JP7734966B2 - Liquid cleaning composition and cleaning method using curable composition - Google Patents

Description

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

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.

If the sealant is a viscous fluid that flows easily, it may be filled into a syringe and applied to the 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.

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

JP 2013-095795 A

However, when syringes filled with sealant are washed and reused, some sealants have the problem of poor cleanability with organic solvents such as acetone.

Furthermore, when the sealant is a curable resin composition, there is an issue that after it is applied to a substrate and cured, the cured sealant adheres to the substrate and is difficult to clean.

Sealant residue that is not thoroughly cleaned off causes a decrease in yield in processes that use sealant.

An object of the present invention is to provide a liquid cleaner composition that uses a curable resin composition such as a sealant to improve the cleaning properties 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.

The present invention provides
[1] A liquid detergent composition comprising 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 also referred to as “present invention 1”);
and,
[2] The present invention relates to a method for cleaning a curable resin composition, which comprises cleaning a curable resin composition containing a curable compound (compound _B1 ) and an amine-based curing agent compound (compound _B2 ) with the liquid cleaning composition described in the above item [1] (hereinafter also referred to as "present invention 2").

In the following, Inventions 1 and 2 will be collectively referred to as "the present invention."

The present invention provides a liquid cleaning 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 cleaning composition.

This is a SUS plate coated with a liquid crystal sealant using cleaning example 1-2 in cleaning test 1. FIG. 1 is a schematic diagram of Step 1 of cleaning test 1. 1 shows examples of the results of Observation 2-2, Observation 2-1A, and Observation 2-2A in Cleaning Test 1. 10 shows examples of the results of Observation 2-2 and Observation 2-2A in Cleaning Test 2.

<<The First Invention>>
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.

[Compound A ₁ ]
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.

Examples of aliphatic diols include alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol; and alicyclic diols, such as cycloalkylene glycols such as cyclohexanediol and cyclohexanedimethanol.

Examples of the aliphatic triol include alkanetriols such as glycerin, trimethylolpropane , trimethylolethane, and hexanetriol.

Examples of aliphatic polyols include polyglycerols such as triglycerol; alkane polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerol, 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 derivatives thereof.

Examples of aliphatic polyols include aliphatic polyhydric alcohols such as polyoxyalkylene polyglyceryl ethers.

[Compound A ₂ ]
The compound _A2 , which is an organic solvent in invention 1, refers to an organic solvent capable of dissolving 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;
at least one compound selected from the group consisting of chlorine compounds such as methylene chloride, chloroform, carbon tetrachloride, and chlorobenzene; and dimethyl sulfoxide; and 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 ]
The compound that releases a base when dissolved in water (compound A ₃ ) is added to adjust the liquid property of the liquid detergent composition of invention 1 to weak alkaline.

As Compound _A3 , hydroxides of alkali metals such as NaOH and KOH and salts of strong acids can be used. However, from the viewpoint of stable pH and ease of adjustment of the amount added, hydroxides of weakly basic divalent or higher metals, organic compounds, acid salts and normal salts are preferred.

Examples of weakly basic hydroxides of divalent or higher metals include manganese hydroxide, iron (II) hydroxide, zinc hydroxide, and lanthanum hydroxide.
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 hydrogencarbonate, formate, acetate (e.g., sodium acetate, potassium acetate, etc.), propionate, and citrate.
From the viewpoint of safety during handling and waste liquid disposal, salts of weak acids are preferred, and sodium bicarbonate is more preferred.

[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,
From the viewpoint of rapid dispersion of the components of the curable resin composition, esters such as ethyl acetate, propyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, diethyl carbonate, dimethyl carbonate, and propylene carbonate may be blended as needed; 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 Corporation));
Antioxidants (phenolic compounds (e.g., 2,6-di-t-butyl-4-methylphenol), sulfur-containing compounds (e.g., dilauryl thiodipropionate), phosphorus compounds (e.g., triphenyl phosphite), etc.); and sequestering agents (e.g., sodium ethylenediaminetetraacetate, sodium citrate), etc.

[Liquid detergent composition]
In 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, still more preferably 20/80 to 65/35, still more preferably 30/70 to 55/45, and still more preferably 40/60 to 50/50, from the viewpoints of flowability and detergency.

[Curable resin composition]
The present invention 1 can be suitably used for cleaning curable resin compositions and cured products thereof that are used for applications such as photocurable adhesives, thermosetting adhesives, sealants (preferably liquid crystal sealants), coating agents, light-shielding agents, gap agents, and impact-resistant absorbers, and can be even more suitably used for cleaning curable resin compositions and cured products thereof that are the present invention 2 described below .

