JP7634313B2 - Dissolving agent for hardened acrylic resin, polycarbonate resin and acrylonitrile-butadiene-styrene resin, and coating agent and adhesive using same - Google Patents

Description

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.

Dichloromethane and trichloroethylene have a high dissolving power for cured resins, and are therefore 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 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).

JP 2003-306700 A

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

The present invention aims to provide a resin dissolving agent that is safe and has high dissolving power for cured acrylic resin, polycarbonate resin, and acrylonitrile-butadiene-styrene resin.

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 an acrylic resin, a polycarbonate resin, and an acrylonitrile-butadiene-styrene resin.
[2] The dissolving agent of [1] further comprising one or more further components (B) 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 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 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 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).
[5] The dissolving agent according to [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) 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).
[6] The dissolving agent according to [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) 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).
[7] The dissolving agent of [1] or [2], wherein the content of the (A) component is more than 99 mass% and less than 100 mass%.
[8] An adhesive for a cured resin product using any one of the dissolving agents [1] to [7], wherein the resin is at least one selected from an acrylic resin, a polycarbonate resin, and an acrylonitrile-butadiene-styrene resin.
[9] A resin coating agent comprising a cured resin dissolved in the solvent according to any one of [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.

The present invention provides a resin dissolving agent that is safe and has high dissolving power for cured acrylic resin, polycarbonate resin, and/or acrylonitrile-butadiene-styrene resin.

[Definition of terms]
"(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 a numerical range, "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 greater than."

[Solubilizer]
The dissolving agent is a solvent composition containing one or more types of resins 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 types of resins selected from an acrylic resin, a polycarbonate resin, and an acrylonitrile-butadiene-styrene resin (ABS resin).

<(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>
(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 Inc.) (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).

<Components other than component (A)>
The dissolving agent may contain components other than the component (A) as long as the effects of the present invention are not impaired. Examples of the components other than the component (A) include an additional component (B) and an additive (C). The dissolving agent may not contain dimethyl carbonate.

<<(B) Further Components>>
The further component (B) 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 components (B) may be used alone or in combination.

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—).
It is preferable that the components (B-5) to (B-8) do not contain halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

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

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

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

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

Hydrochlorofluorocarbons are compounds consisting only of carbon, chlorine, fluorine 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 Inc.).

Halogenated alkynes are compounds in which at least some of the hydrogen atoms of an alkyne have been replaced with halogens, such as 1-chloro-3,3-difluoro-1-propyne.

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

<(B-2) Hydrofluoroolefin>
The component (B-2) is an olefin compound containing carbon atoms, fluorine atoms, and hydrogen atoms, and optionally containing only chlorine atoms and/or bromine atoms. The component (B-2) 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.).

<(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 component (B-3) 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.
As commercially available products of the component (B-3), for example, 1,1,1,3,3-pentafluorobutane is Solkane (registered trademark) 365mfc (manufactured by Nippon Solvay Co., Ltd.), and for 1,1,2,2,3,3,4-heptafluorocyclopentane, Zeorora (registered trademark) H (manufactured by Nippon Zeon Co., Ltd.) is mentioned.

<(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.).

<(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 acyclic, and may have a carbon-carbon double bond. Examples of the (B-5) component include 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, and limonene. The (B-5) component may be a synthetic product.

<(B-6) Ethers (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.

<(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.

<(B-8) Ester>
Examples of the component (B-8) include monoester compounds, ester compounds having two carbonyl groups, and cyclic esters, and are preferably methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, soybean fatty acid methyl esters, methyl lactate, ethyl lactate, propyl lactate, dibasic acid esters, ethyl acetoacetate, γ-butyrolactone, dimethyl oxalate, or diethyl oxalate. The component (B-8) may be one other than dimethyl carbonate or one other than a carbonate ester.

<<(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.

The stabilizer is a component for suppressing decomposition of component (A). 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.

A thickener is a component that increases the viscosity of a 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 thickening agents include silica, sepiolite, bentonite, montmorillonite, thickening polysaccharides, cellulose-based thickening agents, polyacrylic acid, polyacrylic acid esters, alkylamides, etc., and silica is preferred. There are no particular restrictions on the silica 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.).

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

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- Examples include 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, and 2,4-bis[(octylthio)methyl]-o-cresol.

