Liquid cleaning composition and cleaning method using curable composition

Abstract

To provide a liquid washing agent composition which uses a curable resin composition such as a seal agent, and improves washing ability of an appliance contacted the curable resin composition or a curable resin composition residue on a substrate surface or a curable resin composition cured body, and a washing method of a specific curable resin composition using the same composition.SOLUTION: There are provided: a liquid washing agent composition comprising, an aliphatic polyhydric alcohol (compound A1), an organic solvent (compound A2) and a compound (compound A3) which releases a base when being dissolved in water; and a washing method of the curable resin composition for washing by the liquid washing agent composition, the curable resin composition including: a curable compound (compound B1) and an amine based curable agent compound (compound B2).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid detergent composition and a method for cleaning a specific curable resin composition using the liquid detergent composition. [Background technology]

[0002] For example, industrial sealants, which may be curable resin compositions, are used to seal part or all of a substrate surface to prevent the passage of liquids and gases, including viscous fluids, over certain areas of the substrate surface.

[0003] When the sealant is a viscous fluid that flows easily, it may be filled into a syringe and applied to a substrate using a dispenser. After use, the syringe is disassembled into the syringe head, nozzle, and other parts, which are then washed with an organic solvent such as acetone and reused.

[0004] As a sealant, for example, a drop sealant composition containing an epoxy compound, which is a sealant used in the production of liquid crystal display cells, has been disclosed (Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-095795 Summary of the Invention [Problem to be solved by the invention]

[0006] However, when a syringe filled with a sealing agent is washed and reused, there is a problem that some sealing agents have poor washability with organic solvents such as acetone.

[0007] Furthermore, when the sealant is a curable resin composition, there is a problem in that after it is applied to a substrate and cured, the cured sealant adheres to the substrate and is difficult to clean.

[0008] Residue of the sealant that is not sufficiently cleaned off causes a decrease in yield in processes that use the sealant.

[0009] Original Akira is The present invention addresses the problem of providing a liquid detergent composition that improves the cleaning properties of curable resin composition residues or cured products of the curable resin composition on the surfaces of tools or substrates that have come into contact with the curable resin composition, such as sealants, and a cleaning method for specific curable resin compositions using the liquid detergent composition. [Means for solving the problem]

[0010] The present invention provides [1] A liquid detergent composition comprising an aliphatic polyhydric alcohol (compound A1), an organic solvent (compound A2), and a compound that releases a base when dissolved in water (compound A3) (hereinafter also referred to as "present invention 1"); and, [2] A method for cleaning a curable resin composition (hereinafter also referred to as "present invention 2"), in which a curable resin composition containing a curable compound (compound B1) and an amine-based curing agent compound (compound B2) is cleaned with the liquid cleaning composition described in the above item [1].

[0011] In the following, Inventions 1 and 2 will be collectively referred to as "the present invention." [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a liquid cleaner composition that uses a curable resin composition such as a sealant to improve the cleanability of curable resin composition residue or a cured product of the curable resin composition on the surface of an implement or substrate that has come into contact with the curable resin composition, and a cleaning method for a specific curable resin composition using the liquid cleaner composition. [Brief explanation of the drawings]

[0013] [Figure 1] This is a SUS plate coated with a liquid crystal sealant using cleaning example 1-2 in cleaning test 1. [Figure 2]FIG. 1 is a schematic diagram of Step 1 of cleaning test 1. [Figure 3] 10 shows examples of the results of Observation 2-2, Observation 2-1A, and Observation 2-2A in Cleaning Test 1. [Figure 4] 10 shows examples of the results of Observation 2-2 and Observation 2-2A in Cleaning Test 2. DETAILED DESCRIPTION OF THE INVENTION

[0014] <<Invention 1>> Invention 1 is a liquid detergent composition comprising an aliphatic polyhydric alcohol (compound A1), an organic solvent (compound A2) (excluding the compound A1), a compound that releases a base when dissolved in water (compound A3), and water.

[0015] [Compound A1] Examples of the compound A1, which is an aliphatic polyhydric alcohol, include dihydric alcohols (aliphatic diols) having 2 to 20 carbon atoms, trihydric alcohols (aliphatic triols) having 3 to 20 carbon atoms, and tetrahydric to octahydric or higher polyhydric alcohols (aliphatic polyols) having 5 to 20 carbon atoms.

[0016] Aliphatic diols include, for example, Ba, E ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, Triethylene glycol, tetraethylene glycol, Alkylene glycols such as 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol; and Alicyclic diols include cycloalkylene glycols such as cyclohexanediol and cyclohexanedimethanol.

[0017] Examples of aliphatic triols include glycerin, N, T Examples of the alkanetriol include trimethylolpropane, trimethylolethane, and hexanetriol.

[0018] Examples of aliphatic polyols include: Polyglycerols such as triglycerol;Alkane polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, and dipentaerythritol, and intramolecular or intermolecular dehydration products of these or alkane triols; and Sugars such as sucrose, glucose, mannose, fructose, and methyl glucoside and their derivatives

[0019] Examples of the aliphatic polyol include aliphatic polyhydric alcohols such as polyoxyalkylene polyglyceryl ether.

