JP2023097311A - Liquid washing agent composition and washing method of curable composition - Google Patents

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 The present invention relates to a liquid detergent composition and a method for cleaning a specific curable resin composition using the liquid detergent composition.

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

If the sealant is a viscous fluid that easily flows, the syringe may be filled with the sealant and applied to the base material using a dispenser. It can be washed with an organic solvent such as acetone and used repeatedly.

As a sealing agent, for example, a dropping sealing agent composition containing an epoxy compound, which is a sealing agent used in the manufacture of liquid crystal display cells, has been disclosed (Patent Document 1).

JP 2013-095795 A

However, when the syringe filled with the sealant is washed and used repeatedly, there is a problem that the washability with an organic solvent such as acetone is poor depending on the sealant.

Moreover, when the sealing agent is a curable resin composition, there is a problem that the cured sealing agent after being coated on the substrate and cured adheres to the substrate and is difficult to wash.

Residue of the sealant that is not sufficiently cleaned causes deterioration of yield in the process using the sealant.

An object of the present invention is to use a curable resin composition such as a sealant to remove curable resin composition residues or curable resin composition cured bodies on the surfaces of instruments and substrates in contact with the curable resin composition. An object of the present invention is to provide a liquid detergent composition that improves detergency and a method for washing a specific curable resin composition using the liquid detergent composition.

The present invention
[1] A liquid detergent composition containing an aliphatic polyhydric alcohol (compound A ₁ ), an organic solvent (compound A ₂ ), and a compound that releases a base when dissolved in water (compound A ₃ ) (hereinafter referred to as "Invention 1" Also called);
as well as,
[2] A curable resin composition for washing a curable resin composition containing a curable compound (compound B ₁ ) and an amine-based curing agent compound (compound B ₂ ) with the liquid detergent composition described in [1] above. The present invention relates to a method for cleaning an object (hereinafter also referred to as "Invention 2").

In addition, the present inventions 1 and 2 are hereinafter collectively referred to as the "present invention".

According to the present invention, using a curable resin composition such as a sealing agent, the curable resin composition residue or the curable resin composition cured body on the surface of the instrument or substrate in contact with the curable resin composition. It is possible to provide a liquid detergent composition that improves detergency and a method for washing a specific curable resin composition using the liquid detergent composition.

It is a liquid crystal sealant coated SUS plate using Cleaning Example 1-2 in Cleaning Test 1. 1 is a schematic diagram of Step 1 of cleaning test 1. FIG. It is an example of the result of Observation 2-2, Observation 2-1A and Observation 2-2A in Cleaning Test 1. It is an example of the result of Observation 2-2 and Observation 2-2A in Cleaning Test 2.

<<Invention 1>>
The present invention 1 comprises an aliphatic polyhydric alcohol (compound A ₁ ), an organic solvent (compound A ₂ ) (excluding the compound A ₁ ), a compound that releases a base when dissolved in water (compound A ₃ ), and water It is a liquid detergent composition comprising

[Compound A ₁ ]
Compound A ₁ , which is an aliphatic polyhydric alcohol, includes dihydric alcohols having 2 to 20 carbon atoms (aliphatic diols), trihydric alcohols having 3 to 20 carbon atoms (aliphatic triols), and 4 having 5 to 20 carbon atoms. Polyhydric alcohols (aliphatic polyols) with ∼8 valences or higher are included.

Examples of aliphatic diols include
Polyglycerin such as triglycerin;
Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol; and cycloaliphatic diols such as cyclohexanediol, Cycloalkylene glycols such as cyclohexanedimethanol are included.

Aliphatic triols include, for example, alkanetriols such as glycerin, triethylene glycol, tetraethylene glycol, trimethylolpropane, trimethylolethane, and hexanetriol.

Aliphatic polyols include alkanepolyols and intramolecular or intermolecular dehydrates of these or alkanetriols, such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol; and sucrose, glucose, mannose, sugars such as fructose, methylglucoside, and their derivatives)

Aliphatic polyols include, for example, aliphatic polyhydric alcohols such as polyoxyalkylene polyglyceryl ethers.

