TW201842081A - Curable-type composition - Google Patents

Abstract

A curable-type composition, including Component (A) and Component (B) below, Component (A): a mixture of at least one compound selected from the group consisting of a glycerin (meth)acrylate and a polyglycerin (meth)acrylate, in which the mixture has a hydroxy value of 80 mgKOH/g or higher; and Component (B): a compound having an ethylenically unsaturated group and an ionic group.

Description

Hardened composition

FIELD OF THE INVENTION The present invention relates to a hardening type composition, and preferably relates to an active energy ray hardening type composition. The curable composition of the present invention is suitable for use because its cured film has excellent adhesion to the substrate (especially excellent adhesion to plastic substrates), and has excellent anti-fogging properties and dust adhesion resistance. Coating agent, which belongs to these technical fields. In addition, in this specification, acrylate and / or methacrylate are described as (meth) acrylate, and acryloyl and / or methacryloyl are expressed as (meth) acryloyl, acrylic and / or Methacrylic acid is expressed as (meth) acrylic acid.

BACKGROUND ART Active energy ray-curable compositions can be cured by irradiating active energy rays such as ultraviolet rays, visible rays, and electron rays for a very short time, and have high productivity. Therefore, they are widely used as printing inks and coating agents for various substrates. For the purpose of preventing damage to the surface, plastic substrates such as plastic plates and plastic films are protected by hard coating agents. Active energy ray-curable compositions are also used for this purpose.

Plastic substrates are used in protective glasses, goggles, bathroom inner walls, headlight covers and taillight covers for automobiles and locomotives due to their high transparency. When used in high temperature and humidity places or where temperature differences or humidity differences are large, Occasionally, the surface may fog and lose transparency due to condensation. In order to solve these problems, heretofore, a method of coating an anti-fog composition composed of a non-reactive surfactant on the surface of the substrate has been used. This method can initially exert an anti-fog effect after coating, but if the treatment surface is wiped , Anti-fog will be reduced, that is, lack of anti-fog continuity. In addition, although there is a method of applying an anti-fog composition composed of a hydrophilic polymer diluted with an organic solvent on the surface of the substrate, the coating film has insufficient hardness, insufficient solvent resistance, and unsatisfactory anti-fog properties.

In order to solve the above problems, in recent years, an anti-fogging composition hardened by active energy rays such as ultraviolet rays and electron rays has been proposed. Specifically, it is proposed that an anti-fogging agent is composed of a photo-curable ethylenically unsaturated compound containing a hydrophilic group, a photo-curable ethylenically unsaturated compound not containing a hydrophilic group, and a photo-hardening initiator (Patent Literature 1); and, a photo-curable coating composition containing a copolymer of (1) a) 2-hydroxyalkyl (meth) acrylate and b) dialkylaminoalkyl (meth) acrylate, (2 ) Di (meth) acrylate with polyoxyalkylene chain, (3) glycerol diepoxy (meth) acrylic acid adduct, (4) hydroxyalkyl (meth) acrylate and light Polymerization initiator (Patent Document 2).

In addition, an anti-fog coating composition is also proposed, characterized in that it is composed of a hydrophilic monomer and a surfactant (Patent Document 3).

Furthermore, a visible light or active energy ray-curable anti-fog composition containing (meth) acrylate and a reactive surfactant is proposed, which is considered to have excellent surface hardness and excellent anti-fog durability ( Patent Literature 4). Advanced technical literature Patent literature

[Patent Document 1] Japanese Patent Laid-Open No. 55-69678 [Patent Document 2] Japanese Patent Laid-Open No. 3-31369 [Patent Document 3] Japanese Patent Laid-Open No. 3-215589 [Patent Document 4] Japanese Patent Laid-Open 11- Gazette 140109

Disclosure of the Invention Problems to be Solved by the Invention However, the anti-fogging agent of Patent Document 1 and the photo-curable coating composition of Patent Document 2 have a problem that the anti-fogging property cannot be exhibited in a high humidity environment. In addition, the anti-fog coating composition of Patent Document 3 is that the anti-fog property is reduced once the surface of the cured film is wiped, and the anti-fog durability is lacking. In addition, the (meth) acrylate used in the visible light or active energy ray hardening type anti-tank composition of Patent Document 4 is an oligomer with a relatively large molecular weight, and the (meth) acryloyl group accounts for the entire molecule The molar fraction is relatively low, so the surface hardness is insufficient. In addition, the (meth) acrylate constituting the composition has insufficient hydrophilicity and insufficient antifogging properties. Therefore, in order to obtain good anti-fogging properties by using the composition, it is necessary to increase the blending amount of the surfactant. At this time, the hard coating property (the physical properties of the cured film having excellent hardness, etc.) decreases and it is difficult to balance the anti-fogging properties with Hard coating. In addition, the hard coating agent obtained from the conventional active energy ray hardening type composition also has a problem that the hardened film is charged and easily adheres to dust.

