0075] When the curable masking material is photocurable, curing can be achieved by passing the member through a conveyor having a light source (e.g., UV light source, visible light source) inside, or by attaching the light source to a robot and irradiating the coating portion. Also, the coating dispenser and the light source can be attached to the same robot to perform coating and curing simultaneously. As the light source, a conventional light source such as an incandescent bulb, fluorescent lamp, halogen lamp, mercury lamp, xenon lamp, etc. may be used, or an LED light source may be used. [[ID=十六]]

[0076] [[ID=十七]] The wavelength of the light used for photocuring may be 100 to 900 nm, for example, 200 to 500 nm, preferably 300 to 450 nm. The irradiance may be 100 mW / cm 2 or more, for example, 200 mW / cm 2 or more, and may be 100 W / cm 2 or less, for example, 50 W / cm 2The following applies. The curable composition in the embodiments of the present invention has superior rapid curing properties, thus improving workability. From the viewpoint of workability, the light irradiation time may be 1 minute or less, preferably 30 seconds or less, more preferably 10 seconds or less, even more preferably 5 seconds or less, even more preferably 3 seconds or less, particularly preferably 1 second or less, and may also be 0.1 seconds or more, for example, 0.3 seconds or more.

[0077] If the curable masking material is thermosetting, it can be cured using an oven, hot air device, near-infrared lamp, or a robot equipped with these. The heating temperature may be 80 to 150°C, preferably 60 to 130°C, and more preferably 70 to 120°C. From the viewpoint of workability, the heating time for curing may be less than 1 minute, preferably less than 30 seconds, and more preferably less than 10 seconds.

[0078] Conventionally, when masking materials were applied in thick films, even after curing treatments such as heating or light irradiation, the entire masking material would not harden, resulting in the problem of residue adhering to the substrate. The curable masking material of the embodiment of the present invention can harden rapidly and retains appropriate mechanical strength even after hardening. Therefore, even when applied in a wide, thick film, it can be easily peeled off as a single unit without tearing. Furthermore, since the curable masking material of the present invention does not contaminate the substrate after peeling, it does not adversely affect the adhesion when applying adhesive to the exposed surface.

[0079] [Painting Process] The painting process includes applying paint to the substrate surface after the masking process (preferably after the curing process) and before the exposure process. Painting may be carried out by various methods such as brush painting, spray painting, dip painting, powder coating, electrostatic painting, photocuring painting, and baking painting. For painting and drying, the substrate may be heated to 80°C or higher, for example, 100°C or higher, 120°C or higher, 150°C or higher, or 180°C or higher. The heating time may be from 30 seconds to 600 minutes, for example, from 5 minutes to 150 minutes.

[0080] [Exposure process] The exposure step includes peeling off the cured masking material to expose at least a portion of the substrate surface.

[0081] [Joining process] The bonding process includes bonding other components to the exposed portion of the substrate surface. An adhesive may be applied to the substrate surface to bond the other components. Pretreatment, such as priming, may be performed on the substrate surface before applying the adhesive. When using the curable masking material of the embodiment of the present invention, good adhesion to other components is achieved because no adhesion-inhibiting components remain on the substrate surface after peeling the masking material from the substrate. Bonding between the substrate surface and other components can be achieved without pretreatment such as priming. [Examples]

[0082] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, parts and percentages are based on weight.

[0083] The meanings of the abbreviations are as follows: HEA: Hydroxyethyl acrylate HDI: Hexamethylene diisocyanate IPDI: Isophorone diisocyanate UH200: Eternacoll UH-200 (Polycarbonate diol, Mn=2000, manufactured by Ube Industries, Ltd.) 2200A: CAPA2200A (Polyester diol, Mn=2000, manufactured by Ingevity) Adding a negative (-) to the above (for example, HEA-) indicates a derivative structure derived from it.

[0084] The testing method is as follows:

[0085] [Light curing] Photocuring was performed under the following conditions. Wavelength: 395nmUV Light source: LED14W / cm 2 Distance 1 inch Light exposure time: 3 seconds

[0086] [coating] The painting was done by baking paint under the following conditions. Paint: Acrylic paint Conditions: 40 minutes at 100°C or 140°C

[0087] [Tanδ] Tanδ was recorded using a Perkin Elmer DMA 8000 at a rate of 1 Hz and 1°C / second from at least -70°C to 120°C.

