Curable composition

Abstract

The object of this invention is to provide a masking material that exhibits excellent peelability even with reduced drying steps, preferably without drying steps. A curable composition comprising: (A1) of (Formula 1) (CH2=C(R) 1 )-CO-O-R 2 -O-CO-NH-R 3 -NH-CO) n -R 4 The prepolymer represented, where each R 1 Independently, each R is a hydrogen atom or a methyl group. 2 Independently, it is an aliphatic group having 1 to 8 carbon atoms, each R 3 Independently, it is an aromatic or aliphatic group having 1 to 30 carbon atoms, and R 4 It is an aromatic or aliphatic group with a number average molecular weight of at least 500 and having a polycarbonate backbone and / or a polyester backbone, n being an integer from 2 to 4; and (A2) is composed of (Formula 2) (CH2=C(R 5 )-CO-O-R 6 -O-CO-NH) m -R 7 The non-polymer represented, where each R 5 Independently, each R is a hydrogen atom or a methyl group. 6 Independently, it is an aliphatic group having 1 to 8 carbon atoms, R 7 Independently, it is an aromatic or aliphatic group having 1 to 30 carbon atoms, where m is an integer from 2 to 4.

Description

Technical Field

[0001] This invention relates to curable compositions, curable masking materials comprising said curable compositions, and methods for producing bonded bodies using said curable compositions. Background Technology

[0002] When coating various products, masking is performed to protect portions of the substrate so that the coating is applied only to predetermined areas. Masking is typically done by applying a film-like material (such as tape), but this method is not easily automated due to its operational characteristics. It is known that a masking material obtained by dispersing or dissolving a resin in a solvent is applied to the substrate instead of a film-like material (Patent Documents 1 and 2).

[0003] Patent documents [Patent Document 1] US6284826B1 [Patent Document 2] US2003 / 0149164A1 Summary of the Invention [Technical Issues] However, traditional solvent-based masking materials exhibit poor shape retention, resulting in limited freedom of shape application and poor processability. This is particularly problematic when automating the coating process using robots or similar devices. Furthermore, traditional solvent-based masking materials are uneconomical because they require drying ovens to improve peel performance. The objective of this invention is to provide a masking material with excellent shape retention, excellent freedom of shape application, rapid film formation, and high cost-effectiveness. A further objective of this invention is to provide a masking material that exhibits excellent physical properties (e.g., tear strength) after curing and solves the tearing problem associated with peeling after curing.

[0004] [Problem Solution] One embodiment of the present invention is as follows: (Project 1) A curable composition comprising: From (Equation 1): (CH2=C(R) 1 )-CO-OR 2 -O-CO-NH-R 3 -NH-CO) n -R 4 The prepolymer represented is (A1). in, Each R 1 It is either a hydrogen atom or a methyl group. Each R 2 Independently, it is an aliphatic group having 1 to 8 carbon atoms. Each R3 Independently, it is an aromatic or aliphatic group having 1 to 30 carbon atoms, and R 4 It is an aromatic or aliphatic group with a number average molecular weight of at least 500 and having a polycarbonate backbone and / or a polyester backbone, and n is an integer from 2 to 4; and From (Equation 2): (CH2=C(R) 5 )-CO-OR 6 -O-CO-NH) m -R 7 The non-polymer is represented by (A2). in, Each R 5 It is either a hydrogen atom or a methyl group. Each R 6 Independently, it is an aliphatic group having 1 to 8 carbon atoms. R 7 Independently, it is an aromatic or aliphatic group having 1 to 30 carbon atoms, and m is an integer from 2 to 4.

[0005] (Project 2) According to the curable composition of Project 1, the number average molecular weight of the prepolymer (A1) is from 1,000 to 5,000, and the number average molecular weight of the nonpolymer (A2) is at most 750.

[0006] (Project 3) The curable composition according to Item 1 comprises at least 15% by weight of the prepolymer (A1) and at least 15% by weight of the nonpolymer (A2).

[0007] (Project 4) According to the curable composition of Project 1, the tan δ of the cured composition at 10°C to 30°C is at least 0.07.

[0008] (Project 5) The curable composition according to Item 1 includes an acrylic monomer (A3) having an acrylic polymerizable group.

[0009] (Project 6) The curable composition according to Item 1 comprises at least 10% by weight of solid particles (B).

[0010] (Project 7) The curable composition according to Project 1 includes a phosphorus-containing initiator.

[0011] (Project 8) A curable masking material comprising the curable composition according to item 1.

[0012] (Project 9) A method for producing an adhesive, comprising: The masking step includes masking at least a portion of the substrate surface with the curable masking material according to item 8 to provide a masking component; The curing step includes curing the masking component; The exposure step includes peeling off the masking member to expose a portion of the substrate surface; and The bonding step includes bonding other components to the exposed portion of the substrate surface.

[0013] (Project 10) The production method described in Project 9 further includes, The painting step includes painting the substrate.

[0014] (Project 11) According to the production method of Project 9, the masking step includes applying the curable masking material with a thickness of at least 0.1 mm to mask at least a portion of the substrate surface.

[0015] (Project 12) According to the production method described in Project 9, the masking step includes applying the curable masking material with a width of at least 5 mm to mask at least a portion of the substrate surface.

[0016] (Project 13) According to the production method described in Project 9, the substrate is a resin.

[0017] (Project 14) The production method described in Project 9 involves the use of robots.