In view of the above-mentioned problems, the present invention aims to provide a hardening type composition whose cured film has excellent adhesion to a substrate, especially to a plastic substrate, has a good surface hardness, and can be suitably used as a hard The coating agent also has good anti-fog properties under high humidity, and the anti-fog properties can be fully sustained even when the surface of the cured film is wiped, and the anti-dust adhesion performance is also excellent. Means to solve the problem

According to the present invention, there can be provided a hardening composition composed of a specific (meth) acrylate mixture and a compound having an ethylenically unsaturated group and an ionic group, and the resulting cured film has excellent adhesion to the substrate, in particular It has excellent adhesion to plastic substrates, good surface hardness and can be used as a hard coating agent, and it has good anti-fog properties under high humidity, and its anti-fog properties can be fully sustained even when the surface of the cured film is wiped , It is also excellent in preventing dust adhesion. Invention effect

The cured film formed by using the cured composition of the present invention has good adhesion to plastic substrates and high surface hardness, exhibits good anti-fog continuity, and is more excellent in preventing dust adhesion. Therefore, the hardening type composition of the present invention can be suitably used as a coating agent, and is suitable for coating agents for protective glasses and goggles that require anti-fogging properties of the cured film, and headlight covers and taillights of automobiles and locomotives. Cover coating agent.

Forms for Carrying Out the Invention The present invention relates to a hardened composition containing the following components (A) and (B) (hereinafter, it may be referred to simply as "composition"). (A) Component: a mixture of at least one compound selected from the group consisting of glycerin (meth) acrylate and polyglycerin (meth) acrylate, and having a hydroxyl value of 80 mgKOH / g or more. (B) Component: a compound having an ethylenically unsaturated group and an ionic group. Hereinafter, the component (A), the component (B), other components, methods of use, and the like will be described.

1. (A) component (A) component is a mixture of at least one compound selected from the group consisting of glycerin (meth) acrylate and polyglycerin (meth) acrylate, and its hydroxyl value 80mgKOH / g or more. (A) component is a component used to impart good hardness and adhesion to plastics of the cured film of the composition. Because of its good hydrophilicity, it has good compatibility with component (B), and its compatibility with component (B) Reactivity is also excellent. (A) When the component is a mixture of glycerol (meth) acrylate, a compound having at least one hydroxyl group and two (meth) acryloyl groups as the main component is preferred, and it is a polyglycerol (method In the case of a mixture of acrylates, a compound having at least one hydroxyl group and two or more (meth) acryloyl groups as the main component is preferred. (A) When the component is a mixture of polyglycerol (meth) acrylate, the number of repetitions of the structural unit derived from glycerol in the raw material polyglycerin is preferably 2 to 10, more preferably 2 to 5. By setting the number of repetitions of the structural unit derived from glycerol to 10 or less, the shrinkage during curing can be suppressed and the adhesion to the substrate can be improved, and even if the (B) component is added, it can still exhibit good anti-fogging properties. In addition, the phenomenon that the cured film is peeled off from the substrate due to water absorption and swelling due to the increased hardness of the cured film surface and the excessively high hydrophilicity of the cured film can be prevented.