[Compound A ₂ ]
Compound _A2 , which is an organic solvent in Invention 1, refers to an organic solvent capable of dissolving compound _A1 , 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, styrene;
ethers such as diethyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diacetone alcohol;
Nitrogens such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone;
Glycol ethers such as butyl glycol, methyl diglycol, butyl diglycol, 3-methyl-3-methoxybutanol, tetrahydrofuran;
Chlorines such as methylene chloride, chloroform, carbon tetrachloride, and chlorobenzene; and dimethylsulfoxide; at least one compound selected from the group consisting of 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.

[Compound A ₃ ]
A compound that releases a base when dissolved in water (compound A ₃ ) is added to adjust the liquid properties of the liquid detergent composition of the present invention 1 to be weakly alkaline.

Alkali metal hydroxides such as NaOH and KOH and salts of strong acids can also be used as the compound _A3 . Hydroxides, organic compounds, acid salts and normal salts of are preferred.

Weakly basic divalent or higher metal hydroxides include manganese hydroxide, iron(II) hydroxide, zinc hydroxide, lanthanum hydroxide, etc.
Examples of 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, and acetate (eg, acetic acid sodium and potassium acetate), propionate, citrate, etc.
From the viewpoint of safety during handling and waste liquid treatment, weak acid salts are preferred, and sodium hydrogen carbonate is more preferred.

[Optional component]
Various compounds may be blended as optional components within a 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, which are blended as needed from the viewpoint of rapid dispersion of the ingredients of the curable resin composition. Stabilizers (carbazide-based curing agents (e.g., 4,4′-hexamethylenebis(semicarbazide), modified amine compound-based curing agents (e.g., FXR-1020 (manufactured by T&K TOKA), etc.);
Antioxidants (phenolic compounds (e.g. 2,6-di-t-butyl-4-methylphenol, etc.), sulfur-containing compounds (e.g., dilaurylthiodipropionate, etc.), phosphorus compounds (e.g., triphenylphosphite, etc.), etc. ); and sequestering agents (eg, sodium ethylenediaminetetraacetate, sodium citrate, etc.), and the like.

[Liquid detergent composition]
The blending weight ratio (A ₁ /A ₂ ) of Compound A ₁ and Compound A ₂ in Invention 1 is preferably from 5/95 to 95/5, more preferably from 10/90 to 95/5, from the viewpoint of fluidity and washability. 80/20, more preferably 15/85 to 70/30, more preferably 20/80 to 65/35, still more preferably 30/70 to 55/45, still more preferably 40/60 to 50/50.

From the viewpoint of solubility and detergency, the amount of compound _A3 in Invention 1 is preferably 0.01 to 20 parts by weight, more preferably 0.01 to 20 parts by weight, based on a total of 100 parts by weight of compound _A1 and compound _A2 . is 0.02 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, more preferably 0.10 to 5 parts by weight, still more preferably 0.12 to 3 parts by weight.

[Curable resin composition]
The present invention 1 is a curable resin used for applications such as photocurable adhesives, thermosetting adhesives, sealants (preferably liquid crystal sealants), coating agents, light shielding agents, gap agents, and shock absorbers. It can be preferably used for cleaning the composition and its cured body, and can be used more preferably for cleaning the curable resin composition and its cured body of the present invention 2 described below.

<<Invention 2>>
Invention 2 is a curable resin composition for cleaning a curable resin composition containing a curable compound (compound B ₁ ) and an amine-based curing agent compound (compound B ₂ ) with the liquid detergent composition of Invention 1. It is a method of washing things.

[Curable compound (compound B ₁ )]
The compound _B1 is preferably a compound that can be cured by heat, more preferably a compound that can be cured by light and heat. One or more compounds selected from the group consisting of epoxy resins, partially (meth)acrylated epoxy resins and (meth)acrylic resins are preferred, and partially (meth)acrylated epoxy resins are more preferred.

In addition, in this specification,
(Meth) acrylic means methacrylic and / or acrylic,
(meth)acrylate means methacrylate and/or acrylate,
(Meth)acrylated epoxy resin means a resin in which all epoxy groups in the epoxy resin have reacted with (meth)acrylic acid,
A partially (meth)acrylated epoxy resin means a resin in which some 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.