[0020] [Compound A2] The compound A2, which is an organic solvent in the present invention 1, refers to an organic solvent capable of dissolving the compound A1, and is preferably Monohydric alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, and benzyl alcohol; Hydrocarbons such as benzene, toluene, xylene, mineral spirits, cyclohexane, n-hexane, methylcyclohexane, and styrene; ethers such as diethyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and diacetone alcohol; Nitrogen compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; glycol ethers such as butyl glycol, methyl diglycol, butyl diglycol, 3-methyl-3-methoxybutanol, and tetrahydrofuran; Chlorines such as methylene chloride, chloroform, carbon tetrachloride, and chlorobenzene; and at least one compound selected from the group consisting of dimethyl sulfoxide; acetonitrile; More preferably, at least one compound selected from the group consisting of monohydric alcohols, hydrocarbons, and ketones, More preferably, it can be selected from monohydric alcohols and / or acetone.

[0021] [Compound A3] The compound (compound A3) that releases a base when dissolved in water is added to adjust the liquid property of the liquid detergent composition of invention 1 to weak alkaline.

[0022] As Compound A3, hydroxides of alkali metals such as NaOH and KOH and salts of strong acids can be used. However, from the viewpoints of pH stability and ease of adjusting the amount added, hydroxides of weakly basic divalent or higher metals, organic compounds, acid salts and normal salts are preferred.

[0023] Examples of weakly basic hydroxides of divalent or higher metals include manganese hydroxide, iron (II) hydroxide, zinc hydroxide, and lanthanum hydroxide. Weakly basic organic compounds include aqueous ammonia, triethanolamine, and 2-amino-2-methyl-1-propanol. Examples of salts of weak acids include sodium carbonate, sodium hydrogen carbonate, formate, acetate (e.g., sodium acetate and potassium acetate), propionate, citrate, etc. From the viewpoint of safety during handling and waste liquid disposal, salts of weak acids are preferred, and sodium bicarbonate is more preferred.

[0024] [Optional ingredients] Various compounds may be blended as optional components within the range that does not impair the effects of the present invention. for example, Esters such as ethyl acetate, propyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, diethyl carbonate, dimethyl carbonate, and propylene carbonate may be added as needed from the viewpoint of rapid dispersion of the components of the curable resin composition. stabilizers (carbazide-based curing agents (e.g., 4,4'-hexamethylenebis(semicarbazide) and modified amine compound-based curing agents (e.g., FXR-1020 (manufactured by T&K TOKA)); Antioxidants (phenolic compounds (e.g., 2,6-di-t-butyl-4-methylphenol, etc.), sulfur-containing compounds (e.g., dilauryl thiodipropionate, etc.), phosphorus compounds (e.g., triphenyl phosphite, etc.), etc.); and Examples include sequestering agents (such as sodium ethylenediaminetetraacetate and sodium citrate).

[0025] [Liquid detergent composition] In present invention 1, the blending weight ratio of compound A1 to compound A2 (A1 / A2) is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 80 / 20, even more preferably 15 / 85 to 70 / 30, even more preferably 20 / 80 to 65 / 35, even more preferably 30 / 70 to 55 / 45, and even more preferably 40 / 60 to 50 / 50, from the viewpoints of flowability and cleansing ability.

[0026] [Curable resin composition] The present invention 1 can be suitably used for cleaning curable resin compositions used in applications such as photocurable adhesives, thermosetting adhesives, sealants (preferably liquid crystal sealants), coating agents, light-shielding agents, gap agents, and impact-resistant absorbers, as well as cured products thereof. below This can be suitably used for cleaning the curable resin composition of the present invention 2 and its cured product, which will be explained in the section 2.

[0027] [Curable resin composition] The present invention 1 can be suitably used for cleaning curable resin compositions used in applications such as photocurable adhesives, thermosetting adhesives, sealants (preferably liquid crystal sealants), coating agents, light-shielding agents, gap agents, and impact-resistant absorbers, as well as cured products thereof. below This can be suitably used for cleaning the curable resin composition of the present invention 2 and its cured product, which will be explained in the section 2.

[0028] <<Invention 2>> Invention 2 is a method for cleaning a curable resin composition, in which a curable resin composition containing a curable compound (compound B1) and an amine-based curing agent compound (compound B2) is cleaned with the liquid cleaning composition of Invention 1.

[0029] [Curable compound (compound B1)] Compound B1 is preferably a thermosetting compound, more preferably a photocurable and thermosetting compound. Specifically, from the viewpoint of thermosetting property, it is preferably one or more compounds selected from the group consisting of epoxy resins, (meth)acrylated epoxy resins, partially (meth)acrylated epoxy resins, and (meth)acrylic resins, and partially (meth)acrylated epoxy resins are more preferred.

[0030] In this specification, (Meth)acrylic means methacrylic and / or acrylic; (Meth)acrylate means methacrylate and / or acrylate; The (meth)acrylated epoxy resin means a resin in which all of the epoxy groups in the epoxy resin have reacted with (meth)acrylic acid. The partially (meth)acrylated epoxy resin means a resin in which some of the epoxy groups in the epoxy resin have reacted with (meth)acrylic acid, that is, a resin having epoxy groups and (meth)acrylic groups in the resin.

[0031] The epoxy resin is preferably Bisphenol A type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, alicyclic epoxy resins, aliphatic linear epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, phenol novolac type epoxy resins with a triphenolmethane skeleton; Diglycidyl ethers of difunctional phenols, diglycidyl ethers of difunctional alcohols, and their halides and hydrogenated products; Polyfunctional epoxy resins include trifunctional and tetrafunctional epoxy resins; Further examples include epoxy resins described in JP-A-2012-077202.