[0018] [The effects of the invention] Because the curable masking material comprising the curable composition according to embodiments of the present invention exhibits excellent shape retention, it can be applied only to the desired portion and offers excellent freedom in the shape of the coating. Furthermore, it forms a film rapidly and is excellent in terms of economy and peel performance. Therefore, due to the excellent processability of the curable composition according to embodiments of the present invention, automation by robots and the like is easily achieved, thereby improving processability. Moreover, the curable composition according to embodiments of the present invention causes less contamination in the substrate and is unlikely to adversely affect subsequent steps. Furthermore, the present invention provides a masking material that exhibits excellent physical properties after curing and can be easily peeled off. Detailed Implementation

[0019] <Cureable Compositions> The curable composition in the embodiments of the present invention includes: From (Equation 1): (CH2=C(R) 1 )-CO-OR 2 -O-CO-NH-R 3 -NH-CO) n -R 4 The prepolymer represented is (A1). in, Each R 1 It is either a hydrogen atom or a methyl group. Each R 2 Independently, it is an aliphatic group having 1 to 8 carbon atoms. Each R 3 Independently, it is an aromatic or aliphatic group having 1 to 30 carbon atoms, and R 4 It is an aromatic or aliphatic group with a number average molecular weight of at least 500 and having a polycarbonate backbone and / or a polyester backbone, and n is an integer from 2 to 4; and From (Equation 2): (CH2=C(R) 5 )-CO-OR 6 -O-CO-NH) m -R 7 The non-polymer is represented by (A2). in, Each R 5 It is either a hydrogen atom or a methyl group. Each R 6 Independently, it is an aliphatic group having 1 to 8 carbon atoms. R 7 Independently, it is an aromatic or aliphatic group having 1 to 30 carbon atoms, and m is an integer from 2 to 4.

[0020] [Prepolymer (A1)] The curable composition in the embodiments of the present invention includes: From (Equation 1): (CH2=C(R) 1 )-CO-OR 2 -O-CO-NH-R 3 -NH-CO) n -R 4 The prepolymer represented is (A1). in, Each R 1 It is either a hydrogen atom or a methyl group. Each R 2 Independently, it is an aliphatic group having 1 to 8 carbon atoms. Each R 3 Independently, it is an aromatic or aliphatic group having 1 to 30 carbon atoms, and R 4 It is an aromatic or aliphatic group with a number average molecular weight of at least 500 and having a polycarbonate backbone and / or a polyester backbone, and n is an integer from 2 to 4.

[0021] R 1 It can be a hydrogen atom or a methyl group on its own.

[0022] R 2 It is an aliphatic group, and can be an aliphatic hydrocarbon group, preferably an alkylene group.

[0023] R 2 The number of carbons in it is 1 to 8, and can be at least 1, at least 2, or at least 3, and can be at most 8, at most 7, or at most 6.

[0024] R 2 Examples include ethylene group, propylene group, trimethylene group, and butylene group.

[0025] R 3 It is an aromatic group or an aliphatic group, and can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

[0026] R 3 The number of carbons in it is 1 to 30, and can be at least 2, at least 4, at least 6, at least 8 or at least 10, and can be at most 28, at most 24, at most 20 or at most 16.

[0027] R 3 The group can be derived from a diisocyanate compound. In other words, the group can be a diisocyanate compound with both -NCO groups removed. The diisocyanate compound can be an aliphatic diisocyanate or an aromatic diisocyanate. From the perspective of post-curing performance, aliphatic diisocyanates are preferred. Alicyclic diisocyanates can be monocyclic or polycyclic (e.g., bicyclic, tricyclic, or bridged alicyclic diisocyanates).

[0028] Specific examples of diisocyanate compounds include: Acyclic aliphatic polyisocyanates, such as trimethylene diisocyanate, 1,2-propylidene diisocyanate, butylidene diisocyanate (tetramethylene diisocyanate, 1,2-butylidene diisocyanate, 2,3-butylidene diisocyanate, 1,2,3-butylidene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, methyl 2,6-diisocyanate hexanoate, lysine diisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, etc. Monocyclic alicyclic polyisocyanates, such as 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), methyl 3-isocyanate-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylene bis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis(cyclohexyl isocyanate) or mixtures thereof) (Hydrogenated MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexene diisocyanate, bis(isocyanate methyl)cyclohexane (1,3- or 1,4-bis(isocyanate methyl)cyclohexane or mixtures thereof) (Hydrogenated XDI), dimer acid diisocyanate, trans-cyclohexane 1,4-diisocyanate, hydroaddition toluene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylene diisocyanate (hydrogenated TMXDI), etc.; Polycyclic (e.g., bridged ring) alicyclic polyisocyanates, such as norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, methyl diisocyanate bicycloheptane, di(methyl diisocyanate) tricyclodecane, etc. Aromatic diisocyanates, such as toluene diisocyanate (2,4- or 2,6-toluene diisocyanate or mixtures thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or mixtures thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylene diisocyanate (1,3- or 1,4-xylene diisocyanate) Ester or mixture thereof (XDI), tetramethylxylene diisocyanate (1,3- or 1,4-tetramethylxylene diisocyanate or mixture thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- or 1,8-naphthalene diisocyanate or mixture thereof) (NDI), nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

[0029] R 4 It is an aromatic or aliphatic group with a molecular weight of at least 500 and having a polycarbonate and / or polyester backbone.

[0030] R 4 It is n-valent. n is an integer from 2 to 4, preferably 2.

[0031] The polycarbonate backbone can be composed of (Equation 21): -[-R 41 -OC(=O)-O-] q - to indicate: in R 41 It is a divalent hydrocarbon group, and q is an integer.

[0032] R 41 It can be aromatic or aliphatic, preferably linear, branched, or cyclic alkylene groups, more preferably linear alkylene groups. R 41 The number of carbons in it can be from 1 to 15, for example from 2 to 10, preferably from 3 to 7. R 41 Specific examples include trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, and heptamethylene. In the heteropolycarbonate backbone, each R... 41 They can be the same or different.