As the epoxy resin, preferably
bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, Alicyclic epoxy resins, aliphatic linear epoxy resins, glycidyl ester-type epoxy resins, glycidylamine-type epoxy resins, hydantoin-type epoxy resins, isocyanurate-type epoxy resins, phenol novolac-type epoxy resins having a triphenolmethane skeleton;
Diglycidyl-etherified products of bifunctional phenols, diglycidyl-etherified products of bifunctional alcohols, their halides, and hydrogenated products;
As polyfunctional epoxy resins, trifunctional and tetrafunctional epoxy resins, etc.;
In addition, epoxy resins described in JP-A-2012-077202 are also included.

(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 and a catalyst (e.g., benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.) to an epoxy resin, and a polymerization inhibitor (e.g., , methoquinone, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) and performing an esterification reaction at, for example, 80 to 110°C to (meth)acrylate all or part of the epoxy groups. can. The epoxy resin used as a raw material is not particularly limited, and examples thereof include the epoxy resins exemplified above.

In the partially (meth)acrylated epoxy resin, the ratio of (meth)acrylic groups to the total number of moles of (meth)acrylic groups and epoxy groups in the resin is preferably 10 to 90 mol%, more preferably 40. ~60 mol%.

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

The (meth)acrylic resin is not particularly limited as long as it is a resin having a methacrylic and/or acrylic group, and includes (meth)acrylic acid esters.

A hydroxy group-containing (meth)acrylate can be used as the (meth)acrylic resin,
For example, 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)acrylate (glycerin mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, ditrimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc.) , Alkylene oxide-added polyol (meth)acrylate (e.g., alkylene oxide-added trimethylolpropane di(meth)acrylate, alkylene oxide-added pentaerythritol tri(meth)acrylate, alkylene oxide-added dipentaerythritol penta(meth)acrylate, etc.) mentioned.

An alicyclic (meth)acrylate can be used as the (meth)acrylic resin,
For example, 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 , dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and adamantyl (meth)acrylate.

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

Examples of commercially available (meth)acrylate oligomers having a polyisoprene skeleton include "UC-203M" (weight average molecular weight: 35,000) manufactured by Kuraray Co., Ltd. Commercially available (meth)acrylate oligomers containing polybutadiene in the skeleton. Examples thereof include "TE 2000" (weight average molecular weight: 2500) manufactured by Nippon Soda Co., Ltd.

Compound _B1 may be one of these curable compounds, or two or more of them may be used in combination, and from the viewpoint of being curable by both light and heat, it preferably contains a partially (meth)acrylated epoxy resin, For example, partially (meth)acrylated bisphenol A type epoxy resin is more preferable.

[Amine Curing Agent Compound (Compound Part B ₂ )]
The curable resin composition of the present invention 2 contains compound _B2 as a thermosetting agent from the viewpoint of imparting mechanical strength such as breaking strength to the film after thermosetting.

The amine-based curing agent compound (compound B2) has poor solubility and dispersibility in organic solvents, and tends to swell to become more adhesive to the base material. It tends to make cleaning of the composition difficult.

Compound _B2 may have at least one active hydrogen 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;
a secondary di- or polyamine compound having two or more secondary amino groups in the molecule;
Adduct compounds of hydrazide compounds or imidazole compounds, epoxy resins, and urea;
Homogeneous mixed crystals such as polyamine compounds and polyamine compounds;
mixed crystals of different types such as polyamine compounds and hydrazide compounds; and mixed crystals of hydrazide compounds and hydrazide compounds.

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

As hydrazide compounds, monobasic hydrazide having one hydrazide group in the molecule, dibasic hydrazide having two hydrazide groups in the molecule, tribasic hydrazide having three hydrazide groups in the molecule, Polyfunctional hydrazides having 4 or more hydrazide groups within are included.

Specific examples of monobasic hydrazides include acetohydrazide, propionic hydrazide, pentanoic hydrazide, lauric hydrazide, cyclohexanecarbohydrazide, salicylic hydrazide, p-hydroxybenzoic hydrazide, naphthoic hydrazide, and benzenesulfonohydrazide. be done.

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, dodecanoic acid dihydrazide, hexadecane dihydrazide acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, carbohydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 1,4-naphthoic acid dihydrazide, 4,4′-bisbenzene dihydrazide, hydroquinone diglycolic acid dihydrazide, resorcinol diglycolic acid dihydrazide, catechol diglycolic acid dihydrazide, 4,4′-ethylidenebisphenol-diglycolic acid dihydrazide, 4,4′ vinylidenebisphenol-diglycolic acid and dihydrazides.

