Solvent for hardened acrylic resin, polycarbonate resin, and acrylonitrile-butadiene-styrene resin, as well as coating agents and adhesives using the same

Abstract

To provide a resin dissolution agent which is excellent in safety and has high solvency power for a cured product of an acrylic resin, a polycarbonate resin and an acrylonitrile-butadiene-styrene resin (ABS resin).SOLUTION: There are provided a dissolution agent for a cured product of a resin (excluding dissolution agents containing hydrofluorocarbon) which contains (A) one or more selected from the group consisting of (E)-1-chloro-2,3,3-trifluoropropene and (Z)-1-chloro-2,3,3-trifluoropropene, and a further component, wherein the resin is one or more selected from an acrylic resin, a polycarbonate resin and an acrylonitrile-butadiene-styrene resin, (B) the further component is one or more selected from the group consisting of (B-1) halogen-based hydrocarbon (excluding (B-2)), (B-2) hydrofluoroolefin (excluding (A)), (B-4) hydrofluoroether, (B-5) hydrocarbon (excluding (B-1)), (B-6) ether (excluding (B-4)), (B-7) alcohol and (B-8) ester, and the temperature of the dissolution agent when the cured product of the resin is dissolved is 5°C to 40°C; and an adhesive and a coating agent using the dissolution agent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a solvent for cured products of acrylic resin, polycarbonate resin, and acrylonitrile-butadiene-styrene resin, as well as a coating agent and adhesive using the same. [Background technology]

[0002] Dichloromethane and trichloroethylene have a high dissolving power for cured resins, and therefore are used as solvents (resin dissolving agents) for dissolving cured resins. Dichloromethane is also sold as an adhesive for commercial acrylic sheets. However, dichloromethane and trichloroethylene are carcinogenic, and therefore fall under the specific chemical substance hazard prevention regulations (specific chemical substance regulations) of the Industrial Safety and Health Act. For this reason, alternative solvents with fewer safety concerns are being developed. As such a solvent, Patent Document 1 proposes a solvent composition for dissolving plastics that contains 1-bromopropane (normal propyl bromide). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2003-306700 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, the 1-bromopropane described in Patent Document 1 alone does not have sufficient dissolving power for cured acrylic resins, polycarbonate resins, and / or acrylonitrile-butadiene-styrene resins. In addition, the solvents proposed as dissolving agents for cured acrylic resins have safety concerns and problems with dissolving power.

[0005] The present invention aims to provide a resin dissolving agent which is excellent in safety and has high dissolving power for cured acrylic resin, polycarbonate resin, and acrylonitrile-butadiene-styrene resin. [Means for solving the problem]

[0006] The present invention has the following configuration. [1] (A) A dissolving agent for cured resin products, comprising one or more resins selected from the group consisting of (E)-1-chloro-2,3,3-trifluoropropene and (Z)-1-chloro-2,3,3-trifluoropropene, wherein the resin is one or more resins selected from acrylic resin, polycarbonate resin, and acrylonitrile-butadiene-styrene resin. [2] The dissolving agent of [1] further comprising one or more (B) further components selected from the group consisting of (B-1) halogenated hydrocarbons (excluding (B-2) and (B-3)), (B-2) hydrofluoroolefins, (B-3) hydrofluorocarbons, (B-4) hydrofluoroethers, (B-5) hydrocarbons (excluding (B-1)), (B-6) ethers (excluding (B-4)), (B-7) alcohols, and (B-8) esters. [3] The dissolving agent according to [2], wherein the component (B) is one or more selected from the group consisting of the components (B-1) and (B-4), the component (B-1) is one or more selected from the group consisting of (b-1) hydromonobromocarbons and hydromonochlorocarbons, and the content of the component (B) is more than 0 part by mass and not more than 80 parts by mass per 100 parts by mass of the combined total of the components (A) and (B). [4] The dissolving agent according to [2], wherein the component (B) is one or more selected from the group consisting of the components (B-2) and (B-6), and the content of the component (B) per 100 parts by mass of the combined total of the components (A) and (B) is more than 0 part by mass and not more than 90 parts by mass. [5] The dissolving agent of [2], wherein the component (B) is one or more selected from the group consisting of the components (B-3) and (B-7), and the content of the component (B) per 100 parts by mass of the combined total of the components (A) and (B) is more than 0 part by mass and not more than 70 parts by mass. [6] The dissolving agent of [2], wherein the component (B) is one or more selected from the group consisting of the components (B-5) and (B-8), and the content of the component (B) per 100 parts by mass of the combined total of the components (A) and (B) is more than 0 part by mass and not more than 60 parts by mass. [7] A dissolving agent according to [1] or [2], having a content of component (A) of more than 99% by mass but less than 100% by mass. [8] An adhesive for a cured resin product, using any one of the dissolving agents according to [1] to [7], wherein the resin is at least one selected from the group consisting of an acrylic resin, a polycarbonate resin, and an acrylonitrile-butadiene-styrene resin. [9] A resin coating agent comprising a cured resin dissolved in any one of the solvents according to [1] to [7], wherein the resin is at least one selected from the group consisting of an acrylic resin, a polycarbonate resin, and an acrylonitrile-butadiene-styrene resin. Effect of the Invention

[0007] The present invention provides a resin dissolving agent which is excellent in safety and has high dissolving power for cured products of acrylic resin, polycarbonate resin and / or acrylonitrile-butadiene-styrene resin. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] [Terminology definition] "(A) one or more selected from the group consisting of (E)-1-chloro-2,3,3-trifluoropropene and (Z)-1-chloro-2,3,3-trifluoropropene" may be referred to as "component (A)". The same applies to other components such as "(B) further component". With regard to numerical ranges, "to" means that both ends of the range are included. That is, "10 to 90 parts by mass" means "10 parts by mass or more and 90 parts by mass or less." Additionally, "or less" means "the same as or less than," and "or more" means "the same as or more than."