[0032] (Meth)acrylated epoxy resins and partially (meth)acrylated epoxy resins can be obtained by reacting epoxy resins with (meth)acrylic acid. Specifically, a predetermined equivalent ratio of (meth)acrylic acid, a catalyst (e.g., benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.), and a polymerization inhibitor (e.g., methoquinone, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) are added to the epoxy resin, and an esterification reaction is carried out at, for example, 80 to 110°C, thereby (meth)acrylating all or part of the epoxy groups. The epoxy resin used as a raw material is not particularly limited, and examples thereof include the epoxy resins exemplified above.

[0033] The partially (meth)acrylated epoxy resin preferably has a proportion of (meth)acrylic groups of 10 to 90 mol %, more preferably 40 to 60 mol %, based on the total number of moles of (meth)acrylic groups and epoxy groups in the resin.

[0034] The partially (meth)acrylated epoxy resin preferably includes a compound containing one or more epoxy groups and one or more (meth)acrylic groups in one molecule.

[0035] The (meth)acrylic resin is not particularly limited as long as it is a resin having a methacrylic and / or acrylic group, and examples thereof include (meth)acrylic acid esters.

[0036] As the (meth)acrylic resin, a hydroxy group-containing (meth)acrylate can be used, Examples of the hydroxyalkyl (meth)acrylate include hydroxyalkyl (meth)acrylates (e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc.), polyol (meth)acrylates (glycerin mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, ditrimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc.), and alkylene oxide-added polyol (meth)acrylates (e.g., alkylene oxide-added trimethylolpropane di(meth)acrylate, alkylene oxide-added pentaerythritol tri(meth)acrylate, alkylene oxide-added dipentaerythritol penta(meth)acrylate, etc.).

[0037] As the (meth)acrylic resin, an alicyclic (meth)acrylate can be used, Examples include monocyclic (meth)acrylates such as cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, and cyclohexyl (meth)acrylate; bicyclic (meth)acrylates such as isobornyl (meth)acrylate and norbornyl (meth)acrylate; and tricyclic (meth)acrylates such as dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and adamantyl (meth)acrylate.

[0038] As the (meth)acrylic resin, a (meth)acrylate containing at least one selected from polyisoprene, polybutadiene, and polyurethane in the skeleton can be used.

[0039] An example of a commercially available (meth)acrylate oligomer having a polyisoprene skeleton is "UC-203M" (weight average molecular weight 35,000) manufactured by Kuraray Co., Ltd., and an example of a commercially available (meth)acrylate oligomer having a polybutadiene skeleton is "TE 2000" (weight average molecular weight 2,500) manufactured by Nippon Soda Co., Ltd.

[0040] The compound B1 may be a single curable compound or a combination of two or more of these curable compounds. From the viewpoint of being curable by both light and heat, it preferably contains a partially (meth)acrylated epoxy resin, and for example, a partially (meth)acrylated bisphenol A-type epoxy resin is more preferable.

[0041] [Amine-based curing agent compound (compound B2)] The curable resin composition of present invention 2 contains compound B2 as a heat curing agent from the viewpoint of imparting mechanical strength such as breaking strength to the film after heat curing.

[0042] The amine-based curing agent compound (compound B2) has poor solubility and dispersibility in organic solvents, and tends to swell and become prone to sticking to substrates, which tends to make the curable resin composition containing it difficult to clean.

[0043] The compound B2 may have at least one active hydrogen atom in the molecule. primary mono-, di-, and polyamine compounds having one or more primary amino groups in the molecule; secondary mono-, di- and polyamine compounds having one or more secondary amino groups in the molecule; Hydrazide compounds, carbazide compounds, and imidazole compounds; a primary di- or polyamine compound having two or more primary amino groups in the molecule; secondary di- or polyamine compounds having two or more secondary amino groups in the molecule; Adduct compounds of hydrazide compounds or imidazole compounds with epoxy resins or urea; Mixed crystals of the same kind, such as polyamine compounds and polyamine compounds; Examples include mixed crystals of different compounds such as a polyamine compound and a hydrazide compound; and mixed crystals of two hydrazide compounds.

[0044] Specific examples of mono-, di-, and polyamine compounds having one or more primary or secondary amino groups in the molecule include aliphatic primary amines such as methylamine, ethylamine, propylamine, butylamine, ethanolamine, and propanolamine; alicyclic primary monoamines such as cyclohexylamine; aromatic primary amines such as aniline and toluidine; alkylenediamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, cadaverine, and hexamethylenediamine; and 2,4-diamino-6-[2'-methylimidazoline]- ... primary diamines having an imidazolyl group substituted at the 1-position nitrogen atom, such as 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct; polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, tetraethylenetriamine, and tetraethylenepentamine; Examples include alicyclic polyamines such as diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, and isophoronediamine; and aromatic polyamines such as o-xylylenediamine, m-xylylenediamine, p-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone, and preferably aromatic polyamines such as o-xylylenediamine, m-xylylenediamine, and p-xylylenediamine.

[0045] Examples of the hydrazide compound include monobasic acid hydrazides having one hydrazide group in the molecule, dibasic acid hydrazides having two hydrazide groups in the molecule, tribasic acid hydrazides having three hydrazide groups in the molecule, and polyfunctional hydrazides having four or more hydrazide groups in the molecule.

[0046] Specific examples of the monobasic acid hydrazide include acetohydrazide, propionic acid hydrazide, pentanoic acid hydrazide, lauric acid hydrazide, cyclohexanecarbohydrazide, salicylic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, and benzenesulfonohydrazide.