(A) The component can be prepared by transesterification of glycerol and / or polyglycerol (hereinafter also collectively referred to as "(poly) glycerol") and monofunctional (meth) acrylate. In addition, component (A) can also be prepared by the dehydrogenation reaction of (poly) glycerol and (meth) acrylic acid. When glycerin is used as a raw material, the component (A) is a mixture of mono (meth) acrylate, di (meth) acrylate, and tri (meth) acrylate of glycerin. When polyglycerol is used as the raw material, (A) component is mono (meth) acrylate of polyglycerol and di (meth) acrylate, tri (meth) acrylate and tetra (meth) acrylic acid of polyglycerol Poly (meth) acrylate mixtures such as esters. (A) The component is a mixture of at least one compound selected from the group consisting of glycerin (meth) acrylate and polyglycerin (meth) acrylate, and the hydroxyl value is 80 mgKOH / g or more. (A) The hydroxyl value of the component is preferably 80 to 380 mgKOH / g, more preferably 150 to 300 mgKOH / g. (A) When the hydroxyl value of the component is less than 80 mgKOH / g, the anti-fogging property of the cured film of the composition decreases. In addition, the hydroxyl value can be made 380 mgKOH / g or less, thereby further increasing the hardness of the cured film of the composition. In addition, the hydroxyl value in the present invention means the number of hydroxyl groups in 1 g of the sample and the equivalent number of mg of potassium hydroxide.

(A) The component may be a single type, or two or more types may be combined.

1) Preferred component (A) For component (A), at least one compound selected from the group consisting of glycerin (meth) acrylate and polyglycerin (meth) acrylate Among the mixtures, a mixture of glycerin (meth) acrylate is preferable because the hardness of the cured film of the composition is excellent, the adhesion to plastic is excellent, and the anti-fogging property is also good.

Further, as for the mixture of glycerin (meth) acrylate, a mixture containing glycerin di (meth) acrylate (hereinafter also referred to as "GLY-DA") is more preferable. GLY-DA is a compound represented by the following formula (1) or formula (2).

[Chemical Formula 1]

[In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. ]

[Chemical Formula 2]

[In the above formula (2), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. ]

GLY-DA can be obtained in the form of a mixture of the compound represented by formula (1) and the compound represented by formula (2) as long as it is not specifically purified, so it is sufficient to use these directly, the compound represented by formula (1) There is no particular restriction on the mixing ratio with the compound represented by formula (2), and there is no problem in using it in any ratio.

(A) The purity of the GLY-DA contained in the component is preferably 30% or more, more preferably 40% or more, and more preferably 50% or more when calculated using the following formula (3). By making the purity of GLY-DA at least 30%, the composition containing the (A) component can have an excellent curing speed, and the hardness and anti-fogging properties of the cured film can be excellent.

The purity of GLY-DA (%) = [(D × 1.27) / (M × 1.74 + D × 1.27 + T)] × 100… Equation (3) The D, M and T in the calculation formula (3) are provided with ultraviolet light (UV) The high-speed liquid chromatograph (hereinafter also referred to as "HPLC") of the detector analyzes the following values obtained by the component (A).・ D: GLY-DA peak area at 210 nm ・ M: Glycerol mono (meth) acrylate peak area at 210 nm ・ T: Glycerol tri (meth) acrylate peak area at 210 nm The peak area obtained by HPLC means the value measured under the following conditions.・ Detector: UV detector with a detection wavelength of 210nm ・ Column type: A column filled with a silica with a carbon number of 18 and modified with silica gel. Specifically, it is ACQUITY UPLC BEH manufactured by Waters Corporation. C18 (Part No. 186002350, the inner diameter of the column is 2.1 mm, and the length of the column is 50 mm).・ Column temperature: 40 ℃ ・ Dissolution solution composition: 0.03% by weight mixed solution of trifluoroacetic acid aqueous solution and methanol ・ Dissolution solution flow rate: 0.3mL / min

2) Manufacturing method (A) Components can be obtained by various manufacturing methods. For example, it can be obtained by the transesterification reaction of (poly) glycerol with a compound having a (meth) acryloyl group (hereinafter referred to as "monofunctional (meth) acrylate") in the presence of a transesterification catalyst. Or dehydration esterification of (poly) glycerol and (meth) acrylic acid in the presence of an acidic catalyst.

(A) When the component is a mixture of polyglycerol (meth) acrylates, for example, the polyglycerol used as the raw material of the (A) component is a polyether polyol having a structure obtained by polymerizing glycerol or deglycerol alcohol. The number of repetitions of the structural unit derived from glycerin in polyglycerin is preferably 2-10. It means that the hydroxyl value of the average polymerization degree of polyglycerol is 700 ~ 1,200mgKOH / g, and preferably 800 ~ 1,150mgKOH / g, more preferably 850 ~ 1,100mgKOH / g, and more preferably 900 ~ 1,050mgKOH / g. If the hydroxy value of the polyglycerol is 1,200 mgKOH / g or less, curling of the cured product of the composition can be suppressed, and if the hydroxy value is 700 mgKOH / g or more, it is easy to manufacture, and in addition, it is low in viscosity and easy to handle. In addition, the hydroxyl value of polyglycerol is related to the average degree of polymerization. For example, when the average degree of polymerization is 6, it is approximately 970 mgKOH / g.