[0088] [Tensile strength] In accordance with JIS K 6251 or ASTM D412, a hardened sheet material with a thickness of approximately 0.1 to 1 mm was prepared. The sheet was then punched into a dumbbell shape (Type 2), and its tensile strength was measured using a testing machine at a tensile speed of 300 mm / min.

[0089] [stretch] The maximum elongation was measured when measuring tensile strength in accordance with JIS K6251 or ASTM D412.

[0090] [Tear strength] A cured sheet of material with a thickness of approximately 0.35 mm was prepared according to ASTM D 624. Next, this sheet material was punched out to produce sheets in the shape of die C, and the tear strength was measured on an electromechanical device at a speed of 500 mm / min.

[0091] [Evaluation of peelability (unpainted)] A curable composition (masking material) was applied to a substrate (polypropylene resin) to a predetermined thickness, cured under UV conditions as described above, and then the cured material was peeled off the substrate by hand. The evaluation criteria for peelability are as follows. TIFF0007855595000001.tif41150

[0092] [Evaluation of peelability (after painting)] A curable composition was applied to a substrate (PP) to a predetermined thickness and cured under UV light in the above state. Following the curing of the curable composition, the substrate and composition were coated with a topcoat, followed by a clearcoat. The cured material was then peeled off the substrate. The evaluation criteria for peelability are as follows. TIFF0007855595000002.tif57150

[0093] [Adhesion of adhesive after removal of masking material] Adhesion testing is performed after the application, curing, painting, and removal of the masking material. A primer is applied to the substrate surface, the adhesive is applied after 5 minutes, and the adhesion test is performed after curing for 7 days under standard conditions (20°C x 65%). The adhesion test is performed in accordance with the peel adhesion table value method of JASO M338-89. Primer: 435-97 (manufactured by Sunstar Engineering Co., Ltd.) Adhesive: Penguin Cemment #560 (manufactured by Sunstar Giken Co., Ltd.) The evaluation criteria are as follows: TIFF0007855595000003.tif31140

[0094] [Synthesis] The synthesis method is as follows:

[0095] Acrylic component 3 In a reaction vessel equipped with stirring blades, 1000 g of polycarbonate diol with a hydroxyl value of 56 (UH-200, manufactured by Ube Industries, Ltd.) and 659 g of excess isophorone diisocyanate (IPDI) were added and reacted at 70°C for 3 hours with stirring to obtain a mixture of isocyanate-terminated prepolymer and monomer with an NCO content of 12.6%. Furthermore, 573 g of hydroxyethyl acrylate (HEA) was added and reacted at 80°C for 3 hours under a nitrogen atmosphere to obtain a mixture of acrylate-terminated polycarbonate prepolymer and urethane diacrylate. The calculated ratio of prepolymer to urethane diacrylate was 60:40.

[0096] Acrylic component 4 In a reaction vessel equipped with stirring blades, 1000 g of polycarbonate diol with a hydroxyl value of 56 (UH-200, manufactured by Ube Industries, Ltd.) and 455 g of excess isophorone diisocyanate (IPDI) were added and reacted at 70°C for 3 hours with stirring to obtain a mixture of isocyanate-terminated prepolymer and monomer with an NCO content of 8.95%. Further, 359 g of hydroxyethyl acrylate (HEA) was added and the reaction was carried out at 80°C for 3 hours under a nitrogen atmosphere to obtain a mixture of acrylate-terminated polycarbonate prepolymer and urethane diacrylate. Finally, 96 g of isobornyl acrylate was added and the mixture was cooled. The calculated ratio of prepolymer, urethane diacrylate, and monoacrylate was 70:25:5.

[0097] Acrylic component 5 In a reaction vessel equipped with stirring blades, 1000 g of polyester diol with a hydroxyl value of 56 (Ingevity CAPA2200A) and 503 g of excess hexamethylene diisocyanate (HDI) were added and reacted at 70°C for 3 hours with stirring to obtain a mixture of isocyanate-terminated prepolymer and monomer with an NCO content of 13.9%. Further reaction was carried out at 80°C for 3 hours under a nitrogen atmosphere with 579 g of hydroxyethyl acrylate (HEA) added to obtain a mixture of acrylate-terminated polycarbonate prepolymer and urethane diacrylate. The calculated ratio of prepolymer to urethane diacrylate was 60:40.