[0047] Specific examples of dibasic acid hydrazides include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodencanedioic acid dihydrazide, hexadecanedioic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, carbohydrazide, maleic acid dihydrazide, phthal ... Examples of suitable diglycolic acid dihydrazide include maleic acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 1,4-naphthoic acid dihydrazide, 4,4'-bisbenzenedihydrazide, hydroquinone diglycolic acid dihydrazide, resorcinol diglycolic acid dihydrazide, catechol diglycolic acid dihydrazide, 4,4'-ethylidenebisphenol-diglycolic acid dihydrazide, and 4,4'-vinylidenebisphenol-diglycolic acid dihydrazide.

[0048] Examples of the tribasic acid hydrazide include 1,3,5-tris(2-hydrazinocarbonylalkyl)isocyanurates such as 1,3,5-tris(2-hydrazinocarbonylethyl)isocyanurate.

[0049] An example of the polyfunctional hydrazide is polyacrylic acid hydrazide.

[0050] Commercially available organic acid dihydrazides include, for example, VDH (1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin), ADH (adipic acid dihydrazide), UDH (7,11-octadecadiene-1,18-dicarbohydrazide), and LDH (octadecane-1,18-dicarboxylic acid dihydrazide).

[0051] The imidazole compound is an imidazole compound that does not have a primary amino group in the molecule, and examples thereof include: Compounds containing an imidazole ring in which the nitrogen atom at position 1 is unsubstituted, such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-methylimidazoline; Examples of imidazole compounds in which the nitrogen atom at position 1 is substituted include 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and 1-cyanoethyl-2-phenylimidazolium trimellitate.

[0052] Adduct compounds of amine compounds and epoxy resins are amine adduct compounds or amine adduct compound derivatives in which the above-mentioned primary di- or polyamine compounds having two or more primary amino groups in the molecule, secondary di- or polyamine compounds having two or more secondary amino groups in the molecule, hydrazide compounds, or imidazole compounds are adducted to epoxy resins (hereinafter, curing agents containing these compounds will also be referred to as "XX-based curing agents" (for example, "amine adduct-based curing agents") in the case of "XX compound").

[0053] Commercially available amine adduct curing agents include ADEKA Hardener EH5030S from ADEKA Corporation, and Amicure PN-23, Amicure PN-30, Amicure MY-24, and Amicure MY-H from Ajinomoto Fine-Techno Co., Ltd.

[0054] As compound B2, the reaction product of an amine compound and an isocyanate compound disclosed in Patent Document 1 can also be preferably used.

[0055] The compound B2 may be any of the above compounds used alone or in combination.

[0056] [Optional ingredients] (Filler (Compound B3)) Invention 1 also functions favorably when the curable resin composition of Invention 2 further contains Compound B3, which is a filler that is difficult to wash off.

[0057] Compound B3 is added for purposes such as controlling the viscosity of the curable resin composition, improving the strength of the cured product obtained by curing the curable resin composition, or improving the adhesive reliability of the curable resin composition by suppressing linear expansion.

[0058] Examples of the compound B3 include known inorganic fillers and organic fillers, and organic fillers are preferred from the viewpoint of stress relaxation.

[0059] Inorganic fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride.

[0060] Examples of organic fillers include poly(meth)acrylic acid esters such as polymethyl methacrylate and polyethyl (meth)acrylate, polystyrene, copolymers obtained by copolymerizing the monomers that constitute these with other monomers, polyester fine particles, polyurethane fine particles, and rubber fine particles.

[0061] (Photopolymerization initiator) When the curable resin composition of present invention 2 is photocured, the photopolymerization initiator used in combination may be any compound that generates radicals or cations by light and initiates a polymerization reaction. An optimal curing wavelength can be selected depending on the manufacturing process and materials used. For example, in the case of a compound that initiates a polymerization reaction with ultraviolet light, the compound is preferably a compound that initiates a polymerization reaction with light having a wavelength of 100 to 500 nm, more preferably more than 340 and less than 400 nm. In the case of a compound that initiates a polymerization reaction with visible light, the compound is preferably a compound that initiates a polymerization reaction with light having a wavelength of 350 to 800 nm, more preferably 400 to 600 nm, and even more preferably 400 to 500 nm. It is preferable that the curable resin composition has low solubility in substances (e.g., liquids, viscous fluids, liquid crystals, etc.) that come into contact with the applied curable resin composition when applied to a substrate, and has a structure that does not generate decomposition products by itself when irradiated with light, or that the decomposition products do not gasify.

[0062] In the curable resin composition of present invention 2, any compound that has a photosensitizing effect and functions as a photopolymerization initiator is considered to be a photopolymerization initiator, even if it is generally classified as a visible light-sensitizing compound.

[0063] The photopolymerization initiator may be a combination of a photoinitiating compound (a compound that is photoexcited by a visible light-sensitizing compound to become a polymerization initiating species) and a visible light-sensitizing compound.

[0064] In the photopolymerization initiator, the molar ratio of the photoinitiating compound to the visible light-sensitizing compound (photoinitiating compound / visible light-sensitizing compound) is preferably 1 / 5 to 5 / 1, more preferably 1 / 3 to 3 / 1, and even more preferably 1 / 2 to 2 / 1, from the viewpoint of supplying stable and sufficient radicals.

[0065] Specifically, the photopolymerization initiator is Examples of the compounds include benzoins, acetophenones, benzophenones, thioxanthones, α-acyloxime esters, phenyl glyoxylates, benzils, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, polyether compounds having a dialkylaminobenzoyl group, benzoin ethers and anthraquinones, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes.

[0066] The photopolymerization initiator is Preferably, the photoinitiator compound contains a polyether compound having a dialkylaminobenzoyl group, More preferably, the composition contains a thioxanthone compound, which is a visible light sensitizing compound, More preferably, a polyether compound having a dialkylaminobenzoyl group and a thioxanthone compound are used in combination.