As for the component (A), in the aforementioned manufacturing method, the product obtained by the transesterification reaction of (poly) glycerol with a monofunctional (meth) acrylate is less impurities and can be prepared for the purpose (methyl ) Acrylate is more ideal.

Furthermore, the transesterification reaction is preferably a transesterification reaction between (poly) glycerol and a monofunctional (meth) acrylate in the presence of the following catalysts X and Y. Catalyst X: selected from the group consisting of cyclic tertiary amines with azabicyclic structure or their salts or complexes (hereinafter also referred to as "azabicyclic compounds"), amidines or their salts or complexes (hereinafter referred to as (Also known as "amidine compounds"), pyridine ring compounds or their salts or complexes (hereinafter also referred to as "pyridine compounds") and phosphine or their salts or complexes (hereinafter also referred to as "phosphine compounds") More than one compound in the group. Catalyst Y: Zinc-containing compound.

The monofunctional (meth) acrylate is preferably an alkoxyalkyl (meth) acrylate having 1 to 2 carbon atoms, which can promote the dissolution of (poly) glycerol and exhibit excellent reactivity. 2-Methoxyethyl methacrylate is more preferred. In addition, monofunctional (meth) acrylates are particularly desirable because acrylates have excellent reactivity.

For the catalyst X, among the aforementioned compound groups, one or more compounds selected from the group consisting of azabicyclic compounds, amidine-based compounds, and pyridine-based compounds are preferred. These compounds have excellent catalyst activity and are suitable for preparing component (A). After the reaction, they will form a complex with the catalyst Y described later. This complex can be reacted from the end of the reaction by a simple method such as adsorption. The liquid is easily removed. In particular, the azabicyclic compound is hardly soluble in the reaction solution due to its complex with catalyst Y, and can be more easily removed by filtration and adsorption.

As for the catalyst X, quinuclidine, 3-quinine ring ketone, 3-hydroxyquinine ring, triethylenediamine (alias: 1,4-bis) Azabicyclo [2.2.2] octane. Also referred to below as "DABCO"), N-methylimidazole, 1,8-diazabicyclo [5.4.0] undecane-7-ene (hereinafter also referred to as "DABCO") ("DBU"), 1,5-diazabicyclo [4.3.0] nonane-5-ene (hereinafter also referred to as "DBN") and examples of N, N-dimethyl-4- Aminopyridine (hereinafter also referred to as "DMAP") is preferred. Among them, 3-hydroxyquinine ring, DABCO, N-methylimidazole, DBU, and DMAP, which exhibit good reactivity to most polyols and are easily available, are even better.

As long as the catalyst Y is a zinc-containing compound, various compounds can be used, and from the viewpoint of excellent reactivity, zinc organic acid and zinc diketenol are preferred. For catalyst Y, zinc acetate, zinc propionate, zinc acrylate, and zinc methacrylate are preferred as examples of zinc organic acids, and zinc acetonyl pyruvate is preferred as examples of zinc ketone enol salts. . Among them, in terms of catalyst Y, zinc acetate, zinc acrylate, and zinc acetopyruvate, which exhibit good reactivity to most polyols and are readily available, are preferred.

(A) In the manufacturing method of the component, the use ratio of the catalyst X and the catalyst Y is not particularly limited, but it is preferable to use the catalyst X of 0.005 to 10.0 moles, and more preferably 0.05 to 5.0 moles relative to the 1 mole catalyst Y . By using a catalyst X of 0.005 mol or more relative to 1 mol of catalyst Y, the amount of multifunctional (meth) acrylate produced can be increased, and by making it less than 10.0 mol, the amount of by-products can be suppressed The formation and coloring of the reaction solution make the purification step after the reaction easier.