[0098] Acrylic component 6 In a reaction vessel equipped with stirring blades, 1000 g of polyester diol with a hydroxyl value of 56 (Ingevity CAPA2200A) and 455 g of excess isophorone diisocyanate (IPDI) were added and reacted at 70°C for 3 hours with stirring to obtain a mixture of isocyanate-terminated prepolymer and monomer with an NCO content of 8.95%. Further, 359 g of hydroxyethyl acrylate (HEA) was added and reacted at 80°C for 3 hours under a nitrogen atmosphere to obtain a mixture of acrylate-terminated polycarbonate prepolymer and urethane diacrylate. Finally, 96 g of isobornyl acrylate was added, and the mixture was removed after cooling. The calculated ratio of prepolymer, urethane diacrylate, and monoacrylate was 70:25:5.

[0099] [Examples 1-16, Comparative Examples 1-5] The raw materials shown in Table 1 were mixed in a planetary mixer in the composition (parts by weight) shown in Table 1 to obtain a curable composition. Each raw material shown in the table is a main component and may contain manufacturing by-products such as polymers (e.g., dimers). The above tests were performed using the obtained curable composition. The test results are shown in Table 2. [Table 1] TIFF0007855595000005.tif25169

[0100] The ingredients listed in the table are specifically as follows: TIFF0007855595000006.tif24376 TIFF0007855595000007.tif248105

[0101] [Table 2] [Industrial applicability]

[0102] The present invention can be used, for example, in various manufacturing processes that require masking of components. For instance, the curable composition of the present invention can be suitably used as a masking material in automated manufacturing processes (e.g., automobile manufacturing processes) using robots or the like.

Claims

1. (Formula 1): (CH 2 =C(R 1 )-CO-OR 2 -O-CO-NH-R 3 -NH-CO) ｎ -R 4 [In the formula, R １ Each of them is independently a hydrogen atom or a methyl group, R ２ Each of these is independently an aliphatic group having 1 to 8 carbon atoms. R ３ Each of them is independently an aromatic or aliphatic group having 1 to 30 carbon atoms, R ４ This is an aromatic group or aliphatic group with a number average molecular weight of 500 or more, having a polycarbonate backbone and / or polyester backbone. n is an integer between 2 and 4. A prepolymer (A1) represented by, and (Formula 2): (CH 2 =C(R 5 )-CO-OR 6 -O-CO-NH) ｍ -R 7 [In the formula, R ５ Each of them is independently a hydrogen atom or a methyl group, R ６ Each of these is independently an aliphatic group having 1 to 8 carbon atoms. R ７ Each of these is independently an aromatic group or aliphatic group having 1 to 30 carbon atoms. m is an integer between 2 and 4. Nonpolymer (A2) represented by A curable composition comprising, A curable composition comprising 20% ​​by weight or more of the prepolymer (A1) and 20% by weight or more of the nonpolymer (A2).

2. The curable composition according to claim 1, wherein the number average molecular weight of the prepolymer (A1) is 1,000 or more and 5,000 or less, and the number average molecular weight of the nonpolymer (A2) is 750 or less.

3. The curable composition according to claim 1, wherein the tanδ at 10°C to 30°C after curing is 0.07 or more.

4. The curable composition according to claim 1, further comprising other acrylic monomers (A3).

5. The curable composition according to claim 1, comprising 10% by weight or more of solid particles (B).

6. A curable composition according to claim 1, comprising a phosphorus-containing initiator.

7. A curable masking material comprising the curable composition described in claim 1.

8. A masking step comprising providing a masking member that masks at least a portion of the surface of a substrate using the curable masking material described in claim 7; A curing step including curing the masking member; An exposure step, which includes peeling off the masking member to expose a portion of the surface of the substrate; and A bonding step including bonding other members to the exposed portion of the surface of the substrate; A method for producing a compound, including the compound.

9. moreover, A painting process including applying paint to the substrate. A method for producing the compound according to claim 8, including the method described in claim 8.

10. The method for manufacturing a composite according to claim 8, wherein the masking step includes applying the curable masking material to a thickness of 0.1 mm or more to mask at least a portion of the surface of the substrate.

11. The method for manufacturing a composite according to claim 8, wherein the masking step includes applying the curable masking material in a width of 5 mm or more to mask at least a portion of the surface of the substrate.

12. The method for producing the composite according to claim 8, wherein the base material is a resin.

13. A method for manufacturing the composite according to claim 8, using a robot.

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