[0033] q can be at least 3, for example, at least 5, preferably at least 10.

[0034] The polycarbonate backbone can be composed of (Equation 22): -[C(=O)-R 42 -O-]r -express, in R 42 It is a divalent hydrocarbon group, and r is an integer.

[0035] R 42 It can be a straight-chain, branched, or cyclic alkylene group, preferably a straight-chain alkylene group. R 42 The number of carbons in it can be from 1 to 15, for example from 2 to 10, preferably from 2 to 7. 42 Specific examples include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, and heptamethylene. In the polycarbonate backbone, each R... 42 They can be the same or different.

[0036] r can be at least 3, for example, at least 5, preferably at least 10.

[0037] Alternatively, the polyester main chain can be derived from formula (23): -[-C(=O)-R 43 -C(=O)OR 44 -O-] s -express in R 43 and R 44 Each is independently a divalent hydrocarbon group, and s is an integer.

[0038] For example, R 43 It can be a divalent aromatic group having 6 to 10 carbons (e.g., phenylene (p-phenylene)) or an alkylene group having 1 to 15 carbons (e.g., an alkylene group having 2 to 10 carbons), preferably an alkylene group having 2 to 7 carbons. 44 It can be an alkylene group having 1 to 15 carbons, for example, an alkylene group having 2 to 10 carbons, preferably an alkylene group having 2 to 8 carbons.

[0039] s can be at least 3, for example, at least 5, preferably at least 10.

[0040] R 4 The number average molecular weight is at least 500, and can be at least 750, at least 1000, at least 1250, at least 1500, or at least 2500, preferably at least 750. 4 The number average molecular weight can be up to 10,000, up to 7,500, up to 5,000, up to 4,000, up to 3,000, or up to 2,500, preferably up to 4,000. 4 The number-average molecular weight is preferably at most 4000. The number-average molecular weight is a value expressed in polystyrene, measured by gel permeation chromatography (GPC).

[0041] The number average molecular weight of the prepolymer (A1) can be at least 750, at least 1000, at least 1500, at least 2000, at least 2500, or at least 3000, preferably at least 1000. The number average molecular weight of the prepolymer (A1) can be at most 10000, at most 7500, at most 5000, at most 4000, at most 3000, or at most 2500, preferably at most 5000. Molecular weights within the above ranges are advantageous in terms of the physical properties and viscosity after curing. The number average molecular weight is a value expressed in polystyrene, measured by gel permeation chromatography (GPC).

[0042] The viscosity of the prepolymer (A1) at 40°C can be at least 1 Pa. s, for example, at least 10 Pa s, preferably at least 20 Pa The viscosity of the prepolymer (A1) at 40°C can be up to 200 Pa. s, for example, up to 150 Pa s, preferably up to 100 Pa When the viscosity of the prepolymer (A1) at 40°C is within the above range, coating and peeling properties are more suitable. Viscosity measurements were performed at 0.42 rpm and 40°C using a rheometer (DHR-3 manufactured by TA Instruments) equipped with a 20 mm plate.

[0043] [Non-polymer (A2)] The curable composition in the embodiments of the present invention includes: From (Equation 2): (CH2=C(R) 5 )-CO-OR 6 -O-CO-NH) m -R 7 The non-polymer is represented by (A2). in Each R 5 It is either a hydrogen atom or a methyl group. Each R 6 Independently, it is an aliphatic group having 1 to 8 carbon atoms, and R 7 Independently, it is an aromatic or aliphatic group having 1 to 30 carbon atoms. m is an integer from 2 to 4.

[0044] R 5 It can be a hydrogen atom or a methyl group on its own.

[0045] R 6It is an aliphatic group, which can be an aliphatic hydrocarbon group, and preferably an alkylene group.

[0046] R 6 The number of carbons in it is 1 to 8, and can be at least 1, at least 2, or at least 3, and can be at most 8, at most 7, or at most 6.

[0047] R 6 Specific examples include ethylene, propylene, trimethylene, and butylene.

[0048] R 7 It is an aromatic group or an aliphatic group, and can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

[0049] R 7 The number of carbons in it is 1 to 30, and can be at least 2, at least 4, at least 6, at least 8 or at least 10, and can be at most 28, at most 24, at most 20 or at most 16.

[0050] R 7 The group can be derived from a polyisocyanate compound. In other words, the group can be a polyisocyanate compound from which m -NCO groups have been removed. m can be an integer from 2 to 4, preferably 2. The polyisocyanate compound can be an aliphatic polyisocyanate or an aromatic polyisocyanate. From the perspective of post-curing properties, aliphatic polyisocyanates are preferred. Alicyclic polyisocyanates can be monocyclic alicyclic polyisocyanates or polycyclic alicyclic polyisocyanates (e.g., bicyclic alicyclic polyisocyanates, tricyclic alicyclic polyisocyanates, bridged alicyclic polyisocyanates).

[0051] In addition to the above R 3 In addition to diisocyanate compounds mentioned in the explanation, examples of polyisocyanate compounds include triphenylmethane triisocyanate, tri(phenylisocyanate)thiophosphate, polymethylene polyphenylene polyisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, etc.

[0052] The number average molecular weight of the non-polymer (A2) can be at least 100, at least 200, at least 300, at least 400, or at least 500. The number average molecular weight of the non-prepolymer (A2) can be at most 750, at most 700, at most 650, or at most 600, preferably at most 500. When the molecular weight is within the above range, it is advantageous in terms of the physical properties and viscosity after curing. The number average molecular weight can be a value expressed in polystyrene, measured by gel permeation chromatography (GPC).