Examples of amine-based antioxidants include alkylated diphenylamines, 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.

Examples of chelating agents include aminocarboxylic acid-based chelating agents, and preferred are hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, and salts thereof.

Antirust agents include cyclohexylamine, dicyclohexylamine and N,N-bis(2-hydroxyethyl)-N-cyclohexylamine.

Examples of surfactants include nonionic surfactants, and preferred are 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.

Further components other than those listed above are not particularly limited as long as they are components commonly used in the field of solvent compositions and can be used as appropriate.

<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 product.

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

The dissolving agent may also be composed of component (A). Here, a dissolving agent composed of 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 component (A), and in which the content of component (A) in the dissolving agent is 90% by mass or more and less than 100% by mass. A dissolving agent composed of component (A) may also be a dissolving agent that consists only of component (A) and stabilizers, and in which the content of component (A) is more than 99% by mass and less than 100% by mass.

When the dissolving agent contains the (B) component, the total content of the (A) component and the (B) component in the dissolving 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 dissolving agent. In addition, when the dissolving 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.

When the dissolving agent contains the component (B-1) as the component (B), the content of the component (B-1) 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 components (A) and (B-1). The lower limit of the content of the component (B-1) may be 10 parts by mass. The upper limit of the content of the component (B-1) may be 70, 60, 50, 40, 30, or 20 parts by mass.

When the dissolving agent 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.

When the dissolving agent 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 per 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.

When the dissolving agent contains the component (B-4) as the component (B), the content of the component (B-4) 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 components (A) and (B-4). The lower limit of the content of the component (B-4) may be 10 parts by mass. The upper limit of the content of the component (B-4) may be 70, 40, 30, or 10 parts by mass.

When the dissolving agent 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 per 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.

When the dissolving agent 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 per 100 parts by mass of the total of the (A) and (B-6) components. 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.

When the dissolving agent contains the component (B-7) as the component (B), the content of the component (B-7) 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 components (A) and (B-7). The lower limit of the content of the component (B-7) may be 10 parts by mass. The upper limit of the content of the component (B-7) may be 50 or 10 parts by mass.

When the dissolving agent 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) and (B-8) components. 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.

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

When the content of the (B) component (components (B-1) to (B-8)) is as described above, the dissolving power of the cured resin is superior.

The content of 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.

(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).

<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.

Examples of acrylic resins include compounds having an acryloyl group and/or a methacryloyl group, specifically methyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate. Here, (meth)acrylate means at least one of acrylate and methacrylate. It is preferable that the acrylic resin does not have a fluorine atom, and it is particularly preferable that the acrylic resin does not have a halogen atom. Examples of additives that can be 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, so they are used in windshields, windows for aircraft, ships, and automobiles, aquariums, lenses, lighting equipment, displays, signs, etc.

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 for automobiles and other products, including roofs and headlamp lenses.

Acrylonitrile-butadiene-styrene resin is an acrylonitrile-styrene copolymer, which is a copolymer of acrylonitrile and styrene with polybutadiene, a rubbery polymer, dispersed therein, and is mainly composed of the 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 components of automobiles, etc., and is used in wheel caps, wheel covers, dashboards, etc.

(Method of using 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. In addition, the entire cured resin may be dissolved to form a uniform phase with the dissolving agent, or all or a part of the cured resin may become a swollen product swollen by the dissolving agent, and the dissolving agent and the swollen resin may exist in two layers. It is preferable that the entire cured resin is 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.

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

[Uses of dissolving agents]
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.

<Coating Agent>
The coating agent is a composition in which a cured resin is dissolved in a solvent. The coating agent is applied (e.g., coated) to a substrate, and the solvent portion of the coating agent is removed (e.g., volatilized), 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 (e.g., volatilized). In addition, 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. If the content is such, there is no undissolved cured resin, and a homogeneous coating and/or resin molded product can be obtained.

<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.

Specifically, the method for producing an adhesive body includes the steps of (A1) applying the solvent to the adherend surface of one of the substrates to dissolve a portion of the adherend surface of the one of the substrates, and (B1) laminating the other substrate and bonding the substrates together via the adherend surface of the one of the substrates, the portion of which has been dissolved.