[0009] [Dissolving agent] The dissolving agent is a solvent composition containing one or more compounds selected from the group consisting of (A)(E)-1-chloro-2,3,3-trifluoropropene and (Z)-1-chloro-2,3,3-trifluoropropene, and is a solvent composition for dissolving a cured product of one or more resins selected from an acrylic resin, a polycarbonate resin, and an acrylonitrile-butadiene-styrene resin (ABS resin).

[0010] <(A) One or more selected from the group consisting of (E)-1-chloro-2,3,3-trifluoropropene and (Z)-1-chloro-2,3,3-trifluoropropene> (A) At least one member selected from the group consisting of (E)-1-chloro-2,3,3-trifluoropropene and (Z)-1-chloro-2,3,3-trifluoropropene is the main component of the dissolving agent. The (A) component is the main component of the solvent composition. The (A) component may be either one of the isomers or a mixture of both isomers. When the (A) component is a mixture of the (E) isomer and the (Z) isomer, the (A) component may contain, for example, 80% by mass or more of (Z)-1-chloro-2,3,3-trifluoro-1-propene. That is, the (A) component may be composed of 80% by mass or more and less than 100% by mass of (Z)-1-chloro-2,3,3-trifluoro-1-propene and more than 0% by mass and 20% by mass or less of (E)-1-chloro-2,3,3-trifluoro-1-propene. Commercially available products of the component (A) include AMOLEA (registered trademark) AS-300 (manufactured by AGC Corporation) (a mixture of (E)-1-chloro-2,3,3-trifluoropropene (HCFO-1233yd(E)), (Z)-1-chloro-2,3,3-trifluoropropene (HCFO-1233yd(Z)) and a stabilizer).

[0011] <Ingredients other than component (A)> The dissolving agent may contain components other than the component (A) to the extent that the effects of the present invention are not impaired. The components other than the component (A) include the further component (B) and the additive (C). The dissolving agent may not contain dimethyl carbonate.

[0012] <<(B) Further Ingredients>> The (B) further component is at least one selected from the group consisting of (B-1) halogenated hydrocarbons (excluding (B-2) and (B-3)), (B-2) hydrofluoroolefins, (B-3) hydrofluorocarbons, (B-4) hydrofluoroethers, (B-5) hydrocarbons (excluding (B-1) to (B-3)), (B-6) ethers (excluding (B-4)), (B-7) alcohols, and (B-8) esters. Each of the (B) components may be used alone or in combination.

[0013] From the viewpoint of further enhancing the safety of the dissolving agent, it is preferable that the component (B) is a component that does not fall under the Ordinance on Prevention of Harm from Specified Chemical Substances (Specified Ordinance) of the Industrial Safety and Health Law. It is preferable that the components (B-1) to (B-3) and the component (B-5) do not have an ether bond (—O—). Components (B-5) to (B-8) preferably do not contain halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0014] <(B-1) Halogenated hydrocarbons (excluding (B-2) and (B-3))> (B-1) halogenated hydrocarbon is a compound consisting of carbon atoms, halogen atoms and hydrogen atoms. (B-1) component is at least one member selected from the group consisting of hydrochlorofluorocarbons, hydrochloroolefins, hydrobromocarbons, hydrochlorocarbons and halogenated alkynes.

[0015] Hydrobromocarbons are compounds that consist only of carbon, bromine and hydrogen atoms. Examples of hydrobromocarbons include hydromonobromocarbons such as normal propyl bromide (1-bromopropane).

[0016] Hydrochlorocarbons are compounds that consist only of carbon, chlorine and hydrogen atoms. Examples of hydrochlorocarbons include hydromonochlorocarbons such as 1-chlorobutane.

[0017] Hydrochloroolefins are olefin compounds consisting of only carbon, chlorine and hydrogen atoms. Examples of hydrochloroolefins include trans-1,2-dichloroethylene.

[0018] Hydrochlorofluorocarbons are compounds that consist only of carbon atoms, chlorine atoms, fluorine atoms, and hydrogen atoms, and do not have unsaturated bonds such as carbon-carbon double bonds. Examples of hydrochlorofluorocarbons include dichloropentafluoropropane (1,1-dichloro-2,2,3,3,3-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane, etc.), 1-chloro-2,2,3,3-tetrafluoropropane (HCFC-244ca), 2-chloro-3,3,3-trifluoropropane, and 1-chloro-3,3,3-trifluoropropane. Commercially available HCFCs include Asahiklin AK-225 (manufactured by AGC Corporation).