[0053] [Other acrylic monomers (A3)] The curable composition may include other acrylic monomers (A3). Including other acrylic monomers (A3) is advantageous in terms of the physical properties after curing.

[0054] The number of acrylic polymer groups (acrylate groups, acrylamide groups, etc.) in other acrylic monomers (A3) can be at least 1, at least 2, at least 3, at least 4 or at least 5, or at most 6, at most 5, at most 4, at most 3, at most 2 or at most 1, for example 1, 2 or 3.

[0055] Other acrylic monomers (A3) may or may not have urethane and / or urea groups, preferably without these groups.

[0056] The number average molecular weight of other acrylic monomers (A3) may be at least 100, at least 200, at least 300, at least 400, or at least 500. The number average molecular weight of other acrylic monomers (A3) may be at most 1000, at most 750, at most 700, at most 650, or at most 600, preferably at most 500. The number average molecular weight may be a value expressed in polystyrene, measured by gel permeation chromatography (GPC).

[0057] Examples of other monomers (A3) include: alkyl (meth)acrylates (wherein the alkyl group may have at least 1, at least 3, at least 5, at least 7, at least 10, at least 12 carbon atoms, and may have at most 30, at most 27, at most 24, at most 20, at most 16 carbon atoms), such as methyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, isodecanyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, etc.; hydroxyl-containing (meth)acrylates, such as methyl hydroxy (meth)acrylate, ethyl hydroxy (meth)acrylate, etc.; (poly)alkylene glycol-containing (meth)acrylates, such as diethylene glycol monoethyl ether acrylate, dipropylene glycol monoethyl ether acrylate, polyethylene glycol monoethyl ether acrylate, polypropylene glycol monoethyl ether acrylate, etc.; (poly)alkylene glycol-containing (meth)acrylates... Acrylates; (meth)acrylates containing ethylene oxide groups, such as glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, etc.; monomers containing aromatic groups, such as styrene, 2-hydroxy-3-phenoxypropyl acrylate, etc.; monomers containing isocyanate groups, such as 2-ethyl (meth)acrylate isocyanate, etc.; monomers containing Si groups, such as trimethylsilyl acrylate, trialkoxysilyl acrylate, etc.; monomers containing acid functional groups, such as (meth)acrylic acid, 3-(acryloyloxy)propane-1-sulfonic acid and its salts, etc.; monomers containing cyclic groups, such as adamantyl acrylate and cyclohexyl acrylate, etc.; fluorinated monomers, such as 1H,1H,2H,2H-tridecylfluoro-n-octyl (meth)acrylate, etc.; amide monomers, such as acrylamide, N-alkylacrylamide, etc.

[0058] [Solid particles (B)] The curable composition in this invention includes solid particles (B). Solid particles (B) are particles that are solid at room temperature and are not particularly limited, as long as the curable composition desired by this invention can be obtained. Examples of solid particles (B) may include carbonates, oxides, or hydroxides of alkali metals or alkaline earth metals, such as calcium carbonate, calcium hydroxide, calcium oxide, magnesium hydroxide, etc.; silica, such as fumed silica and precipitated silica; carbon, such as carbon black, graphite, etc.; mineral fillers, such as alumina, talc, mica, and clay, etc.; glass beads; balls, such as shirasu balls, glass balls, silicon balls, plastic balls, etc.; inorganic fibers, such as glass fibers, metal fibers, etc.; 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, etc.; and needle-like crystalline fillers, such as chrysotile and wollastonite, etc. Solid particles (B) may be surface-treated (e.g., fatty acid-treated) particles.

[0059] The median particle size of the solid particles (B) may be at least 0.003 μm, for example, at least 0.5 μm. Preferably, the median particle size of the solid particles (B) is at most 20 μm, more preferably at most 10 μm, and even more preferably at most 5 μm. The median particle size is the diameter of the 50% weight-cumulative particle size distribution as measured by a laser diffraction / scattering type particle size distribution measuring device.

[0060] The solid particles (B) can be carbonates, oxides or hydroxides of alkali metals or alkaline earth metals, such as silica or alumina. From the perspective of improving coating performance and peeling performance, carbonates, especially calcium carbonate, are preferred.

[0061] [Polymerization initiator (C)] The curable compositions of embodiments of the present invention may include polymerization initiators. 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 targeted by the present invention is obtained. When the curable composition is used as a photomask, a photoinitiator is typically used. Examples of polymerization initiators include benzoin initiators, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-allyl benzoin, 2-chlorobenzoin, etc.; acetophenone initiators, such as 1-hydroxy-cyclohexyl-phenyl ketone, diethoxyacetophenone, hydroxyacetophenone, 2-hydroxy-2-methyl-1-phenylprop-1-one, α-aminoacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.; and benzophenone initiators, such as benzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4-chlorodiphenyl ketone, etc. Methyl ketones, etc.; thioxanthone initiators, such as 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc.; azo initiators, such as azobisisobutyronitrile; peroxide initiators, such as benzoyl peroxide; quinone initiators, such as anthraquinone, 2-chloroanthraquinone, phenanthrene, etc.; phosphorus-containing initiators, such as: phosphine oxide initiators, such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide; and phosphonate initiators, such as ethylphenyl(2,4,6-trimethylbenzoyl)phosphonate, etc.