[0067] The polyether compound having a dialkylaminobenzoyl group includes a compound represented by the following formula (1): [ka] (in formula (1), n1 is 0 to 50, preferably 1 to 45), and a compound represented by the following formula (2): [ka] (in formula (2), n2 is 0 to 50, preferably 1 to 45).

[0068] The photopolymerization initiator may be used alone or in combination of two or more.

[0069] (coupling agent) The curable resin composition in the present invention 2 may contain a coupling agent.

[0070] The coupling agent is added for the purpose of further improving the adhesion of the curable resin composition to a substrate (for example, a liquid crystal display substrate).

[0071] Examples of the coupling agent include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatepropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane.

[0072] The coupling agents may be used alone or in combination of two or more.

[0073] (polymerization inhibitor) Examples of the polymerization inhibitor used in the present invention include phenol-based polymerization inhibitors and phenothiazine-based polymerization inhibitors.

[0074] Phenol-based polymerization inhibitors include 2,2-methylene-bis(4-methyl-6-tertiarybutylphenol) (BHT), catechol, picric acid, tertiarybutylcatechol, 2,6-ditertiarybutyl-p-cresol, and 4,4'-thiobis[ethylene(oxy)(carbonyl)(ethylene)]bis[2,6-bis(1,1-dimethylethyl)phenol].

[0075] Examples of phenothiazine-based polymerization inhibitors include phenothiazine, bis(α-methylbenzyl)phenothiazine, 3,7-dioctylphenothiazine, and bis(α,α-dimethylbenzyl)phenothiazine.

[0076] The phenolic polymerization inhibitor such as BHT can also be used as an antioxidant.

[0077] (others) The curable resin composition in present invention 2 may contain a dispersant, a coloring component such as a pigment or a dye, a storage stabilizer, a plasticizer, a viscoelasticity modifier, and a surfactant modifier (a wetting agent or an antifoaming agent).

[0078] When utilizing the photocurability of the curable resin composition of present invention 2, it is preferable to use coloring components such as pigments and dyes in an amount that does not affect the ultraviolet transmittance.

[0079] [Curable resin composition] The amount of compound B1 in the curable resin composition is determined from the viewpoints of viscosity that allows it to be handled as a sealant and mechanical properties such as mechanical strength and viscoelasticity of the cured product. The content is preferably 10 to 90% by weight, more preferably 20 to 85% by weight, and even more preferably 30 to 80% by weight.

[0080] The amount of compound B2 in the curable resin composition is determined from the viewpoint of mechanical properties such as mechanical strength and viscoelasticity of the cured product. With respect to 1100 parts by weight of compound B, The amount is preferably 1 to 40 parts by weight, and more preferably 5 to 35 parts by weight.

[0081] The compounding amount of the compound B3 in the curable resin composition is, from the viewpoint of controlling the linear expansion coefficient and maintaining the shape after the sealant application, 1100 parts by weight of the compound B3. The amount is preferably 2 to 40 parts by weight, and more preferably 5 to 30 parts by weight.

[0082] The amount of the photopolymerization initiator in the curable resin composition is, for example, 1100 parts by weight of the compound B from the viewpoint of temporary fixation by photocuring. The amount is preferably 0.1 to 10.0 parts by weight, and more preferably 0.5 to 5.0 parts by weight.

[0083] The amount of the coupling agent in the curable resin composition may be adjusted as needed. With respect to 1100 parts by weight of compound B, The amount is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight.

[0084] [Method for cleaning curable resin composition] The second aspect of the present invention is a method for cleaning a substrate that has come into contact with the curable resin composition described above (hereinafter referred to as "curable resin composition"), by cleaning the substrate with the liquid cleaning composition described in claim 1.

[0085] In present invention 2, examples of the substrate that has come into contact with the curable resin composition include components that constitute a syringe or are attached to a syringe, such as a syringe tube, syringe head, or nozzle, filled with the curable resin composition in order to apply the curable resin composition, a container, a dispenser that dispenses the curable resin composition, a tube or pipe through which the curable resin composition has passed, a jig or part that fixes them, and a spatula used to scoop up the resin composition.

[0086] Examples of materials for the substrate include metals such as SUS; ceramics such as glass and earthenware; plastics, Teflon, and silicon.

[0087] Examples of methods for cleaning a substrate that has come into contact with the curable resin composition of invention 2 include the following. (1) The substrate that has been contacted with the curable resin composition is subjected to the liquid cleaning composition of the present invention 1 depending on the curing state of the attached resin and the volatility of the organic solvent. Preferably, the temperature is 5 to 50°C, more preferably 10 to 40°C, and even more preferably 15 to 30°C. After immersion for preferably 10 minutes to 10 days, more preferably 15 minutes to 5 days, even more preferably 30 minutes to 24 hours, even more preferably 1 to 6 hours, even more preferably 1 to 3 hours, and even more preferably 1 to 2 hours, the product is rinsed, if necessary, with water or an organic solvent such as acetone or acetone containing 5% or more of water, and then dried naturally at room temperature or by air blowing.

[0088] (2) The substrate that has come into contact with the curable resin composition is immersed in the liquid cleaning composition of Invention 1, and then subjected to ultrasonic cleaning (preferably degassing ultrasonic cleaning) by irradiating the substrate with ultrasonic waves while the substrate is still immersed. Thereafter, the substrate is rinsed with water or an organic solvent such as acetone or acetone containing 5% or more of water, as needed, and then dried.