[0019] The halogenated alkyne is a compound in which at least a portion of the hydrogen atoms of an alkyne is substituted with a halogen, and examples thereof include 1-chloro-3,3-difluoro-1-propyne.

[0020] The number of halogen atoms contained in the component (B-1) is not particularly limited as long as it is 1 or more, but may be 1. Thus, the halogen-based hydrocarbon (B-1) may be one or more selected from the group consisting of (b-1) hydromonobromocarbons and hydromonochlorocarbons.

[0021] <(B-2) Hydrofluoroolefin> The component (B-2) is an olefin compound containing carbon, fluorine and hydrogen atoms, and optionally containing only chlorine and / or bromine atoms, and is other than the component (A). Examples of the component (B-2) include cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z)), 2-bromo-3,3,3-trifluoro-1-propene, 1,1-dichloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, 1,3-dichloro-2,3,3-trifluoropropene, and 1-chloro-1,3,3-trifluoropropene. Commercially available products of the component (B-2) include CELEFIN (registered trademark) 1233Z (HCFO-1233zd(Z)) (manufactured by Central Glass Co., Ltd.).

[0022] <(B-3) Hydrofluorocarbon> The component (B-3) is a compound consisting of carbon atoms, fluorine atoms, and hydrogen atoms, and is a compound having no carbon-carbon double bonds. Examples of the (B-3) component include 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,2,2,3,3,4-heptafluorocyclopentane (HFC-c447ef), and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane. Commercially available products of the component (B-3) include Solkane (registered trademark) 365mfc (manufactured by Nippon Solvay Co., Ltd.) for 1,1,1,3,3-pentafluorobutane, and Zeorora (registered trademark) H (manufactured by Nippon Zeon Co., Ltd.) for 1,1,2,2,3,3,4-heptafluorocyclopentane.

[0023] <(B-4) Hydrofluoroether> The component (B-4) is a compound consisting of carbon atoms, fluorine atoms, hydrogen atoms and an ether bond (-O-). Examples of the (B-4) component include methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (also known as 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane, HFE-347pc-f), 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)pentane, 1,1,1,2,3,4,4,4-octafluoro-2-methoxy-3-(trifluoromethyl)butane, and methyl perfluoropropyl ether. Commercially available products of component (B-4) include 3M (trademark) Novec (trademark) 7100 high performance liquid, 3M (trademark) Novec (trademark) 7200 high performance liquid, 3M (trademark) Novec (trademark) 7300 high performance liquid, 3M (trademark) Novec (trademark) 7000 high performance liquid (manufactured by 3M Japan Ltd.), and Asahiklin AE-3000 (manufactured by AGC Inc.).

[0024] <(B-5) Hydrocarbons (excluding (B-1) to (B-3))> The (B-5) component is composed of only carbon and hydrogen, may be linear or branched, may be cyclic or noncyclic, and may have a carbon-carbon double bond. (B-5) component includes hexane, isohexane, cyclohexane, normal heptane, isoheptane, normal octane, isooctane, isononane, 2-methyl-2-butene, 2-methyl-1-pentene, 2-methyl-2-pentene, 3-ethyl-2-butene, 2,3-dimethyl-2-butene, 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, methylcyclohexane, ethylcyclohexane, limonene, etc. The (B-5) component may be a synthetic product.

[0025] <(B-6) Ether (excluding (B-4))> Examples of the (B-6) component include dipropyl ether, diisopropyl ether, tetrahydrofuran, methyltetrahydrofuran, 4-methyltetrahydropyran, 1,2-dimethoxyethane (monoglyme), 1,3-dioxolane, diethyl ether, diisobutyl ether, dibutyl ether, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, etc. The (B-6) component does not contain a hydroxy group.

[0026] <(B-7) Alcohol> Examples of the component (B-7) include monoalcohol solvents, and preferred examples include ethanol, methanol, 1-propanol, isopropyl alcohol, 1-butanol, isobutyl alcohol, phenoxyethanol, benzyl alcohol, diacetone alcohol, 2-propyn-1-ol, and 1-methoxy-2-propanol.

[0027] <(B-8) Ester> Examples of the (B-8) component include monoester compounds, ester compounds having two carbonyl groups, and cyclic esters, and are preferably methyl acetate, ethyl acetate, normal propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, soybean fatty acid methyl ester, methyl lactate, ethyl lactate, propyl lactate, dibasic acid ester, ethyl acetoacetate, γ-butyrolactone, dimethyl oxalate, or diethyl oxalate. The (B-8) component may be neither dimethyl carbonate nor carbonate.

[0028] <<(C) Additives>> Examples of the (C) component include stabilizers, thickeners, ultraviolet absorbers, antioxidants, chelating agents, rust inhibitors, surfactants, and stabilizers. Specific examples of the (C) component are known to those skilled in the art as additives for resin dissolving agents, and commercially available products can be used. The (C) component may be used alone or in combination.

[0029] The stabilizer is a component for suppressing the decomposition of the (A) component. The stabilizer may be a halogenated alkyne such as 1-chloro-3,3-difluoro-1-propyne, a nitroalkane-based solvent such as nitromethane, nitroethane, or nitropropane, an amine-based solvent such as n-propylamine, diisopropylamine, N-methylpyrrole, or N-methylmorpholine, or an epoxide such as 1,2-butylene oxide, epichlorohydrin, propylene oxide, cyclohexene oxide, cyclopentene oxide, pentene oxide, heptene oxide, octene oxide, alkyl glycidyl ether, or alkyl glycidyl ester. The stabilizer may also be a stabilizer described in WO2017 / 122801.