[0062] Polymerization initiators may include phosphorus-containing initiators, particularly phosphorus-containing aromatic initiators (e.g., aromatic phosphonates). When the curable composition is applied thickly (e.g., at least 0.2 mm thick, particularly at least 0.5 mm thick), the light transmittance decreases exponentially, potentially leading to difficulties in curing the entire curable composition. In the curable compositions of the embodiments of the present invention, by combining the prepolymer (A), solid particles (B), and phosphorus-containing initiator, both deep-layer curing properties and rapid curing properties can be achieved simultaneously. This is particularly effective when the curable composition is thick-painted. Peel performance is further improved by performing subsequent steps, such as baking the coating, after sufficient curing.

[0063] [Other components] The curable composition of this invention may include other components. There are no particular limitations on the other components, as long as the curable composition of this invention is obtained.

[0064] The curable composition may include monomers or polymers other than prepolymers (A1), nonpolymers (A2), and other acrylic monomers (A3) as one of the other components.

[0065] Curable compositions may include antioxidants as one of the other components. Examples of antioxidants include phenolic antioxidants (such as hindered phenols), aromatic amine antioxidants, sulfur antioxidants, phosphorus antioxidants, etc. By including antioxidants, the peeling properties of the masking material are improved even after high-temperature heating.

[0066] The curable composition includes other components in appropriate amounts, such as colorants (e.g., bengara, titanium dioxide, other colored pigments, dyes, etc.), solvents (e.g., water, polar organic solvents, non-polar organic solvents, etc.), silane compounds (e.g., silane compounds having functional groups such as amino, mercapto, epoxy, (meth)acrylate, vinyl, etc.), epoxy compounds that may have polyoxyalkylene groups, plasticizers, UV absorbers / light stabilizers (e.g., benzotriazole, hindered amines, etc.), thixotropic agents (e.g., colloidal silica, organobentonite, fatty acid amides, hydrogenated castor oil, etc.), viscosity modifiers, sensitizers, polymerization inhibitors, etc.

[0067] [Composition of the curable composition] The amount of prepolymer (A1) relative to the curable composition may be at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 30% by weight, or at least 40% by weight, and preferably at least 10% by weight. The amount of prepolymer (A) relative to the curable composition may be at most 90% by weight, at most 75% by weight, at most 60% by weight, at most 45% by weight, or at most 30% by weight, preferably at most 60% by weight.

[0068] The amount of non-polymer (A2) relative to the curable composition may be at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 30% by weight, or at least 40% by weight, and preferably at least 10% by weight. The amount of non-polymer (A2) relative to the curable composition may be at most 90% by weight, at most 75% by weight, at most 60% by weight, at most 45% by weight, or at most 30% by weight, preferably at most 60% by weight.

[0069] The amount of monomer (A3) relative to the curable composition can be up to 30% by weight, up to 25% by weight, up to 20% by weight, up to 15% by weight, or up to 10% by weight. In the curable composition, when the amount of monomer (A3) is within the above range, unreacted substances are unlikely to remain in the cured product, and the substrate is unlikely to be contaminated after the masking material is removed.

[0070] The amount of solid particles (B) relative to the curable composition may be 0% by weight, at least 1% by weight, at least 5% by weight, at least 10% by weight, at least 15% by weight, or at least 25% by weight of the curable composition. The amount of solid particles (B) relative to the curable composition may be up to 65% by weight, up to 50% by weight, up to 35% by weight, or up to 15% by weight.

[0071] The amount of polymerization initiator (C) relative to the curable composition may be at least 0.01% by weight, at least 0.05% by weight, at least 0.1% by weight, or at least 0.5% by weight. The amount of polymerization initiator (C) relative to the curable composition may be at most 5% by weight, at most 4% by weight, at most 3% by weight, at most 2.5% by weight, or at most 2% by weight.

[0072] The amount of other components relative to the curable composition may be at least 0.1% by weight, for example at least 1% by weight. The amount of other components relative to the curable composition may be at most 25% by weight, for example at most 10% by weight. Weight percentages may be based on the portion excluding solvent.

[0073] In the curable composition, the content of the antioxidant may be at least 0.01% by weight, at least 0.1% by weight, at least 0.3% by weight, at least 0.5% by weight, or at least 1% by weight. The content of the antioxidant may be at most 7.5% by weight, at most 5% by weight, at most 3.5% by weight, at most 1.5% by weight, or at most 1% by weight.

[0074] [Viscosity of the curable composition] The curable composition has a viscosity of at least 10 Pa at 40°C. s, at least 20 Pa s or at least 30Pa s, for example, at least 50 Pa s, and preferably at least 100 Pa The viscosity of the curable composition at 40°C can be up to 300 Pa. s, at most 250Pa s, or at most 200 Pa s, and preferably up to 180 Pa The TI (thixotropic index) value of the curable composition at 40°C can be at least 0.3, at least 0.6, or at least 0.8, for example, at least 1. The TI value of the curable composition at 40°C can be at most 3, at most 2.5, or at most 2, preferably at most 1.8. The curable composition of embodiments of the present invention can be in fluid form exhibiting the above-described viscosity or TI value. Coating performance and peeling performance are more preferred when the viscosity or TI value of the curable composition is within the above range. The TI value is calculated as the ratio of the viscosity at 0.42 rpm to the viscosity at 4.2 rpm.

[0075] [The viscoelasticity of the composition after curing] The cured curable composition (i.e., the cured material) may have a tan δ of at least 0.07, at least 0.08, at least 0.09, at least 0.10, at least 0.11, at least 0.12, at least 0.13, or at least 0.14, preferably at least 0.08, and more preferably at least 0.10, in the range of 10°C to 30°C. The cured curable composition (i.e., the cured material) may also have a tan δ of at most 0.50, at most 0.40, at most 0.30, at most 0.25, at most 0.20, or at most 0.18, preferably at most 0.25, and more preferably at most 0.20, in the range of 10°C to 30°C. By using the cured composition of this application, a cured material having the above-mentioned specific tan δ was obtained, and good physical properties of the cured material were developed. Tan δ was measured, for example, using a Perkin Elmer DMA 8000 at a rate of 1 Hz and 1°C / second.