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

The method of applying the solvent is not particularly limited, and examples include coating, spraying, and using a 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 fully 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 increases the adhesive strength.

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. Note that, unless otherwise specified, parts are parts by weight.

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

1. (A) Component (a-1): AMOLEA (registered trademark) 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.)

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 (Solkan 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 Inc.)
(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.)

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

4. Other equipment 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)

Test Example 1: Acrylic resin dissolution test An 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 then 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 was completely dissolved within 2 hours.
◯: The cured resin completely dissolved within more than 2 hours and within 8 hours.
●: The hardened resin completely dissolved within more than 8 hours and within 24 hours.
x: The cured resin did not dissolve within 24 hours.

When the acrylic test piece dissolved (when the dissolving power result was "●, ○, ◎"), the solvent in which the acrylic test piece dissolved was a uniform liquid phase. Furthermore, when the solvent was evaporated, the acrylic resin hardened again, and it was 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 solvent in which the acrylic test piece (hardened acrylic resin) dissolved could also be used as a coating agent.

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.

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 at room temperature (20°C) for 1 minute. The surface condition of the polycarbonate plate was then checked using a micro spatula as follows to evaluate the dissolving power of the cured polycarbonate resin. In Test Example 2, "◎" or "◯" indicated that the dissolving power of the cured polycarbonate resin was excellent, and "△" or "×" indicated that the dissolving power of the cured polycarbonate resin was poor.
◎: The surface is dissolved, and sticky polycarbonate dissolved in the microspatula adheres to the surface. ○: The surface is dissolved, and sticky polycarbonate dissolved in the microspatula adheres to the surface, but the amount of the dissolved polycarbonate adheres to the surface by visual inspection is less than half that of the ◎ case. △: Changes such as whitening are observed on the surface, but the polycarbonate dissolved in the microspatula does not adhere to the surface. ×: There is no change in the surface condition.

Test Example 3: Adhesion Test (1) Adhesion Test of Acrylic Resin Two (1) acrylic plates (cut into 10 mm length × 30 mm width × 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 was 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 body was obtained by leaving it for 30 minutes. The adhesion of the bonded body 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

(2) Adhesion test of polycarbonate resin The test was carried out in the same manner as in "(1) Adhesion test of acrylic resin", except that "two (1) acrylic plates" were replaced with "two polycarbonate resin plates".

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

The results are summarized in Tables 1 to 9.

From Tables 2 and 3, it can be seen that the dissolving agent consisting of component (A) and the dissolving agent containing components (A) and (B) were excellent in dissolving the cured acrylic resin. Furthermore, the dissolving agent consisting of component (A) and the dissolving agent containing components (A) and (B) with specific compositions were even more excellent in dissolving the cured acrylic resin. Furthermore, the composition in which the cured acrylic resin was dissolved in the dissolving agent consisting of component (A) or the dissolving agent containing components (A) and (B) had excellent coating properties.

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, a solvent consisting of component (A) and a solvent containing components (A) and (B) are highly safe.

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

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 (7)

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). The dissolving agent according to claim 1, wherein the (B) component is at least one selected from the group consisting of the (B-1) and (B-4) components, the (B-1) component is at least one selected from the group consisting of (b-1) hydromonobromocarbons and hydromonochlorocarbons, and the content of the (B) component is 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) components. The dissolving agent according to claim 1, wherein the (B) component is one or more selected from the group consisting of the (B-2) component and the (B-6) component, and the content of the (B) component is 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) component and the (B) component. The dissolving agent according to claim 1, wherein the component (B) is component (B-7), and the content of the component (B) is more than 0 parts by mass and not more than 70 parts by mass per 100 parts by mass of the total of the components (A) and (B). The dissolving agent according to claim 1, wherein the (B) component is one or more selected from the group consisting of the (B-5) component and the (B-8) component, and the content of the (B) component is 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) component. An adhesive for cured resin products using the dissolving agent according to any one of claims 1 to 5, the resin being at least one selected from acrylic resin, polycarbonate resin, and acrylonitrile butadiene styrene resin. A resin coating agent in which a cured resin is dissolved in the dissolving agent according to any one of claims 1 to 5, the resin being at least one selected from acrylic resin, polycarbonate resin, and acrylonitrile butadiene styrene resin.