[Curable resin composition]
The present invention 1 can be suitably used for cleaning curable resin compositions and cured products thereof that are used for applications such as photocurable adhesives, thermosetting adhesives, sealants (preferably liquid crystal sealants), coating agents, light-shielding agents, gap agents, and impact-resistant absorbers, and can be even more suitably used for cleaning curable resin compositions and cured products thereof that are the present invention 2 described below .

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

[Curable compound (compound B ₁ )]
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.

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 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.

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, linear aliphatic 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 having a triphenolmethane skeleton;
diglycidyl ethers of difunctional phenols, diglycidyl ethers of difunctional alcohols, and halides and hydrogenated products thereof;
Polyfunctional epoxy resins include trifunctional and tetrafunctional epoxy resins;
Further, epoxy resins described in JP 2012-077202 A can be used.

(Meth)acrylated epoxy resins and partially (meth)acrylated epoxy resins can be obtained by reacting epoxy resin 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.) is 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 the raw material is not particularly limited, and examples include the epoxy resins exemplified above.

Partially (meth)acrylated epoxy resins preferably have a (meth)acrylic group ratio 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.

Partially (meth)acrylated epoxy resins preferably contain compounds containing one or more epoxy groups and one or more (meth)acrylic groups per molecule.

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

As the (meth)acrylic resin, a hydroxy group-containing (meth)acrylate can be used,
Examples thereof 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.), 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.).

As the (meth)acrylic resin, an alicyclic (meth)acrylate can be used,
Examples of the acrylate 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.

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

A commercially available (meth)acrylate oligomer with a polyisoprene backbone is, for example, "UC-203M" (weight average molecular weight: 35,000) manufactured by Kuraray Co., Ltd., and a commercially available (meth)acrylate oligomer with a polybutadiene backbone is, for example, "TE 2000" (weight average molecular weight: 2,500) manufactured by Nippon Soda Co., Ltd.

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.

[Amine-based curing agent compound (compound B ₂ )]
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.

Amine-based curing agent compounds (compound B2) have poor solubility and dispersibility in organic solvents and tend to swell, making them prone to adhering to substrates, which tends to make curable resin compositions containing them difficult to clean.

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;
a secondary di- or polyamine compound 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.

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, 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, with aromatic polyamines such as o-xylylenediamine, m-xylylenediamine, and p-xylylenediamine being preferred.

Hydrazide compounds 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.

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

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, and Examples 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'-bisbenzene dihydrazide, 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.

Examples of tribasic acid hydrazides include 1,3,5-tris(2-hydrazinocarbonylalkyl)isocyanurates such as 1,3,5-tris(2-hydrazinocarbonylethyl)isocyanurate.

Examples of polyfunctional hydrazides include polyacrylic acid hydrazide.

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).

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;
Imidazole compounds in which the nitrogen atom at position 1 is substituted include, for example, 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 is an amine adduct compound or amine adduct compound derivative in which the aforementioned primary di- or polyamine compound having two or more primary amino groups in the molecule, secondary di- or polyamine compound having two or more secondary amino groups in the molecule, hydrazide compound, or imidazole compound is adducted to an epoxy resin (hereinafter, curing agents containing these compounds will also be referred to as "XX-based curing agents" (e.g., "amine adduct-based curing agents")).

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

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

The compound _B2 may be any of the above compounds used alone or in combination.

[Optional ingredients]
(Filler (Compound _B3 ))
Invention 1 also functions favorably when the curable resin composition of Invention 2 further contains Compound B ₃ , which is a filler that is difficult to wash off.

Compound _B3 is added for the purposes of controlling the viscosity of the curable resin composition, improving the strength of the cured product obtained by curing the curable resin composition, or suppressing linear expansion to improve the adhesive reliability of the curable resin composition.

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

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.

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 make up these with other monomers, polyester fine particles, polyurethane fine particles, and rubber fine particles.

(Photopolymerization initiator)
When the curable resin composition of the 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 optimum 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; and 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.

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

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.

In the photopolymerization initiator, the molar ratio of the photoinitiator compound to the visible light-sensitized compound (photoinitiator compound/visible light-sensitized 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.

Specifically, the photopolymerization initiator is
Examples of the organic solvent 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.

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.

The polyether compound having a dialkylaminobenzoyl group includes a compound represented by the following formula (1):

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

(wherein n2 is an integer of 0 to 50, preferably 1 to 45) is preferred.

The photopolymerization initiator may be used alone or in combination of two or more types.

(Coupling Agent)
The curable resin composition in the second invention may contain a coupling agent.