[0076] <Cureable masking materials> The curable masking material of this invention is not particularly limited, as long as it comprises a curable composition and can mask a portion of the substrate. By using the masking material to mask the substrate surface during the coating process, it is possible to prevent the masked substrate surface from being coated.

[0077] <Methods for producing binders> The present invention also provides a novel method for producing an adhesive, the method comprising a masking step, a curing step, an exposure step, and an bonding step. Furthermore, the method may further include a painting step after the masking step (preferably after the curing step) and before the exposure step.

[0078] In the method for producing an adhesive according to an embodiment of the present invention, although a drying step may be performed if necessary, the film can be formed by reducing the number of drying steps or by eliminating the drying step altogether. From a processability perspective, it is preferable to reduce the number of drying steps, and more preferably to perform the process without a drying step. Therefore, a drying oven may not be necessary.

[0079] [Concealment Steps] The masking step includes providing a masking member that at least masks at least a portion of the substrate surface. The masking member is obtained by applying the aforementioned curable masking material to the substrate surface.

[0080] Curable masking materials can be applied in the form of wide, thick film beads. The nozzle shape can be a round bead nozzle, a wide and thin bead nozzle, a flat nozzle, or a fan nozzle, and can be selected according to the purpose. If a certain degree of wide masking is required, a wide and thin bead nozzle or a fan nozzle is preferred. Wider coverage can also be achieved by using shot nozzles, slit nozzles, or by using vortex coating or spraying methods with controlled discharge speed. For example, the curable composition can be supplied from a container to a substrate via a material supply hose using a supply pump. Automated coating of the target area can be performed using a coating dispenser fixed to a robot. A metering pump can be placed between the feed pump and the dispenser to stabilize the supply of masking material. A feed pump or dispenser with a metering device can be used.

[0081] The coating thickness of the curable masking material can be at least 0.1 mm, at least 0.2 mm, at least 0.5 mm, at least 1 mm, at least 1.5 mm, at least 3 mm, or at least 5 mm. The coating thickness of the curable masking material can be at most 30 mm, at most 15 mm, or at most 10 mm. When the coating thickness is within the above ranges, the paint film and the cured masking material are difficult to integrate after painting, thus making it easier to peel off only the masking material. Therefore, it becomes easier, for example, to automatically peel off the masking material using grippers, peelers, etc., equipped in a robot.

[0082] The coating width of the curable masking material can be at least 3 mm, at least 5 mm, or at least 10 mm. The coating width of the curable masking material can be at most 75 mm, at most 50 mm, or at most 30 mm.

[0083] The coating thickness and coating width of the aforementioned curable masking material can refer to the thickness and width after curing or coating.

[0084] The substrate material is not limited and can be metal (e.g., steel), resin (e.g., acrylic resin, olefin resin (usually polypropylene), polyamide resin, polyimide resin, polycarbonate resin, etc.), glass, ceramic, etc.

[0085] [Curing Step] The curing step includes curing the masking member. The masking member in this embodiment of the invention is excellent in terms of rapid curing. Furthermore, in this embodiment of the invention, the cured material obtained by curing the masking member has moderate flexibility and toughness, and is not easily broken upon peeling.

[0086] In this embodiment of the invention, the curing of the masking component is achieved by activating a polymerization initiator and advancing polymerization. The curing of the masking component can be performed by light irradiation or by heating the curable composition. From a processability perspective, curing by light irradiation (e.g., UV irradiation, visible light irradiation, etc.) is preferred.

[0087] When the curable masking material is photocurable, curing can be achieved by passing the material through a conveyor with an internal light source (e.g., a UV light source or a visible light source), or by irradiating the coated area with a robot holding a handheld light source. Furthermore, the dispenser and light source used for coating can be equipped with the same robot to perform coating and curing simultaneously. Conventional light sources such as incandescent lamps, fluorescent lamps, halogen lamps, mercury lamps, and xenon lamps can be used as the light source, or LED light sources can be used.

[0088] The wavelength used for photopolymerization can be from 100 to 900 nm, for example, 200 to 500 nm, preferably 300 to 450 nm. The irradiance can be at least 100 mW / cm². 2 For example, at least 200mW / cm 2 And it can be up to 100W / cm 2 For example, at most 50W / cm 2 Because the curable composition in the embodiments of the present invention has improved rapid curing properties, it can improve processability. From the perspective of processability, the light irradiation time can be at most 1 minute, preferably at most 30 seconds, more preferably at most 10 seconds, even more preferably at most 5 seconds, even more preferably at most 3 seconds, particularly preferably at most 1 second, and can be at least 0.1 seconds, for example, at least 0.3 seconds.

[0089] When the curable masking material is thermosetting, it can be cured using an oven, hot air equipment, near-infrared lamps, or a robot equipped with these. The heating temperature can be from 80°C to 150°C, preferably from 60°C to 130°C, and more preferably from 70°C to 120°C. From a processability point of view, the heating time for curing can be up to 1 minute, preferably up to 30 seconds, and more preferably up to 10 seconds.

[0090] Traditionally, when masking materials are applied as thick films, even curing processes such as light irradiation or heating cannot completely cure the material, resulting in residues adhering to the substrate. The curable masking material in this invention can cure rapidly and possesses sufficient mechanical strength after curing and heating. Therefore, even when applied as a wide and thick film, the entire masking material can be peeled off without breakage. Furthermore, since the curable masking material of this invention does not contaminate the substrate after peeling, adhesion is not adversely affected when adhesives are applied to exposed surfaces.