[0030] The thickener is a component that increases the viscosity of the dissolving agent. This makes it easier for the dissolving agent to remain on the solid substrate to which the cured resin is attached, and the dissolving effect is efficiently increased. Examples of the thickener include silica, sepiolite, bentonite, montmorillonite, thickening polysaccharides, cellulose-based thickeners, polyacrylic acid, polyacrylic acid esters, alkylamides, etc., and silica is preferred. The silica is not particularly limited as long as it is normally used as a thickening agent, and commercially available products can be used. Examples of commercially available silica products include AEROSIL 200, AEROSIL RY 200, AEROSIL RX 200, AEROSIL R 202, AEROSIL R 208, and AEROSIL 200CF (all manufactured by Nippon Aerosil Co., Ltd.).

[0031] The ultraviolet absorber and the antioxidant are components that improve the stability of the solvent composition during long-term storage, etc. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and hindered amine-based ultraviolet absorbers. Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.

[0032] Phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio- Diethylene bis[3-(3,5-di-t-butyl-hydroxyphenyl)propionate], octadodecyl-3-[3,5-di-t-butyl-4-hydroxyphenyl]propionate], N,N-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,4-bis[(octylthio)methyl]-o-cresol, and the like.

[0033] Examples of the amine-based antioxidant include alkylated diphenylamine, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, N,N-di-sec-butyl-p-phenylenediamine, p-phenylenediamine derivatives, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethyl)isocyanurate. Examples of sulfur-based antioxidants include 2,4-bis[(octylthio)methyl]-o-cresol, dilauryl-3,3-thiodipropionate, dimyristyl-3,3-didipropionate, distearyl-3,3-thiodipropionate, pentaerythrityl tetrakis(3-laurylthiopropionate), ditridecyl-3,3-thiodipropionate, 2-mercaptobenzimidazole, bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide, etc. Examples of phosphorus-based antioxidants include tris-nonylphenyl phosphite, triphenyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(isodecyl)phosphite, etc.

[0034] The chelating agent may be an aminocarboxylic acid-based chelating agent, and preferred are hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, and salts thereof.

[0035] Rust inhibitors include cyclohexylamine, dicyclohexylamine, and N,N-bis(2-hydroxyethyl)-N-cyclohexylamine.

[0036] The surfactant may be a nonionic surfactant, and preferred examples thereof include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, fatty acid esters of sorbitol and sorbitan, sucrose fatty acid esters, silicone surfactants, and fluorine-based surfactants.

[0037] The components other than the above-mentioned components are not particularly limited as long as they are components commonly used in the field of solvent compositions, and can be used as appropriate.

[0038] <Composition> In the dissolving agent, the contents of the component (A) and optional components are preferably as follows, from the viewpoint of the dissolving power of the cured resin.

[0039] The content of the (A) component in the dissolving agent is preferably 10% by mass or more and 100% by mass or less. The lower limit of the content of the (A) component may be 50, 60, 80, 90, 95, 98, or 99% by mass. The content of the (A) component may be more than 99% by mass and less than 100% by mass.

[0040] The dissolving agent may be composed of the component (A). Here, the dissolving agent composed of the component (A) refers to a dissolving agent that contains only additives (C) such as stabilizers, thickeners, rust inhibitors, surfactants, UV absorbers, and antioxidants in addition to the component (A), and the content of the component (A) in the dissolving agent is 90% by mass or more and less than 100% by mass. The dissolving agent composed of the component (A) may also be a dissolving agent that consists only of the component (A) and a stabilizer, and the content of the component (A) is more than 99% by mass and less than 100% by mass.

[0041] When the solubilizing agent contains the (B) component, the total content of the (A) component and the (B) component in the solubilizing agent is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 99% by mass or more in the solubilizing agent. In addition, when the solubilizing agent contains the (B) component, from the viewpoint of further increasing the dissolving power of the cured resin product, the content of the (B) component is preferably as follows.

[0042] When the solubilizer contains the (B-1) component as the (B) component, the content of the (B-1) component is preferably more than 0 parts by mass and not more than 80 parts by mass per 100 parts by mass of the total of the (A) and (B-1) components. The lower limit of the content of the (B-1) component may be 10 parts by mass. The upper limit of the content of the (B-1) component may be 70, 60, 50, 40, 30, or 20 parts by mass.

[0043] When the solubilizer contains the (B-2) component as the (B) component, the content of the (B-2) component is preferably more than 0 parts by mass and not more than 90 parts by mass per 100 parts by mass of the total of the (A) and (B-2) components. The lower limit of the content of the (B-2) component may be 10 or 20 parts by mass. The upper limit of the content of the (B-2) component may be 30 or 80 parts by mass.

[0044] When the solubilizer contains the (B-3) component as the (B) component, the content of the (B-3) component is preferably more than 0 parts by mass and not more than 70 parts by mass relative to 100 parts by mass of the total of the (A) and (B-3) components. The lower limit of the content of the (B-3) component may be 10 parts by mass. The upper limit of the content of the (B-3) component may be 60, 40, 30, or 10 parts by mass.