The combination of catalyst X and catalyst Y is preferably a combination of catalyst X as an azabicyclic compound and catalyst Y as an organic acid zinc, especially azabicyclic compound as DABCO and zinc organic acid as zinc acetate and / or acrylic acid The combination of zinc is preferred. In addition to producing (poly) glycerol poly (meth) acrylate with good yield, this combination has excellent color tone after the reaction (for example, less yellow feeling), so it can be suitably used in transparent varnish and hard For coatings, etc., where colorless transparency is the main point. Furthermore, since the above catalyst can be obtained relatively cheaply, it will become an economically advantageous manufacturing method.

(A) In the method of manufacturing the component, the reaction temperature is preferably 40 to 180 ° C, and more preferably 60 to 160 ° C. The reaction temperature can be higher than 40 ℃ to speed up the reaction speed. Setting below 180 ℃ can inhibit the thermal polymerization of (meth) acryloyl group in the raw materials or products and inhibit the coloring of the reaction liquid, which can make the purification step after the reaction complete Tend to be simple.

(A) In the method of producing the component, the reaction pressure is not particularly limited as long as the predetermined reaction temperature can be maintained, and it can be carried out under reduced pressure or under pressure. The reaction pressure should be 0.000001 ~ 10MPa (absolute pressure).

In the production method of the component (A), as the transesterification reaction proceeds, a monohydric alcohol derived from a monofunctional (meth) acrylate may be by-produced. When a part of (poly) glycerol (for example, 50 mol%) hydroxy (meth) acrylate is esterified, the monohydric alcohol can be coexisted in the reaction system in a balanced state, and the catalyst can be removed by adsorption or deactivated. After the operation, the monofunctional (meth) acrylate of the monohydric alcohol and the raw material is distilled off, whereby a product whose acrylate rate is controlled can be produced stably.

(A) The method for producing the component may be carried out without using a solvent, but a solvent may be used if necessary. Specific examples of the solvent include hydrocarbons, ethers, crown ethers, esters, ketones, carbonate compounds, arsenic, arsenic, urea or its derivatives, phosphine oxides, ionic liquids, poly Silicone oil and water. Among these solvents, hydrocarbons, ethers, carbonate compounds and ionic liquids are preferred. These solvents may be used alone, or two or more kinds may be arbitrarily combined and used as a mixed solvent.

(A) In the method of manufacturing the component, inert gas such as argon, helium, nitrogen, or carbon dioxide gas can be introduced into the system for the purpose of maintaining a good color tone of the reaction liquid, or for the purpose of preventing the polymerization of (meth) acryl acetyl groups Introduce oxygen-containing gas into the system. Specific examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium. Oxygen-containing gas can be introduced into the reaction solution or blown into the reaction solution (so-called bubbling).

(A) In the method for producing the component, it is preferable to add a polymerization inhibitor to the reaction liquid for the purpose of preventing the polymerization of (meth) acryloyl group. Examples of the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors. Specific examples of organic polymerization inhibitors include hydroquinone, tertiary butyl hydroquinone, hydroquinone monomethyl ether, 2,6-bis (tertiary butyl) -4-methylphenol, 2,4,6 -Phenolic compounds such as tri- (tertiary butyl) phenol and 4-tertiary butyl catechol, quinone compounds such as benzoquinone, phenothiol , N-nitrosophenylhydroxylamine and N-oxyl compounds, etc. Examples of N-oxyl compounds include 2,2,6,6-tetramethylpiperidine-1-oxide, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4 -Penoxy-2,2,6,6-tetramethylpiperidine-1-oxide and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxide and the like. As for the polymerization inhibitor, among the aforementioned compounds, N-oxyl compounds are preferably used. The N-oxyl compound is preferably the aforementioned compound. Furthermore, the polymerization inhibitor is preferably used in combination with the N-oxyl compound and other polymerization inhibitors. At this time, the polymerization inhibitors other than N-oxyl compounds are phenolic compounds and Preferably, and phenolic compounds are better. The polymerization inhibitor may be added singly or in any combination of two or more, and may be added from the beginning of the production method of the component (A), or may be added in the middle. In addition, the required amount can be added at once, or can be added in portions. In addition, it can be continuously added through a rectification tower. As for the addition ratio of the polymerization inhibitor, it is preferably 5 to 30,000 wtppm, more preferably 25 to 10,000 wtppm, relative to the total weight of the reaction liquid. By setting the addition ratio of the polymerization inhibitor to 5wtppm or more, the effect of inhibiting polymerization can be exerted, and the coloring of the reaction liquid can be suppressed by setting it to 30,000wtppm or less, so that the purification process after the reaction ends tends to be simple, and in addition, (A) The hardening speed of the component is low.