Tribasic acid hydrazides include, for example, 1,3,5-tris(2-hydrazinocarbonylalkyl)isocyanurates such as 1,3,5-tris(2-hydrazinocarbonylethyl)isocyanurates.

Examples of polyfunctional hydrazides include polyacrylic acid hydrazides.

Examples of commercially available organic acid dihydrazides include VDH (1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin), ADH (adipic acid dihydrazide), UDH (7,11-octadecadien-1, 18-dicarbohydrazide) and LDH (octadecane-1,18-dicarboxylic acid dihydrazide).

The imidazole compound is an imidazole compound that does not have a primary amino group in the molecule, for example
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;
Imidazole compounds substituted at the nitrogen atom at position 1, such as 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.

The adduct compound of an amine compound and an epoxy resin includes the above-described primary di- or polyamine compounds having two or more primary amino groups in the molecule, and the secondary di- or polyamine compounds having two or more secondary amino groups in the molecule. An amine adduct compound or amine adduct compound derivative obtained by adducting a class di- or polyamine compound, hydrazide compound, or imidazole compound to an epoxy resin It is also called “○○○-type curing agent” (for example, “amine adduct-type curing agent”).

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

A reaction product of an amine compound and an isocyanate compound disclosed in Patent Document 1 can also be preferably used as the compound _B2 .

Compound _B2 may be used alone or in combination with the above compounds.

[Optional component]
(Filler (Compound B ₃ ))
Invention 1 functions favorably even when the curable resin composition of Invention 2 further contains Compound _B3 , which is a hard-to-clean filler.

The compound part _B3 improves the adhesive reliability of the curable resin composition by controlling the viscosity of the curable resin composition, improving the strength of the cured product obtained by curing the curable resin composition, or suppressing the linear expansion property. It is added for purposes such as

Examples of the compound portion _B3 include known inorganic fillers and organic fillers, and organic fillers are preferable from the viewpoint of stress relaxation.

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. is mentioned.

As organic fillers, poly(meth)acrylic acid esters such as poly(methyl methacrylate) and poly(ethyl(meth)acrylate), polystyrene, copolymers obtained by copolymerizing these monomers with other monomers, polyesters Microparticles, polyurethane microparticles, and rubber microparticles are included.

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

In the curable resin composition of the present invention 2, those that have a photosensitizing effect and function as a photopolymerization initiator are generally classified as visible-light-sensitizing compounds, and photopolymerization initiators. do.

The photopolymerization initiator may be a combination of a photoinitiator compound (a compound that is photoexcited by a visible light-sensitizing compound and becomes a polymerization initiation species) and a visible light-sensitizing compound.

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

Specifically, the photopolymerization initiator is
Benzoins, acetophenones, benzophenones, thioxanthones, α-acyloxime esters, phenylglyoxylates, benzils, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, dialkylaminobenzoyl group-containing poly Ether compounds, benzoin ethers and anthraquinones, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducible dyes and the like.

The photoinitiator is
Preferably, it contains a polyether compound having a dialkylaminobenzoyl group, which is a photoinitiator compound,
More preferably, it contains a thioxanthone compound that is a visible light-sensitizing compound,
More preferably, a polyether compound having a dialkylaminobenzoyl group and a thioxanthone compound are used in combination.

（式（１）中、ｎ１は、０～５０であり、好ましくは１～４５である）で表される化合物が好ましく、下記式（２）：

（式（２）中、ｎ２は、０～５０であり、好ましくは１～４５である）で表されるチオキサントン類化合物が好ましい。 As a polyether compound having a dialkylaminobenzoyl group, the following formula (1):

(In formula (1), n1 is 0 to 50, preferably 1 to 45) is preferably a compound represented by the following formula (2):

A thioxanthone compound represented by (wherein n2 is 0 to 50, preferably 1 to 45) is preferred.

A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type.

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

A 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).

Coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane.

A coupling agent may be used independently and may be used in combination of 2 or more types.

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

Phenolic polymerization inhibitors include 2,2-methylene-bis(4-methyl-6-tert-butylphenol) (BHT), catechol, picric acid, tert-butyl catechol, 2,6-ditert-butyl-p- cresol, and 4,4′-thiobis[ethylene(oxy)(carbonyl)(ethylene)]bis[2,6-bis(1,1-dimethylethyl)phenol].