[0045] When the solubilizer contains the (B-4) component as the (B) component, the content of the (B-4) component is preferably more than 0 parts by mass and not more than 80 parts by mass relative to 100 parts by mass of the total of the (A) and (B-4) components. The lower limit of the content of the (B-4) component may be 10 parts by mass. The upper limit of the content of the (B-4) component may be 70, 40, 30, or 10 parts by mass.

[0046] When the solubilizer contains the (B-5) component as the (B) component, the content of the (B-5) component is preferably more than 0 parts by mass and not more than 60 parts by mass relative to 100 parts by mass of the total of the (A) and (B-5) components. The lower limit of the content of the (B-5) component may be 10 parts by mass. The upper limit of the content of the (B-5) component may be 50, 20, or 10 parts by mass.

[0047] When the solubilizer contains the (B-6) component as the (B) component, the content of the (B-6) component is preferably more than 0 parts by mass and not more than 90 parts by mass relative to 100 parts by mass of the total of the (A) component and the (B-6) component. The lower limit of the content of the (B-6) component may be 10 parts by mass. The upper limit of the content of the (B-6) component may be 60 parts by mass.

[0048] When the solubilizer contains the (B-7) component as the (B) component, the content of the (B-7) component is preferably more than 0 parts by mass and not more than 70 parts by mass per 100 parts by mass of the total of the (A) and (B-7) components. The lower limit of the content of the (B-7) component may be 10 parts by mass. The upper limit of the content of the (B-7) component may be 50 or 10 parts by mass.

[0049] When the solubilizer contains the (B-8) component as the (B) component, the content of the (B-8) component is preferably more than 0 parts by mass and not more than 60 parts by mass per 100 parts by mass of the total of the (A) component and the (B-8) component. The lower limit of the content of the (B-8) component may be 10 parts by mass. The upper limit of the content of the (B-8) component may be 30 parts by mass.

[0050] Therefore, when the (B) component is one or more selected from the group consisting of the (B-1) component and the (B-4) component, the content of the (B) component may be more than 0 part by mass and not more than 80 parts by mass per 100 parts by mass of the combined total of the (A) component and the (B) component. In addition, when the (B) component is one or more selected from the group consisting of the (B-2) component and the (B-6) component, the content of the (B) component may be more than 0 part by mass and not more than 90 parts by mass per 100 parts by mass of the combined total of the (A) component and the (B) component. When the (B) component is one or more selected from the group consisting of the (B-3) component and the (B-7) component, the amount of the (B) component per 100 parts by mass of the combined total of the (A) component and the (B) component may be more than 0 part by mass and not more than 70 parts by mass. When the (B) component is one or more selected from the group consisting of the (B-5) component and the (B-8) component, the amount of the (B) component per 100 parts by mass of the combined total of the (A) component and the (B) component may be more than 0 part by mass and not more than 60 parts by mass.

[0051] When the content of the component (B) (component (B-1) to component (B-8)) is within the above range, the dissolving power of the cured resin is superior.

[0052] The content of the additive (C) in the dissolving agent is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably less than 1% by mass, of the dissolving agent.

[0053] (Method of preparing the dissolving agent) The solubilizer can be produced by mixing the raw material components, component (A), and optional components (B) and / or (C).

[0054] <Cured product of one or more resins selected from acrylic resin, polycarbonate resin, and acrylonitrile-butadiene-styrene resin> The cured resin includes a cured resin only and a cured resin composition including additives added to the resin. The cured resin also includes a cured resin that is cured by accelerating the curing reaction of the resin, and a solidified resin that is solidified by volatilization of additives added to the resin, such as a reactive diluent, and an increase in viscosity.

[0055] Examples of the acrylic resin include compounds having an acryloyl group and / or a methacryloyl group, and specifically, methyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate. Here, (meth)acrylate means at least one of acrylate and methacrylate. The acrylic resin preferably does not have a fluorine atom, and particularly preferably does not have a halogen atom. Examples of additives that are mixed with the acrylic resin include additives such as a curing agent, a curing accelerator, a filler, a stabilizer, a plasticizer, a lubricant, a flame retardant, a flame retardant assistant, an antistatic agent, a colorant, an electrostatic charge imparting agent, a sliding property improver, an impact resistance improver, and a reactive diluent. Acrylic resins are easy to process and have excellent transparency, and are therefore used in windshields, windows for aircraft, ships, and automobiles, aquariums, lenses, lighting equipment, displays, signs, and the like.

[0056] Polycarbonate resin is a type of thermoplastic plastic. The junctions between monomer units are composed of carbonate groups (-O-(C=O)-O-). Additives that are mixed into polycarbonate resin include curing agents, curing accelerators, fillers, stabilizers, plasticizers, lubricants, flame retardants, flame retardant assistants, antistatic agents, colorants, electrostatic charge imparting agents, sliding property improvers, impact resistance improvers, and reactive diluents. Polycarbonate resin is widely used in components of automobiles, etc., and is used in roofs, headlamp lenses, etc.