[0089] The conditions for ultrasonic irradiation during ultrasonic cleaning are as follows: Depending on the amount of substrate, the size of the cleaning bath, the number of ultrasonic vibrators, and the amount of cleaning solution, The output per ultrasonic vibrator is preferably 15 to 2000 W, more preferably 20 to 1200 W, and even more preferably 30 to 600 W. Depending on the damage to the substrate and the type of dirt, The frequency is preferably 15 to 270 kHz, more preferably 20 to 150 kHz, and even more preferably 30 to 105 kHz. Depending on the volatilization of the liquid detergent composition, the time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes, and even more preferably 30 to 60 minutes.

[0090] The ultrasonic cleaning may be repeated multiple times. When the ultrasonic cleaning is repeated multiple times, it is preferable to appropriately replace the immersed liquid cleaning composition with an unused liquid cleaning composition.

[0091] Example [Cleaning Composition Examples 1 to 28 and Comparative Examples 1 to 3]

[0092] [1] Raw materials (Compound A1) (1) Ethylene glycol (manufacturer: Kanto Chemical Co., Ltd., quality: Grade 1) (2) Triethylene glycol (manufacturer: Kanto Chemical Co., Ltd., quality: Grade 1) (3) Tetraethylene glycol (manufacturer: Kanto Chemical Co., Ltd., quality: Grade 1) (4) The following formula (3): Polyoxyethylene polyglyceryl ether (manufacturer: Sakamoto Pharmaceutical Co., Ltd., product name: SC-E750, number average molecular weight: 750, hydroxyl value: approximately 300) represented by JPEG0007734966000003.jpg35127

[0093] (Compound A2) (1) Ethanol (manufacturer: Kanto Chemical Co., Ltd., quality: special grade) (2) Acetone (Manufacturer: Kanto Chemical Co., Ltd., Quality: Grade 1)

[0094] (Compound A3) (1) Sodium bicarbonate (Manufacturer: Kanto Chemical Co., Ltd., Quality: Grade 1) (2) 2-aminoethanol (manufacturer: Tokyo Chemical Industry Co., Ltd., liquid, pH = 12.1 (100 g / l, HO, 20 °C) (3) 3-amino-1-propanol (manufacturer: Kanto Chemical Co., Ltd., liquid, pH = 11.6 (10 g / l, HO, 20 °C) (4) 2-(2-aminoethoxy)ethanol (manufacturer: Tokyo Chemical Industry Co., Ltd., liquid, pH = 10.2 (10 g / l, H2O, 20 °C) (5) 2-amino-2-ethyl-1,3-propanediol (manufacturer: east Kyokasei Kogyo Co., Ltd., solid)

[0095] (optional ingredient) (1) Stabilizer: 4,4'-hexamethylenebis(semicarbazide) (curing agent described in WO2014 / 010446)

[0096] [2] Compounding conditions The other raw materials were weighed out so that the weight parts would be as shown in Table 1 relative to a total of 100 parts by weight (100 g) of Compound A1 and Compound A2. Compound A1 and Compound A2 were charged into a beaker (300 ml), and the other raw materials were then added. The mixture was stirred with a stirrer at 70°C for 300 minutes, and volatile raw materials were added in accordance with the degree of volatilization, to obtain the liquid detergent compositions of Examples 1 to 28 and Comparative Examples 1 to 3.

[0097] [3] Liquidity (solubility) The dissolution states of the liquid detergent compositions of Examples 1 to 28 and Comparative Examples 1 to 3 obtained under the above-mentioned blending conditions were observed, and If it has dissolved without any residue, it is marked as 〇. If a small amount of undissolved material is visible or the solution is cloudy, it is rated as △. If the original ingredients remain almost the same, mark it as "X"; It was evaluated as follows.

[0098] [Table 1]

[0099] [Liquid crystal sealant] (raw materials) (1-1) Compound B1 (1-1-1) The following formula (4): Partially methacrylated bisphenol A epoxy resin represented by JPEG0007734966000005.jpg23127 (produced by the method described in paragraph 0092 of WO2014 / 057871)

[0100] (1-2) Compound B2 (1-2-1) ADEKA Hardener EH-5057P (ADEKA Corporation, amine adduct curing agent) (1-2-2) ADEKA Hardener EH-5030S (ADEKA Corporation, amine adduct curing agent) (1-2-3) ADEKA Hardener EH-5015S (ADEKA Corporation, amine adduct curing agent) (1-2-4) ADEKA Hardener EH-4358S (ADEKA Corporation, amine adduct curing agent) (1-2-5) ADEKA Hardener EH-5011S (manufactured by ADEKA Corporation, imidazole-based hardener) (1-2-6) FXR-1020 (T&K TOKA, modified amine compound curing agent) (1-2-7) FXR-1081 (T&K TOKA, modified amine compound curing agent)

[0101] (1-3) Compound B3 (1-3-1) Zefiac F-351 (Adeka Industries, core-shell acrylic resin filler) (1-3-2) Seahoster KE-C050HG (Nippon Shokubai Co., Ltd., spherical silica particles)

[0102] (1-4)Optional components (1-4-1) Photopolymerization initiator 1: a compound represented by formula (1) (wherein n1=1) (prepared by the method described in paragraph 0058 of WO2012 / 077720) (1-4-2) Photopolymerization initiator 2: a compound represented by formula (2) (wherein n2=1) (prepared by the method described in paragraph 0060 of WO2012 / 077720) (1-4-3) Silane coupling agent: KBM403 (Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltriethoxysilane) (1-4-4) Polymerization inhibitor: 2,6-di-t-butyl-4-cresol (BHT) (Tokyo Chemical Industry Co., Ltd.)