Phenothiazine-based polymerization inhibitors include phenothiazine, bis(α-methylbenzyl)phenothiazine, 3,7-dioctylphenothiazine, and bis(α,α-dimethylbenzyl)phenothiazine.

Phenolic polymerization inhibitors such as BHT can also be used as antioxidants.

(others)
The curable resin composition of the present invention 2 contains dispersants, coloring components such as pigments and dyes, storage stabilizers, plasticizers, viscoelasticity modifiers, and surfactant modifiers (wetting agents and antifoaming agents). good too.

When utilizing the photocurability of the curable resin composition of the present invention 2, it is preferable to use coloring components such as pigments and dyes within a range that does not affect the ultraviolet transmittance.

[Curable resin composition]
From the viewpoint of viscosity that can be handled as a sealant and mechanical properties such as mechanical strength and viscoelasticity of the cured product, the amount of compound _B1 in the curable resin composition is
It is preferably 10 to 90% by weight, more preferably 20 to 85% by weight, still more preferably 30 to 80% by weight.

From the viewpoint of mechanical properties such as mechanical strength and viscoelasticity of the cured product, the amount of compound _B2 in the curable resin composition is
For 100 parts by weight of compound B ₁ ,
It is preferably 1 to 40 parts by weight, more preferably 5 to 35 parts by weight.

The amount of compound _B3 in the curable resin composition is, from the viewpoint of controlling the coefficient of linear expansion and maintaining the shape after seal application, relative to 100 parts by weight of compound _B1 ,
It is preferably 2 to 40 parts by weight, more preferably 5 to 30 parts by weight.

The amount of the photopolymerization initiator in the curable resin composition is, for example, from the viewpoint of temporary fixability by photocuring, with respect to 100 parts by weight of the compound B ₁ ,
It is preferably 0.1 to 10.0 parts by weight, more preferably 0.5 to 5.0 parts by weight.

If necessary, the amount of the coupling agent in the curable resin composition is
For 100 parts by weight of compound B ₁ ,
It is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.

[Method for cleaning curable resin composition]
The second aspect of the present invention is a curable resin composition-contacting substrate for cleaning a substrate contacted by the above-mentioned curable resin composition (hereinafter referred to as "curable resin composition") with the liquid detergent composition according to claim 1. It is a cleaning method for materials.

In the present invention 2, the substrate with which the curable resin composition is in contact means, for example, a syringe tube, syringe head, or nozzle filled with the curable resin composition for coating the curable resin composition. Components that constitute a syringe or are attached to a syringe, such as containers, dispensers that discharge curable resin compositions, tubes and pipes through which curable resin compositions pass, jigs and parts for fixing them, for scooping resin compositions The spatula used for

Materials for the substrate include metals such as SUS; ceramics such as glass and pottery; plastics, Teflon, silicon and the like.

Examples of the method for cleaning the substrate contacted by the curable resin composition of the present invention 2 include the following.
(1) Depending on the cured state of the adhered resin and the volatility of the organic solvent, the liquid detergent composition of the present invention 1 is applied to the base material in contact with the curable resin composition,
preferably 5 to 50°C, more preferably 10 to 40°C, still more preferably 15 to 30°C,
Immersion for preferably 10 minutes to 10 days, more preferably 15 minutes to 5 days, still more preferably 30 minutes to 24 hours, still more preferably 1 to 6 hours, still more preferably 1 to 3 hours, still more preferably 1 to 2 hours After that, if necessary, the substrate is rinsed with water, or an organic solvent such as acetone or acetone containing 5% or more of water, and dried at room temperature by air drying or the like.

(2) Ultrasonic cleaning (preferably degassing ultrasonic cleaning) by immersing the base material in contact with the curable resin composition in the liquid detergent composition of the present invention 1, and then irradiating ultrasonic waves while the base material is immersed. After that, if necessary, it is rinsed with water, or an organic solvent such as acetone or acetone containing 5% or more of water, and dried.

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 transducers, and the amount of cleaning liquid,
The output per ultrasonic transducer is preferably 15 to 2000 W, more preferably 20 to 1200 W, still more preferably 30 to 600 W,
Depending on the type of damage and dirt to be given to the base material,
The frequency is preferably 15 to 270 kHz, more preferably 20 to 150 kHz, still more preferably 30 to 105 kHz,
It is preferably 1 to 120 minutes, more preferably 10 to 60 minutes, still more preferably 30 to 60 minutes, depending on the volatilization of the liquid detergent composition.