Coupling agents are added to further improve the adhesion of the curable resin composition to the substrate (e.g., liquid crystal display substrate).

Examples of coupling agents include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane.

Coupling agents may be used alone or in combination of two or more types.

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

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

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

Phenol-based polymerization inhibitors such as BHT can also be used as antioxidants.

(others)
The curable resin composition in the second aspect of the present invention 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).

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 amounts that do not affect UV transmittance.

[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.

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.
Compound B ₁ relative to 100 parts by weight
The amount is preferably 1 to 40 parts by weight, more preferably 5 to 35 parts by weight.

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 seal application,
The amount 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 fixation by photocuring, based on 100 parts by weight of the compound _B1 .
The amount is preferably 0.1 to 10.0 parts by weight, more preferably 0.5 to 5.0 parts by weight.

The amount of the coupling agent in the curable resin composition may be adjusted as needed.
Compound B ₁ relative to 100 parts by weight
The amount 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 method for cleaning a substrate that has come into contact with the curable resin composition described above (hereinafter referred to as the "curable resin composition"), by cleaning the substrate with the liquid cleaning composition described in the first aspect of the present invention.

In present invention 2, examples of substrates that 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 for coating the curable resin composition, a container, a dispenser that dispenses the curable resin composition, a tube or pipe through which the curable resin composition passes, a jig or part that secures them, and a spatula used to scoop up the resin composition.

Examples of substrate materials include metals such as SUS; ceramics such as glass and pottery; plastics, Teflon, and silicon.

Examples of methods for cleaning a substrate that has come into contact with the curable resin composition of present invention 2 include the following.
(1) The substrate that has been contacted with the curable resin composition is then subjected to the liquid cleaning composition of the present invention 1 depending on the curing state of the adhered 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 film 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, for example.

(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. If necessary, the substrate is then rinsed with water or an organic solvent such as acetone or acetone containing 5% or more water, and then 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 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.

Ultrasonic cleaning may be repeated multiple times. If repeated multiple times, it is preferable to replace the immersed liquid cleaning composition with unused liquid cleaning composition as appropriate.

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

[1] Raw material (compound A ₁ )
(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 represented by the formula (manufacturer: Sakamoto Pharmaceutical Co., Ltd., product name: SC-E750, number average molecular weight: 750, hydroxyl value: approximately 300)

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

(Compound A ₃ )
(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, H ₂ O, 20°C)
(3) 3-amino-1-propanol (manufacturer: Kanto Chemical Co., Ltd., liquid, pH = 11.6 (10 g/l, H ₂ O, 20°C)
(4) 2-(2-aminoethoxy)ethanol (manufacturer: Tokyo Chemical Industry Co., Ltd., liquid, pH = 10.2 (10 g/l, H ₂ O, 20°C)
(5) 2-amino-2-ethyl-1,3-propanediol (manufacturer: Tokyo Chemical Industry Co., Ltd., solid)

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

[2] Blending Conditions Compound _A1 and Compound _A2 were combined to form 100 parts by weight (100 g) of other raw materials, and the other raw materials were weighed out in the amounts shown in Table 1. Compound _A1 and Compound _A2 were charged into a beaker (300 ml), and the other raw materials were added. The mixture was stirred at 70°C with a stirrer for 300 minutes. Volatile raw materials were added in accordance with the degree of evaporation, thereby obtaining the liquid detergent compositions of Examples 1 to 28 and Comparative Examples 1 to 3.

[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.
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.

[Liquid crystal sealant]
(raw materials)
(1-1) Compound B ₁
(1-1-1) The following formula (4):
Partially methacrylated bisphenol A epoxy resin represented by the formula (prepared by the method described in paragraph 0092 of WO 2014/057871)

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

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

(1-4) Optional Component (1-4-1) Photopolymerization Initiator 1: Compound represented by formula (1) (where n1=1) (prepared by the method described in paragraph 0058 of WO2012/077720)
(1-4-2) Photopolymerization initiator 2: Compound represented by formula (2) (where 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) (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Combination conditions)
The other raw materials were weighed out so that the weight parts were as shown in Table 2 relative to 100 parts by weight (5 g) of compound B ₁ , and compound B ₁ and compound B ₂ 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 disperse uniformly, thereby obtaining liquid crystal sealants 1 to 4.

[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, SS-01T for 1 ml tuberculin)
(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 Corporation tabletop ultrasonic cleaner CUC-O2L)
(5) Ultrasonic cleaner (NSD ultrasonic cleaner US-20PS)
(6) Glass container (250 ml beaker)
(7) Pure water (purified water obtained using Makuace manufactured by KURITA)

(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 produce a liquid crystal sealant-coated SUS plate (Figure 1).