[0103] (Composition conditions) The other raw materials were weighed out to the weight parts shown in Table 2 relative to 100 parts by weight (5 g) of compound B1, and compound B2 were filled into a plastic cup (20 ml). After that, the other raw materials were added and mixed, and the mixture was kneaded at 25°C for 2 minutes using a Three-One Motor (RW28basic, manufactured by IKA Corporation) to uniformly disperse the mixture, thereby obtaining liquid crystal sealants 1 to 4.

[0104] [Table 2]

[0105] [Cleaning Examples 1-1 to 1-28 and Cleaning Comparison Examples 1-1 to 1-2] (Tools: Common to cleaning conditions 1 to 3) (1) Syringe (TERUMO, 1 ml tuberculin SS-01T) (2) SUS plate (SUS304 manufactured by Engineering Test Services, 2.0 mm x 25 mm x 200 mm) (3) Glass slide (Matsunami Glass Industry, white cut plate No. 2, 1.0-1.2 mm x 26 mm x 76 mm) (4) Ultrasonic cleaner (As One CUC-O2L tabletop ultrasonic cleaner) (5) Ultrasonic cleaner (NSD ultrasonic cleaner US-20PS) (6) Glass container (250ml beaker) (7) Pure water (purified water obtained using Makuace manufactured by KURITA)

[0106] (Cleaning condition 1: When the substrate is SUS) (1) In a 25°C environment, 0.1 ml of liquid crystal sealant filled in a syringe is applied to the center of a SUS plate in a length of 2 cm using a dispenser, and left for 1 hour to create a liquid crystal sealant-coated SUS plate (Figure 1).

[0107] (2) The SUS plate coated with the liquid crystal sealant is vertically submerged in an immersion tank containing a glass container filled with 150 mL of the liquid cleaning composition of the Example or Comparative Example so that the entire liquid crystal sealant portion is immersed (Figure 2), and the following steps are carried out.

[0108] (Step 1) The SUS plate coated with the liquid crystal sealant was left submerged vertically for 5 minutes. Observe the condition of the liquid crystal sealant on the SUS plate coated with the liquid crystal sealant.

[0109] (Step2-1) After Step 1, the SUS plate coated with the liquid crystal sealant is submerged in the immersion tank. After irradiating the specimen with ultrasonic waves for 5 minutes at an output of 20 W and a frequency of 38 kHz using an ultrasonic cleaner (CUC-O2L), The SUS plate coated with the liquid crystal sealant is taken out of the immersion tank, rinsed with acetone, and dried by air blowing, and the state of the liquid crystal sealant on the SUS plate coated with the liquid crystal sealant is observed (observation 2-1).

[0110] (Step 2-2) After Observation 2-1, the cleaning composition in the immersion tank was replaced with the same unused cleaning composition, Repeat the operation of Step 2-1 and observe the state of the liquid crystal sealant on the SUS plate (Observation 2-2).

[0111] In Observation 2-2, white traces of the liquid crystal sealant on the substrate surface were found. If it is not visible, the test is terminated. If the defect is visible, vertically submerge the same liquid crystal sealant-coated SUS plate in an immersion tank containing 150 mL of the same unused liquid cleaning composition in a glass container so that the entire liquid crystal seal area is immersed, and then perform the following Step 1A, Step 2-1A, and Step 2-2A.

[0112] (Step 1A) The SUS plate coated with the liquid crystal sealant is left submerged vertically for 5 minutes.

[0113] (Step2-1A) After Step 1A, the SUS plate coated with the liquid crystal sealant is submerged in the immersion tank. After irradiating the SUS plate with ultrasonic waves at an output of 650 W and a frequency of 38 kHz for 1 hour using an ultrasonic cleaner (US-20PS), remove the SUS plate with the liquid crystal sealant from the immersion tank, rinse with acetone, and dry with air blower, and observe the state of the liquid crystal sealant on the SUS plate (Observation 2-1A).

[0114] (Step2-2A) After Observation 2-1A, the cleaning composition in the immersion tank was replaced with the same unused cleaning composition. Repeat the operation of Step 2-1A and observe the state of the liquid crystal sealant on the liquid crystal sealant-coated SUS plate (Observation 2-2A).

[0115] (3) Cleanability is judged as follows:

[0116] In observation 2-2, If no white traces of the liquid crystal sealant were visible on the surface of the substrate, the result was marked as "Good";

[0117] In Observation 2-2A, If no white traces of the liquid crystal sealant were visible on the surface of the substrate, the result was marked "△";

[0118] In Observation 2-2A, If white traces of the liquid crystal sealant application were visible on the surface of the substrate, the result was marked "X."

[0119] FIG. 3 shows the results under cleaning condition 1. Observation 2-1 (good condition) when the liquid cleaning composition of cleaning example 1-2 was used The state of Observation 2-1A and the state of Observation 2-2A (x state) when the liquid detergent composition (acetone) of Comparative Cleaning Example 1-2 was used are shown.

[0120] (Cleaning condition 2: When the substrate is glass) (1) Replace the SUS plate with a glass plate, and use a glass plate coated with liquid crystal sealant. Cleaning and observation are performed for each step under the same conditions as Cleaning Condition 1.

[0121] (2) In the case of the liquid cleaning composition of Comparative Example 2 (acetone): cleaning and observation are carried out in Step 2-2 and Step 2-2A under the same conditions as cleaning condition 1.