Ultrasonic cleaning may be repeated multiple times, and when repeated multiple times, it is preferable to appropriately replace the immersed liquid cleaning composition with unused liquid cleaning composition.

"Example"
[Detergent Composition Examples 1 to 28 and Comparative Examples 1 to 3]

で表されるポリオキシエチレンポリグリセリルエーテル（製造元：阪本薬品工業株式会社、製品名：ＳＣ－Ｅ７５０、数平均分子量：７５０、水酸基価：約３００） [1] Raw material (compound A ₁ )
(1) Ethylene glycol (manufacturer: Kanto Chemical Co., Ltd., quality: Shika 1st grade)
(2) Triethylene glycol (manufacturer: Kanto Chemical Co., Ltd., quality: Shika 1st grade)
(3) Tetraethylene glycol (manufacturer: Kanto Chemical Co., Ltd., quality: Shika 1st grade)
(4) Formula (3) below:

Polyoxyethylene polyglyceryl ether represented by (manufacturer: Sakamoto Yakuhin Kogyo Co., Ltd., product name: SC-E750, number average molecular weight: 750, hydroxyl value: about 300)

(Compound _A2 )
(1) Ethanol (manufacturer: Kanto Chemical Co., Ltd., quality: special grade)
(2) Acetone (manufacturer: Kanto Chemical Co., Ltd., quality: Shika 1st grade)

(Compound A ₃ )
(1) Sodium bicarbonate (manufacturer: Kanto Chemical Co., Ltd., quality: Shika 1st grade)
(2) 2-aminoethanol (manufacturer: Tokyo Chemical Industry Co., Ltd., liquid, pH = 12.1 (100g/l, _H2O , 20°C)
(3) 3-amino-1-propanol (manufacturer: Kanto Chemical Co., Ltd., liquid, pH = 11.6 (10g/l, _H2O , 20°C)
(4) 2-(2-aminoethoxy) ethanol (manufacturer: Tokyo Chemical Industry Co., Ltd., liquid, pH = 10.2 (10g/l, _H2O , 20°C)
(5) 2-amino-2-ethyl-1,3-propanediol (manufacturer: Tokyo Chemical Industry Co., Ltd., solid)

(Optional component)
(1) Stabilizer: 4,4'-hexamethylenebis(semicarbazide) (curing agent described in WO2014/010446)

[2] Blending conditions Weigh other raw materials so that the parts by weight shown in Table 1 are added to a total of 100 parts by weight (100 g) of compound A ₁ and compound A ₂ , and add the compound to a beaker (300 ml). After filling A ₁ and compound A ₂ , add other raw materials, stir with a stirrer at 70 ° C. for 300 minutes, add volatile raw materials according to the degree of volatilization, 28 and Comparative Examples 1 to 3 were obtained.

[3] Liquidity (solubility)
Observing the dissolution state of the liquid detergent compositions of Examples 1 to 28 and Comparative Examples 1 to 3 obtained under the above formulation conditions,
〇 when dissolved without undissolved residue
△,
× when the raw material that was originally blended remains almost as it is,
and evaluated.

で表される部分メタクリル化ビスフェノールＡ型エポキシ樹脂（ＷＯ2014/057871段落0092記載の方法で製造した） [Liquid crystal sealant]
(material)
(1-1) Compound B ₁
(1-1-1) Formula (4) below:

Partially methacrylated bisphenol A type epoxy resin represented by (produced by the method described in paragraph 0092 of WO2014/057871)

(1-2) compound _B2
(1-2-1) ADEKA HARDNER EH-5057P (manufactured by ADEKA, amine adduct curing agent)
(1-2-2) ADEKA HARDNER EH-5030S (manufactured by ADEKA, amine adduct curing agent)
(1-2-3) ADEKA HARDNER EH-5015S (manufactured by ADEKA, amine adduct curing agent)
(1-2-4) ADEKA HARDNER EH-4358S (manufactured by ADEKA, amine adduct curing agent)
(1-2-5) ADEKA HARDNER EH-5011S (manufactured by ADEKA, imidazole curing agent)
(1-2-6) FXR-1020 (manufactured by T&K TOKA, modified amine compound-based curing agent)
(1-2-7) FXR-1081 (manufactured by T&K TOKA, modified amine compound-based curing agent)