[0091] [Painting Steps] The painting step involves coating the substrate surface after the masking step (preferably after the curing step) and before the exposure step. Painting can be performed by various methods, such as brush painting, spray painting, dip painting, powder coating, electrostatic painting, UV curing, and baking. For painting and drying, the substrate can be heated to at least 80°C, for example, at least 100°C, at least 120°C, at least 150°C, or at least 180°C. The heating time can range from 30 seconds to 600 minutes, for example, from 5 minutes to 150 minutes.

[0092] [Exposure Steps] The exposure step includes peeling off the masking member after curing to expose at least a portion of the substrate surface.

[0093] [Bonding Steps] The bonding step includes bonding other components to exposed portions of the substrate surface. An adhesive may be applied to the substrate surface to bond the other components. The substrate surface may be pretreated, for example, with a primer, before applying the adhesive. By using the curable masking material in this embodiment of the invention, excellent adhesion between the substrate surface and other components is achieved because no adhesion-inhibiting components remain on the substrate surface after the masking components are peeled off from the substrate. Other components can be bonded to the substrate surface without pretreatment (e.g., primer treatment).

[0094] <Example> The invention will now be described in more detail by way of examples and comparative examples, but the invention is not limited to these examples. Furthermore, unless otherwise stated, parts and percentages are based on parts by weight.

[0095] The meanings of the abbreviations are as follows.

[0096] HEA: Hydroxyethyl acrylate HDI: Hexamethylene diisocyanate IPDI: Isophorone diisocyanate UH200: Eternacoll UH-200 (Polycarbonate Diol, M) n =2000, manufactured by Ube Industries, Ltd. 2200A: CAPA2200A (Polyester Diol, M) n =2000, manufactured by Ingevity).

[0097] Adding a hyphen (-) above (such as HEA-) indicates a derived structure derived from it.

[0098] The testing method is as follows.

[0099] [Photocuring] Photocuring is performed under the following conditions.

[0100] Wavelength: 395nm UV.

[0101] Light source: LED, 14W / cm² 2 , 1 inch apart.

[0102] Light exposure time: 3 seconds.

[0103] [Painting] Paint is applied by baking under the following conditions.

[0104] Coating: Acrylic coating.

[0105] Conditions: 100℃ or 140℃ for 40 minutes.

[0106] [Tan δ] tan δ was recorded at a rate of 1 Hz and 1 °C / sec over a range of at least -70 °C to 120 °C using a Perkin Elmer DMA 8000.

[0107] [Tensile Strength] Prepare cured sheets of approximately 0.1 mm to 1 mm thickness according to JIS K 6251 or ASTM D412. Then, stamp the sheets to prepare dumbbell-shaped sheets (No. 2) and measure the tensile strength using a testing machine at a speed of 300 mm / min.

[0108] [Elongation] When measuring tensile strength, the maximum elongation is measured according to JIS K6251 or ASTM D412.

[0109] [Tear strength] A sheet of cured material approximately 0.35 mm thick was prepared according to ASTM D 624. The sheet was then stamped to form a C-shaped sheet according to a die, and the tear strength was measured on an electromechanical instrument at a speed of 500 mm / min.

[0110] [Evaluation of peel performance (without coating)] The curable composition was applied to a substrate (polypropylene resin) at a certain thickness and UV-cured under the conditions described above. The cured material was then peeled off the substrate by hand to evaluate the peel performance. Furthermore, the ease with which the material would break during hand peeling was also evaluated. The evaluation criteria are as follows:

[0111] [Evaluation of peel performance (after painting process)] The curable composition was applied to a substrate (PP) at a certain thickness and UV-cured under the conditions described above. After the composition cured, a topcoat was applied to both the substrate and the composition, followed by a clear varnish. The cured material was then peeled off from the substrate and evaluated as follows:

[0112] [Adhesion after removing masking components] Adhesion testing was conducted after applying the masking material, curing the coating, and removing the masking components. The primer was applied to the substrate surface. After 5 minutes, the adhesive was applied. Adhesion testing was performed after curing for 7 days under standard conditions (20°C × 65%). Adhesion testing was conducted according to the peel adhesion evaluation method in JASO M 338-89.

[0113] Primer: 435-97 (Sunstar Engineering, Inc.) Adhesive: Penguin Cemment #560 (SunStar Engineering, Inc.) The evaluation criteria are as follows:

[0114] 〔synthesis〕 The synthesis method is as follows.

[0115] Acrylic component 3 1000 g of polycarbonate diol (UH-200, manufactured by Ube Industries, Ltd.) with a hydroxyl value of 56 and 659 g of excess isophorone diisocyanate (IPDI) were added to a reactor equipped with a stirring blade, and the mixture was stirred at 70 °C for 3 hours to obtain a mixture of isocyanate-terminated prepolymer (with 12.6% NCO) and monomers. Additionally, 573 g of hydroxyethyl acrylate (HEA) was added, and the mixture was reacted at 80 °C for 3 hours under a nitrogen atmosphere to obtain a mixture of acrylate-double-terminated polycarbonate prepolymer and urethane diacrylate. The calculated ratio of prepolymer to urethane diacrylate was 60:40.

[0116] Acrylic component 4 1000 g of polycarbonate diol (UH-200, manufactured by Ube Industries, Ltd.) with a hydroxyl value of 56 and 455 g of excess isophorone diisocyanate (IPDI) were added to a reactor equipped with a stirring blade, and the mixture was stirred at 70 °C for 3 hours to obtain a mixture of isocyanate-terminated prepolymer (with 8.95% NCO) and monomers. Additionally, 359 g of hydroxyethyl acrylate (HEA) was added, and the mixture was reacted at 80 °C for 3 hours under a nitrogen atmosphere to obtain a mixture of acrylate-dual-terminated polycarbonate prepolymer and urethane diacrylate. Furthermore, 96 g of isobornyl acrylate was added, followed by cooling. The calculated ratio of prepolymer, urethane diacrylate, and monoacrylate was 70:25:5.