[0057] Acrylonitrile-butadiene-styrene resin is an acrylonitrile-styrene copolymer, which is a copolymer of acrylonitrile and styrene with polybutadiene, a rubber-like polymer, dispersed therein, and is mainly composed of three components: acrylonitrile, butadiene, and styrene. Additives that are mixed into acrylonitrile-butadiene-styrene resin include curing agents, curing accelerators, fillers, stabilizers, plasticizers, lubricants, flame retardants, flame retardant assistants, antistatic agents, colorants, electrostatic charge imparting agents, sliding improvers, impact resistance improvers, and reactive diluents. Acrylonitrile-butadiene-styrene resin is widely used in interior and exterior parts of automobiles, etc., and is used in wheel caps, wheel covers, dashboards, etc.

[0058] (How to use the dissolving agent) The method for dissolving a cured resin using a dissolving agent includes a step of contacting the cured resin with the dissolving agent. In the step of contacting the cured resin with the dissolving agent, the cured resin is dissolved in the dissolving agent. The contact time between the dissolving agent and the cured resin is not particularly limited as long as it is a time that can achieve the desired effect. The contact time is preferably 5 seconds to 24 hours, more preferably 10 seconds to 8 hours, and particularly preferably 10 minutes to 2 hours. When it is within the above time range, the cured resin can be sufficiently dissolved. The cured resin may be entirely dissolved to form a uniform phase with the dissolving agent, or the cured resin may be entirely or partially swollen by the dissolving agent to become a swollen product, and the dissolving agent and the swollen resin may exist in two layers. It is preferable that the cured resin is entirely dissolved to form a uniform phase with the dissolving agent. In addition, when the amount of the cured resin to be dissolved exceeds the saturated dissolving amount of the dissolving agent, a part of the cured resin may remain undissolved.

[0059] The temperature of the dissolving agent when it is brought into contact with the cured resin product is not particularly limited, but is preferably 0 to 50°C, and particularly preferably 5 to 40°C.

[0060] [Use of dissolving agent] The solvent can dissolve the cured resin, and therefore can be used as a coating agent for the resin, an adhesive for the cured resin, and the like.

[0061] <Coating agent> The coating agent is a composition in which a cured resin is dissolved in a solvent. The coating agent is applied (for example, coated) to a substrate, and the solvent portion of the coating agent is removed (for example, volatilized), thereby forming a coating film of the cured resin. In addition, a resin molded product of a desired shape can be obtained by pouring the coating agent into a mold of any shape and removing the solvent portion of the solvent agent (for example, volatilized). Note that a part of the cured resin may be undissolved in the coating agent. However, the content of the cured resin in the coating agent is preferably equal to or less than the saturated solubility of the cured resin. With such a content, there is no undissolved cured resin, and a homogeneous coating and / or resin molded product can be obtained.

[0062] <Adhesive> The adhesive can be used as a solvent adhesive that dissolves the cured resin and bonds it. This allows the bonding surfaces to be firmly bonded without the need for an intermediate material such as a reactive curing adhesive. A method for manufacturing an adhesive using the adhesive includes a step of contacting the adhesive with a solvent.

[0063] Specifically, the method for producing an adhesive structure includes the steps of (A1) applying the solvent to a surface to be adhered of one of the substrates to dissolve a portion of the surface to be adhered of one of the substrates, and (B1) laminating the other substrate and bonding the substrates together via the partially dissolved surface to be adhered of the one of the substrates.

[0064] The method for producing an adhesive body includes a step of (A1) applying the solubilizing agent to a surface to be adhered of one substrate to dissolve a part of the surface to be adhered of the one substrate, a step of (B2) applying the solubilizing agent to a surface to be adhered of the other substrate to dissolve a part of the surface to be adhered of the other substrate, and a step of (C2) bonding one substrate to the other substrate to bond the substrates together via the partially dissolved surface to be adhered of the one substrate and the partially dissolved surface to be adhered of the other substrate. The method for producing an adhesive body may include a step of bonding an additional substrate by repeating the steps (A1) and (B1) as well as the steps (A1), (B2) and (C2).

[0065] The method of applying the dissolving agent is not particularly limited, and examples thereof include coating, spraying, and spray gun. The time for bonding the substrates together is not particularly limited as long as the desired effect can be achieved. The contact time is preferably 1 minute to 10 hours, and particularly preferably 30 minutes to 2 hours. When the time is within the above range, the adhesive strength between the substrates is sufficiently exerted. After the step of bonding the substrates together, a step of heating at a temperature of 50 to 80°C may be included as the case may be. This further accelerates curing and further increases the adhesive strength. EXAMPLES

[0066] 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. In addition, unless otherwise specified, parts are parts by weight.

[0067] (Products used) The components used in the examples are as follows: The dissolving agents in Examples 1, 85, 114 and Comparative Examples 1 to 23 were prepared by using the following components as they were, and the dissolving agents in Examples 2 to 84, 86 to 113 and 115 to 153 were prepared by mixing the following components.

[0068] 1. Component (A) (a-1) AMOLEA® AS-300 (a mixture of more than 99% by mass of (E)-1-chloro-2,3,3-trifluoropropene and (Z)-1-chloro-2,3,3-trifluoropropene and less than 1% by mass of a stabilizer) (manufactured by AGC Inc.)