(1-3) Compound B ₃
(1-3-1) Zephiac F-351 (manufactured by Adeka Kogyo Co., Ltd., core-shell type acrylic resin filler)
(1-3-2) Seahoster KE-C050HG (manufactured by Nippon Shokubai Co., Ltd., silica spherical fine particles)

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

(Blending conditions)
With respect to 100 parts by weight (5 g) of compound B ₁ , other raw materials were weighed so that the parts by weight shown in Table 2 were obtained, and a plastic cup (20 ml) was filled with compound B ₁ and compound B ₂ . , and other raw materials were added and mixed, and kneaded at 25° C. for 2 minutes by a three-one motor (RW28basic manufactured by IKA Co.) to uniformly disperse liquid crystal sealants 1 to 4.

[Washing Examples 1-1 to 1-28 and Washing Comparative Examples 1-1 to 1-2]
(Tools: common for cleaning conditions 1 to 3)
(1) Syringe (TERUMO, SS-01T for 1 ml tuberculin)
(2) SUS plate (SUS304 manufactured by Engineering Test Service, 2.0 mm × 25 mm × 200 mm)
(3) Slide glass (manufactured by Matsunami Glass Industry, white cut plate No. 2, 1.0 to 1.2 mm × 26 mm × 76 mm)
(4) Ultrasonic cleaner (desktop ultrasonic cleaner CUC-O2L manufactured by AS ONE)
(5) Ultrasonic cleaner (NSD ultrasonic cleaner US-20PS)
(6) Glass container (250ml beaker)
(7) Pure water (pure water obtained by KURITA Makuace)

(Cleaning condition 1: when the base material is SUS)
(1) In an environment of 25 ° C, apply 0.1 ml of liquid crystal sealant filled in a syringe to the center of the SUS plate with a dispenser to a length of 2 cm, and leave it for 1 hour to make the liquid crystal sealant coated SUS plate. (Fig. 1).

(2) The liquid crystal sealant-coated SUS plate is placed in an immersion tank in which a glass container is filled with 150 mL of the liquid cleaning composition of Example or Comparative Example, and the liquid crystal sealant-coated SUS plate is completely immersed in the liquid crystal seal portion. Sink vertically (Fig. 2) and perform the following steps.

(Step 1)
Leave the liquid crystal sealant coated SUS plate vertically submerged for 5 minutes,
Observe the state of the liquid crystal sealant on the SUS plate coated with the liquid crystal sealant.

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

(Step2-2)
After observation 2-1, replace the cleaning composition in the immersion tank with the same unused cleaning composition,
Repeat Step 2-1 to observe the state of the liquid crystal sealant on the SUS plate coated with the liquid crystal sealant (Observation 2-2).

In Observation 2-2, white traces of liquid crystal sealant coating on the base material surface,
If not visible, terminate the test and
If visible, the same liquid crystal sealant-coated SUS plate was placed in an immersion tank filled with 150 mL of the same unused liquid cleaning composition in a glass container, and the liquid crystal sealant-coated SUS plate was completely immersed in the liquid crystal seal part. Sink the board vertically and perform Step 1A, Step 2-1A and Step 2-2A below.

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

(Step2-1A)
After Step 1A, while the liquid crystal sealant coated SUS plate is submerged in the immersion tank,
After irradiating ultrasonic waves with an output of 650 W and a frequency of 38 kHz with an ultrasonic cleaner (US-20PS) for 1 hour, the SUS plate coated with the liquid crystal sealant is taken out from the dipping tank, rinsed with acetone and air blown to dry, and the liquid crystal seal is applied. Observe the state of the liquid crystal sealant on the agent-coated SUS plate (Observation 2-1A).

(Step2-2A)
After observation 2-1A, replace the cleaning composition in the immersion tank with the same unused cleaning composition,
Repeat Step 2-1A to observe the state of the liquid crystal sealant on the SUS plate coated with the liquid crystal sealant (Observation 2-2A).