[0117] Acrylic component 5 1000 g of polyester glycol (CAPA2200A, manufactured by Ingevity) with a hydroxyl value of 56 and 503 g of excess hexamethylene diisocyanate (HDI) were added to a reactor equipped with a stirring blade. The mixture was stirred at 70 °C for 3 hours to obtain a mixture of isocyanate-terminated prepolymer (with 13.9% NCO) and monomers. Additionally, 579 g of hydroxyethyl acrylate (HEA) was added, and the mixture was reacted at 80 °C for 3 hours under a nitrogen atmosphere to obtain a mixture of acrylate-double-terminated polycarbonate prepolymer and urethane diacrylate. The calculated ratio of prepolymer to urethane diacrylate was 60:40.

[0118] Acrylic component 6 1000 g of polyester glycol (CAPA2200A, manufactured by Ingevity) with a hydroxyl value of 56 and 455 g of excess isophorone diisocyanate (IPDI) were added to a reactor equipped with a stirring blade. The mixture was stirred at 70 °C for 3 hours to obtain a mixture of isocyanate-terminated prepolymer (with 8.95% NCO) and monomers. Additionally, 359 g of hydroxyethyl acrylate (HEA) was added, and the mixture was reacted at 80 °C for 3 hours under a nitrogen atmosphere to obtain a mixture of acrylate-double-terminated polycarbonate prepolymer and urethane diacrylate. Furthermore, 96 g of isobornyl acrylate was added, followed by cooling. The calculated ratio of prepolymer, urethane diacrylate, and monoacrylate was 70:25:5.

[0119] (Examples 1 to 16, Comparative Examples 1 to 5) The raw materials shown in Table 1 were mixed using a planetary mixer according to the formulations (parts by weight) shown in Table 1 to obtain a curable composition. Each raw material in the table is its main component and may contain manufacturing byproducts such as polymers (e.g., dimers). The obtained curable compositions were subjected to the tests described above. The test results are shown in Table 2.

[0120] Table 1

[0121] The value is the number of weight parts. Specifically, the raw materials shown in Table 1 are as follows:

[0122] [Table 2]

[0123] Industrial applicability This invention can be used in various manufacturing processes that require masking of components. For example, the curable compositions of this invention can be suitably used as masking materials in automated manufacturing processes such as those involving robots (e.g., automobile manufacturing processes).

Claims

1. A curable composition comprising: (A1) From (Equation 1): (CH2=C(R) 1 )-CO-OR 2 -O-CO-NH-R 3 -NH-CO) n -R 4 The prepolymer referred to is in, Each R 1 It is either a hydrogen atom or a methyl group, Each R 2 Independently, it is an alkylene group having 1 to 8 carbon atoms. Each R 3 Independently, it is an aliphatic group having 1 to 30 carbon atoms, and R 4 It is an aliphatic group with a number average molecular weight of at least 500 and having a polycarbonate backbone and / or a polyester backbone, and n is an integer from 2 to 4; and (A2) From (Equation 2): (CH2=C(R) 5 )-CO-OR 6 -O-CO-NH) m -R 7 The non-polymer represented in, Each R 5 It is either a hydrogen atom or a methyl group, Each R 6 Independently, it is an alkylene group having 1 to 8 carbon atoms. R 7 Independently, it is an aliphatic group having 1 to 30 carbon atoms, and m is an integer from 2 to 4; The curable composition comprises at least 10% by weight of solid particles (B). The curable composition comprises at least 15% by weight of the prepolymer (A1) and at least 15% by weight of the nonpolymer (A2).

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

3. The curable composition according to claim 1, wherein the curable composition comprises at least 20% by weight of the prepolymer (A1) and at least 20% by weight of the nonpolymer (A2).

4. The curable composition according to claim 1, wherein, After curing, the tan δ at 10°C to 30°C is at least 0.07, wherein the tan δ is measured at a frequency of 1 Hz and the temperature is increased at a rate of 1°C / second within the temperature range.

5. The curable composition according to claim 1, wherein the curable composition comprises other acrylic monomers (A3).

6. The curable composition according to claim 1, wherein the curable composition comprises at least 15% by weight of solid particles (B).

7. The curable composition according to claim 1, wherein the curable composition comprises a phosphorus-containing initiator.

8. A curable masking material comprising the curable composition according to claim 1.

9. A method for producing an adhesive, comprising: The masking step includes masking at least a portion of the substrate surface with the curable masking material according to claim 8 to provide a masking member; The curing step includes curing the masking component; The exposure step includes peeling off the masking member to expose a portion of the substrate surface; as well as The bonding step includes bonding other components to the exposed portion of the substrate surface.

10. The production method according to claim 9, further comprising: The coating step includes coating the substrate.

11. The production method according to claim 9, wherein, The masking step includes applying the curable masking material with a thickness of at least 0.1 mm to mask at least a portion of the substrate surface.

12. The production method according to claim 9, wherein, The masking step includes applying the curable masking material with a width of at least 5 mm to mask at least a portion of the substrate surface.

13. The production method according to claim 9, wherein, The substrate is resin.

14. The production method according to claim 9, wherein, The masking step, the curing step, or the exposure step is performed using a robot equipped with a coating dispenser, clamp, peeler, or light source.

Images