[0069] 2.(B) Component (b1-1) 1-Bromopropane (manufactured by ICL JAPAN Co., Ltd.) (b1-2) 1-chlorobutane (Tokyo Chemical Industry Co., Ltd.) (b2-1) cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(Z), manufactured by Central Glass Co., Ltd.) (B3-1) 365MFC: 1,1,1,3,3-pentafluorobutane (Solcan MFC365, manufactured by Nippon Solvay Co., Ltd.) (b4-1) 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (ASAHIKLIN AE-3000, manufactured by AGC Corporation) (b4-2) A mixture of 20 parts by mass or more and 80 parts by mass or less of methyl nonafluorobutyl ether and 20 parts by mass or more and 80 parts by mass or less of methyl nonafluoroisobutyl ether (3M Japan Ltd., 3M (trademark) Novec (trademark) 7100 high-performance liquid) (b5-1) Isooctane (manufactured by Sankyo Chemical Co., Ltd.) (b6-1) 1,2-dimethoxyethane (Tokyo Chemical Industry Co., Ltd.) (b7-1) Ethanol (manufactured by Hayashi Pure Chemical Industries, Ltd.) (b7-2) Solmix AP-1 (manufactured by Japan Alcohol Sales Co., Ltd., ethanol 85.50% by mass, 2-propanol 13.40% by mass, methanol 1.10% by mass, moisture 0.20% by mass or less) (b8-1) sec-butyl acetate (Tokyo Chemical Industry Co., Ltd.)

[0070] 3. Hardened acrylic resin, polycarbonate resin or ABS resin (1) An acrylic plate (manufactured by Acrylic Sunday Co., Ltd.; Acrylic Sunday EX plate; color number EX001, thickness 2 mm) was used as the cured acrylic resin. (2) A polycarbonate resin plate (manufactured by Hikari Corporation, 30 mm x 10 mm x 2 mm) was used as a cured product of polycarbonate resin (PC resin). (3) An ABS resin plate (manufactured by Takachi Electric Industry Co., Ltd., 300 mm x 200 mm x 1.0 mm) was used as a cured material of acrylonitrile butadiene styrene resin (ABS resin).

[0071] 4.Other Facilities Test tube: PYREX (registered trademark) (manufactured by Corning; 10 x 75 mm) Wrap: Food packaging wrap film (manufactured by Riken Fabro Co., Ltd.; width 22 cm x 100 m)

[0072] Test example 1: Acrylic resin dissolution test The acrylic plate was cut into 20 mm x 10 mm pieces to obtain acrylic test pieces. 4 g of the dissolving agent shown in Tables 1 to 3 was placed in a test tube, and the cut acrylic test pieces were immersed in the solution. The solution was left at room temperature (18 to 22°C), and the dissolving power of the cured acrylic resin was evaluated as follows. ◎: The hardened resin completely dissolved within 2 hours. ○: The hardened resin completely dissolved within more than 2 hours and within 8 hours. ●: All hardened resin dissolved within more than 8 hours but within 24 hours. ×: The cured resin did not dissolve within 24 hours.

[0073] When the acrylic test pieces dissolved (when the dissolving power result was "●, ○, or ◎"), the dissolving agent into which the acrylic test pieces had dissolved was a uniform liquid phase. Furthermore, when the solvent was evaporated, the acrylic resin hardened again, making it possible to freely change the shape of the acrylic resin. Furthermore, the color of the hardened acrylic resin maintained the color of the dissolved acrylic resin and was transparent. Therefore, the dissolving agent into which the acrylic test pieces (hardened acrylic resin) had dissolved could also be used as a coating agent.

[0074] On the other hand, if the acrylic test piece did not dissolve (the dissolving power result was "X"), there was no damage or change to the surface of the acrylic test piece.

[0075] Test Example 2: Polycarbonate resin dissolution test 50 mg of each of the dissolving agents shown in Tables 4 to 6 was dropped onto a polycarbonate plate using a Pasteur pipette, and then the plate was left for 1 minute at room temperature (20°C). The surface condition of the polycarbonate plate was then checked using a microspatula as follows to evaluate the dissolving power of the cured polycarbonate resin. In Test Example 2, the dissolving power of the cured polycarbonate resin was judged to be excellent in the case of "◎" or "◯", and the dissolving power of the cured polycarbonate resin was judged to be poor in the case of "△" or "×". ◎: The surface is melted, and the molten, sticky polycarbonate adheres to the micro spatula. ○: The surface is melted, and the polycarbonate melted and sticky is attached to the microspatula, but the amount of the melted polycarbonate adhered to the microspatula is less than half of that in the case of "◎" △: Whitening or other changes in the surface are observed, but the polycarbonate dissolved in the micro spatula does not adhere to the surface. ×: No change in surface condition

[0076] Test example 3: Adhesion test (1) Acrylic resin adhesion test Two (1) acrylic plates (cut to 10 mm length x 30 mm width x 2 mm thickness) were used. The solvent of each example shown in Tables 7 to 9 was dropped with a Pasteur pipette onto the center of the surface formed by the length and width of one of the acrylic plates in a line in the horizontal direction of one of the acrylic plates. Next, the other acrylic plate was placed vertically against the surface of the other acrylic plate to which the solvent had been applied, and the other acrylic plate was attached so that the thickness (2 mm) of the other acrylic plate was in contact with the solvent. The excess solvent was wiped off with a tissue. The bonded structure was left for 30 minutes to obtain a bonded structure. The adhesiveness of the bonded structure was evaluated by the following method. (Adhesion test) One acrylic plate was lifted with a finger, and it was confirmed whether the other acrylic plate could be separated. The adhesion was evaluated according to the following criteria. ○: The acrylic plate did not come off, ×: The acrylic plate came off

[0077] (2) Polycarbonate resin adhesion test The test was conducted in the same manner as in "(1) Acrylic resin adhesion test", except that the "two (1) acrylic plates" were replaced with "two polycarbonate resin plates".