(3) Detergency is judged as follows:

Observation 2-2,
"○" when no white traces of the liquid crystal sealant coating on the base material surface were visible;

In observation 2-2A,
"△" when the white traces of the liquid crystal sealant application traces on the base material surface were not visible;

In observation 2-2A,
"x" when white traces, which are coating traces of the liquid crystal sealant, can be visually recognized on the base material surface.

In FIG. 3, in washing condition 1,
Observation 2-1 (O state) when using the liquid detergent composition of Cleaning Example 1-2 and Observation 2 when using the liquid detergent composition (acetone) of Comparative Cleaning Example 1-2 The state of -1A and the state of observation 2-2A (x state) are shown.

(Washing condition 2: when the substrate is glass)
(1) Replace the SUS plate with a glass plate to use a glass plate coated with a liquid crystal sealant, and perform cleaning and observation in each step under the same conditions as the cleaning condition 1.

(2) In the case of the liquid detergent composition (acetone) of Comparative Example 2: Washing and observation in Steps 2-2 and 2-2A are performed under the same conditions as in washing condition 1.

(3) For liquid detergent compositions other than Comparative Example 2: After Step 2-1 or Step 2-1A,
Replace "unused detergent composition" in Step 2-2 and Step 2-2A of Cleaning Condition 1 with "unused pure water",
After irradiating ultrasonic waves under the same conditions as Step 2-2 and Step 2-2A while the liquid crystal sealant coated glass plate is vertically submerged in unused pure water in the immersion tank so that the liquid crystal seal part is completely immersed, The glass plate coated with the liquid crystal sealant was taken out from the pure water, rinsed with acetone, dried by blowing air, and observed 2-2 and 2-2A were performed.

In FIG. 4, in washing condition 2,
Observation 2-2 (O state) when using the liquid detergent composition of Cleaning Example 1-2 and Observation 2 when using the liquid detergent composition (acetone) of Comparative Cleaning Example 1-2 -2A state (X state) is shown.

[Washing 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 in a Labran screw tube (9 cc), immersed in 15 mg of compound B ₂ (curing agent), sealed, and tested. As a screw tube for use, perform the following ultrasonic cleaning.

(2) After irradiating the liquid detergent composition in which the compound B ₂ (curing agent) was immersed in the test screw tube with an ultrasonic cleaner (CUC-O2L) at an output of 20 W and a frequency of 38 kHz for 5 minutes, Observe the state of compound B ₂ (curing agent) immersed in the liquid detergent composition in the labran screw tube, and judge the detergency as follows:

(3) Compound B ₂ (curing agent) immersed in the liquid detergent composition is
It does not adhere to the bottom or inner wall of the labrun screw tube and is dispersed in the liquid detergent composition,
"○" indicates a case where even if it adheres to the bottom or inner wall of the Lab-run screw tube, it disperses in the liquid detergent composition when the Lab-run screw tube is shaken;
"x" when it adheres to the bottom or inner wall of the lab run screw tube and remains attached even when the lab run screw tube is shaken.

Table 3 shows the results for washing conditions 1 and 2 (Fig. 3),
Table 4 summarizes the results for washing condition 3 (FIG. 4).

According to Tables 3 and 4, the liquid crystal sealing agent containing an amine-based curing agent compound adhered to the base material in contact with the liquid crystal sealing agent or the amine-based curing agent compound used in the liquid crystal sealing agent is the liquid cleaning agent of the present invention 1. It was found that when washed with the agent composition, it was possible to wash at a level of ◯ or △.

Claims (6)

A liquid detergent composition containing an aliphatic polyhydric alcohol (compound A ₁ ), an organic solvent (compound A ₂ ) (excluding compound A ₁ ), and a compound (compound A ₃ ) that releases a base when dissolved in water . The liquid detergent composition according to claim 1, for cleaning a curable resin composition containing a curable compound (compound _B1 ) and an amine-based curing agent compound (compound _B2 ). The liquid detergent composition according to claim 2, wherein the curable resin composition further contains a filler (compound _B3 ). 3. The liquid detergent composition according to claim 2, wherein said curable resin composition is a sealant. 5. The liquid detergent composition according to claim 4, wherein said curable resin composition is a sealant for liquid crystal display elements. A method for cleaning a substrate in contact with a curable resin composition, comprising cleaning a substrate contacted by the curable resin composition according to any one of claims 2 to 4 with the liquid detergent composition according to claim 1.

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