(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 then carried out.

(Step 1)
The SUS plate coated with liquid crystal sealant was left submerged vertically for 5 minutes.
The state of the liquid crystal sealant on the SUS plate coated with the liquid crystal sealant was observed.

(Step 2-1)
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 bath, 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).

(Step 2-2)
After Observation 2-1, the cleaning composition in the immersion tank was replaced with the same unused cleaning composition.
The operation of Step 2-1 is repeated, and the state of the liquid crystal sealant on the SUS plate coated with the liquid crystal sealant is observed (Observation 2-2).

In Observation 2-2, there are white traces on the surface of the substrate, which are traces of the liquid crystal sealant.
If it is not visible, the test is terminated.
If the defect is visible, the same liquid crystal sealant-coated SUS plate is vertically immersed in an immersion tank containing 150 mL of the same unused liquid cleaning composition in a glass container so that the entire liquid crystal sealant portion is immersed, and Step 1A, Step 2-1A, and Step 2-2A are carried out as follows.

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

(Step 2-1A)
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), the SUS plate with the liquid crystal sealant was removed from the immersion tank, rinsed with acetone, and dried with air blowing, and the state of the liquid crystal sealant on the SUS plate was observed (Observation 2-1A).

(Step 2-2A)
After Observation 2-1A, the cleaning composition in the immersion tank was replaced with the same unused cleaning composition.
The operation of Step 2-1A is repeated, and the state of the liquid crystal sealant on the SUS plate coated with the liquid crystal sealant is observed (Observation 2-2A).

(3) Cleanability is judged as follows:

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";

In Observation 2-2A,
"△" indicates that no white traces of the liquid crystal sealant applied to the substrate surface were visible;

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."

FIG. 3 shows the results under cleaning condition 1.
Observation 2-1 (◯ state) when the liquid detergent composition of Cleaning Example 1-2 was used, and Observation 2-1A and Observation 2-2A (× state) when the liquid detergent composition (acetone) of Cleaning Comparative Example 1-2 was used are shown.

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

(2) In the case of the liquid cleaning composition of Comparative Example 2 (acetone): Cleaning and observation were performed in Step 2-2 and Step 2-2A under the same conditions as Cleaning Condition 1.

(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 the liquid crystal sealant was vertically submerged 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. Then, the glass plate coated with the liquid crystal sealant was taken out of the pure water, rinsed with acetone, and dried with air blowing, and observations 2-2 and 2-2A were carried out, and the cleaning ability was judged using the same criteria as in cleaning condition 1.

FIG. 4 shows the results under cleaning condition 2.
Observation 2-2 (◯ state) when the liquid detergent composition of Cleaning Example 1-2 was used, and Observation 2-2A (× state) when the liquid detergent composition (acetone) of Cleaning Comparative Example 1-2 was used are shown.

[Cleaning Examples 2-1 to 2-28 and Comparative Examples 2-1 to 2-2]
(Cleaning 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 B ₂ (curing agent) was immersed in it, and the tube was sealed to prepare a test screw tube, which was then subjected to the following ultrasonic cleaning.

(2) The liquid detergent composition in the test screw tube in which compound B ₂ (curing agent) 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 B ₂ (curing agent) immersed in the liquid detergent composition in the Labolan screw tube is observed, and the cleaning ability is evaluated as follows:

(3) The compound B ₂ (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".

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

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 (4)

A liquid cleaning composition for sealants for liquid crystal display elements, comprising as main components 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 ),
The compound _A1 is
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,
the compound _A2 is an organic solvent capable of dissolving the compound _A1 ;
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;
the compound _A3 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;
the blending weight ratio (A ₁ /A ₂ ) of the compound A ₁ to the compound A ₂ is 5/95 to 70/30 ;
A liquid detergent composition, wherein the compound _A3 is contained in an amount of 0.01 to 20 parts by weight relative to 100 parts by weight of the total of the compound _A1 and the compound _A2 (excluding the cases where the liquid detergent composition is one of the following aspects 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;
[Embodiment 2] The following formula (X): R ⁴ —O—(R ⁵ —O) _m —R ⁶ (X)
(wherein ^R4 represents an alkyl group or an allyl group having 1 to 8 carbon atoms, ^R5 represents an alkylene group having 2 to 4 carbon atoms, ^R6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acyl group or an 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.) The liquid cleaning composition according to claim 1, for cleaning a curable resin composition containing a curable compound (compound B ₁ ) and an amine-based curing agent compound (compound B ₂ ). The liquid detergent composition according to claim 2, wherein the curable resin composition further comprises a filler (compound B ₃ ). 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.