[0078] (3) Adhesion test of acrylonitrile-butadiene-styrene resin The test was conducted in the same manner as in "(1) Acrylic resin adhesion test", except that the "two (1) acrylic plates" were replaced with "two ABS resin plates".

[0079] The results are summarized in Tables 1 to 9.

[0080] [Table 1]

[0081] [Table 2]

[0082] [Table 3]

[0083] [Table 4]

[0084] [Table 5]

[0085] [Table 6]

[0086] [Table 7]

[0087] [Table 8]

[0088] [Table 9]

[0089] From Tables 2 and 3, the solubilizer consisting of component (A) and the solubilizer containing component (A) and component (B) were excellent in dissolving the cured acrylic resin. Also, the solubilizer consisting of component (A) and the solubilizer containing component (A) and component (B) having a specific composition were more excellent in dissolving the cured acrylic resin. Also, the composition in which the cured acrylic resin was dissolved in the solubilizer consisting of component (A) or the solubilizer containing component (A) and component (B) had excellent coating properties.

[0090] Neither component (A) nor component (B) falls under the specific chemical substance hazard prevention regulations (specific chemical substance regulations) of the Industrial Safety and Health Act. Therefore, the solvent consisting of component (A) and the solvent containing components (A) and (B) are highly safe.

[0091] From Tables 5 and 6, the dissolving agent consisting of component (A) and the dissolving agent containing component (A) and component (B) were excellent in dissolving the cured polycarbonate resin. Furthermore, the dissolving agent consisting of component (A) and the dissolving agent containing component (A) and component (B) having a specific composition were even more excellent in dissolving the cured polycarbonate resin.

[0092] As can be seen from Tables 8 and 9, the adhesives using the solvent consisting of component (A) and the solvent containing components (A) and (B) were able to dissolve at least a portion of the resin, and therefore had excellent adhesive strength for acrylic resin, polycarbonate resin (PC resin), and acrylonitrile-butadiene-styrene resin (ABS resin).

Claims

1. A dissolving agent for a cured resin product, comprising: (A) one or more members selected from the group consisting of (E)-1-chloro-2,3,3-trifluoropropene and (Z)-1-chloro-2,3,3-trifluoropropene; and (B) a further component, the resin is at least one selected from an acrylic resin, a polycarbonate resin, and an acrylonitrile-butadiene-styrene resin; The (B) further component is at least one selected from the group consisting of (B-1) halogenated hydrocarbons (excluding (B-2)), (B-2) hydrofluoroolefins (excluding (A)), (B-4) hydrofluoroethers, (B-5) hydrocarbons (excluding (B-1)), (B-6) ethers (excluding (B-4)), (B-7) alcohols, and (B-8) esters; The content of the component (A) in the dissolving agent is 10% by mass or more and less than 100% by mass, The temperature of the dissolving agent when dissolving the cured resin is 5° C. to 40° C. A solvent for hardened resin (excluding solvents containing hydrofluorocarbons).

2. The dissolving agent according to claim 1, wherein the component (B) is one or more selected from the group consisting of the component (B-1) and the component (B-4), the component (B-1) is one or more selected from the group consisting of (b-1) hydromonobromocarbon and hydromonochlorocarbon, and the content of the component (B) is more than 0 part by mass and not more than 80 parts by mass per 100 parts by mass of the total of the components (A) and (B).

3. The dissolving agent according to claim 1, wherein the component (B) is one or more selected from the group consisting of the component (B-2) and the component (B-6), and the content of the component (B) is more than 0 part by mass and not more than 90 parts by mass per 100 parts by mass of the total of the components (A) and (B).

4. The dissolving agent according to claim 1, wherein the component (B) is a component (B-7), and the content of the component (B) is more than 0 part by mass and not more than 70 parts by mass per 100 parts by mass of the total of the components (A) and (B).

5. The dissolving agent according to claim 1, wherein the component (B) is one or more selected from the group consisting of the component (B-5) and the component (B-8), and the content of the component (B) is more than 0 part by mass and not more than 60 parts by mass per 100 parts by mass of the total of the components (A) and (B).

6. An adhesive for a cured resin product, using the dissolving agent according to any one of claims 1 to 5, wherein the resin is at least one selected from the group consisting of an acrylic resin, a polycarbonate resin, and an acrylonitrile-butadiene-styrene resin.

7. A resin coating agent comprising a cured resin dissolved in the dissolving agent according to any one of claims 1 to 5, wherein the resin is at least one selected from the group consisting of an acrylic resin, a polycarbonate resin, and an acrylonitrile-butadiene-styrene resin.

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