[0122] (3) In the case of liquid detergent compositions other than Comparative Example 2: after Step 2-1 or Step 2-1A, In Step 2-2 and Step 2-2A of cleaning condition 1, "unused cleaning agent composition" was replaced with "unused purified water," The glass plate coated with liquid crystal sealant was submerged vertically in unused pure water in an immersion tank so that the entire liquid crystal sealant portion was immersed, and ultrasonic waves were irradiated under the same conditions as in Step 2-2 and Step 2-2A.The glass plate coated with liquid crystal sealant was then removed from the pure water, rinsed with acetone, and dried with an air blower. Observation 2-2 and Observation 2-2A were then performed, and the cleaning ability was judged using the same criteria as in Cleaning Condition 1.

[0123] FIG. 4 shows the results under cleaning condition 2. Observation 2-2 (good condition) when the liquid detergent composition of Cleaning Example 1-2 was used The state (x state) of Observation 2-2A when the liquid detergent composition (acetone) of Comparative Cleaning Example 1-2 was used is shown.

[0124] [Cleaning Examples 2-1 to 2-28 and Comparative Examples 2-1 to 2-2] (Washing condition 3) (1) 3 mL of each of the liquid detergent compositions of Examples 1 to 7 and Comparative Examples 1 and 2 was filled into a 9 cc Labolan screw tube, 15 mg of compound B2 (curing agent) was immersed in, and the tube was sealed to prepare a test screw tube, which was then subjected to the following ultrasonic cleaning.

[0125] (2) The liquid detergent composition in the test screw tube in which compound B2 (hardener) is immersed is irradiated with ultrasonic waves at an output of 20 W and a frequency of 38 kHz for 5 minutes using an ultrasonic cleaner (CUC-O2L). Then, the state of compound B2 (hardener) immersed in the liquid detergent composition in the Labolan screw tube is observed, and the cleaning ability is evaluated as follows:

[0126] (3) The compound B2 (hardening agent) immersed in the liquid cleaning composition is The particles are dispersed in the liquid detergent composition without adhering to the bottom or inner wall of the Labolan screw tube. If the particles adhere to the bottom or inner wall of the Labolan screw tube but disperse in the liquid detergent composition when the Labolan screw tube is shaken, they are marked with "Good"; If the substance adheres to the bottom or inner wall of the Labolan screw tube and remains adhered even after shaking the Labolan screw tube, it is marked as "X".

[0127] Table 3 shows the results for cleaning conditions 1 and 2 (Fig. 3). Table 4 summarizes the results for washing condition 3 (FIG. 4).

[0128] [Table 3]

[0129] [Table 4]

[0130] According to Tables 3 and 4, it was found that the liquid crystal sealant containing an amine-based curing agent compound attached to a substrate with which the liquid crystal sealant came into contact or the amine-based curing agent compound used in the liquid crystal sealant could be cleaned with the liquid cleaning composition of Invention 1 at a level of roughly 0 or △.

Claims

1. Aliphatic polyhydric alcohol (compound A １ ), organic solvent (compound A ２ ) and a compound that releases a base when dissolved in water (Compound A ３ A liquid cleaning composition for a sealant for a liquid crystal display element, comprising as a main component: Compound A １ but, one or more alkylene glycols selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol; one or more alkanetriols selected from the group consisting of glycerin, trimethylolpropane, trimethylolethane, and hexanetriol; one or more alkane polyols selected from the group consisting of polyglycerols such as triglycerol, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerol, and dipentaerythritol, and intramolecular or intermolecular dehydration products of these or alkane triols; and one or more aliphatic polyhydric alcohols selected from the group consisting of polyoxyalkylene polyglyceryl ethers, Compound A ２ Compound A １ is an organic solvent that can dissolve one or more monohydric alcohols selected from the group consisting of methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, and benzyl alcohol; and one or more organic solvents selected from the group consisting of one or more ketones selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and diacetone alcohol; Compound A ３ is one or more compounds selected from the group consisting of sodium hydrogen carbonate, triethanolamine, 2-aminoethanol, 2-(2-aminoethoxy)ethanol, 3-amino-1-propanol, 2-amino-2-methyl-1-propanol, and 2-amino-2-ethyl-1,3-propanediol; Compound A １ and Compound A ２ The blending weight ratio (A １ / A ２ ) is 5 / 95 to 70 / 30, Compound A ３ The blending weight parts of the compound A １ and Compound A ２ and 0.01 to 20 parts by weight based on 100 parts by weight of the total of the above (excluding the cases where the liquid detergent composition is one of the following embodiments 1 to 3: [Aspect 1] The organic solvent contains at least one compound selected from the group consisting of N-methyl-2-pyrrolidone, normal propyl bromide, γ-butyrolactone, monoethanolamine, diethanolamine, and triethanolamine; [Aspect 2] The following formula (X): R ４ -O-(R ５ -O) ｍ -R ６ (X) (In the formula, R ４ represents an alkyl group or an aryl group having 1 to 8 carbon atoms, and R ５ represents an alkylene group having 2 to 4 carbon atoms, and R ６ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group or allyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 8; and [Embodiment 3] An embodiment in which water is blended.

2. Curable compound (compound B １ ) and an amine-based curing agent compound (Compound B ２ 2. The liquid cleaning composition according to claim 1, for cleaning a curable resin composition containing

3. The curable resin composition further contains a filler (compound B ３ 3. The liquid detergent composition according to claim 2, comprising:

4. A method for cleaning a substrate that has come into contact with the curable resin composition according to claim 2 or 3, comprising cleaning the substrate with the liquid cleaning composition according to claim 1.

Images