3) Content ratio Hereinafter, (A) component, or (A) component and (C) component will be collectively called curable component. When the total amount of the curable composition is 100% by weight, the curable composition content of the curable composition is preferably 30 to 99% by weight, and more preferably 40 to 80% by weight. The ratio of the curable components in the curable composition can be more than 30% by weight, so that the cured film of the curable composition has sufficient hard coating properties, and the surface resistance can be sufficiently reduced, and it can be borrowed below 99% by weight. The cured film of the curable composition is given sufficient anti-fogging properties and is excellent in curability when irradiated with active energy rays.

2. Component (B) The component (B) is a compound having an ethylenically unsaturated group and an ionic group. (B) The component is a component that imparts good anti-fog properties to the cured film and low surface resistance required to prevent dust from adhering by hardening the hardening composition. (B) The component is chemically bonded in the cured film by the reaction of the ethylenic unsaturated group. Even if the surface of the cured film is wetted or wiped, it can maintain excellent anti-fog properties and can be made into an object with excellent repetitive anti-fog properties.

The content ratio of the component (B) is preferably 0.01 to 20 parts by weight, and more preferably 1 to 15 parts by weight relative to 100 parts by weight of the total amount of the curable components. By setting the ratio of (B) component to 0.01 weight or more, the cured film of the composition can have excellent anti-cavity and low surface resistance, and by setting it to 20 weight parts or less, the hard coating property of the cured film and the Good adhesion to the substrate.

(B) As long as the component is a compound having an ethylenically unsaturated group and an ionic group, various compounds can be used. Examples of ethylenically unsaturated groups include (meth) acryloyl, (meth) allyl, vinyl, and styryl groups. From the viewpoint of good reactivity with the (B) component and the ethylenically unsaturated group of the component (A) and the component (C) described later and excellent curability, the (meth) acryloyl group is suitable, More preferably, it is acryl.

(B) Since the component has an ionic group, not only can the anti-fogging property and low surface resistance be obtained without damaging the original hard coating property of the cured film of the composition, but also this effect can be obtained even in a small content ratio. In the component (B), the ionic group can be exemplified by salts of strong acids, specifically sulfonates such as ammonium sulfonate, sodium sulfonate and potassium sulfonate, ammonium alkyl sulfate, sodium alkyl sulfate and potassium alkyl sulfate Alkyl sulfates and carboxylates such as ammonium carboxylate, sodium carboxylate and potassium carboxylate.

The ionic group is preferably an alkyl sulfate or sulfonate group from the viewpoint that the desired effect can be obtained even when the content of the component (B) is small. Furthermore, examples of the relative cation constituting the sulfonate include second-order ammonium ions, third-order ammonium ions, and fourth-order ammonium ions. Specifically, the second-stage ammonium ion can be exemplified by dimethylamine, diethylamine, di-1-propylamine, di-2-propylamine, di-n-butylamine, di-2-butylamine, di-1-pentylamine , Di-2-pentylamine, di-3-pentylamine, dineopentylamine, dicyclopentylamine, di-1-hexylamine, di-2-hexylamine, di-3-hexylamine, dicyclohexylamine , Methylethanolamine and ethylethanolamine are ionized by protonation. The third-level ammonium ion can be exemplified by trimethylamine, triethylamine, tri-1-propylamine, tri-2-propylamine, tri-n-butylamine, tri-2-butylamine, tri-1-pentylamine, tri-2- Amylamine, tri-3-pentylamine, trineopentylamine, tricyclopentylamine, tri-1-hexylamine, tri-2-hexylamine, tri-3-hexylamine, tricyclohexylamine, dimethylethanolamine , Ethyl methyl ethanolamine, diethyl ethanolamine, lauryl diethanolamine and bis (2-methoxyethyl) methylamine are ionized by protonation. Among them, it is preferably an ion formed by protonation of methylethanolamine, ethylethanolamine, dimethylethanolamine, diethylethanolamine or lauryldiethanolamine, and more preferably methylethanolamine, ethylethanolamine or lauryldiethanolamine The ions produced by each protonation are more preferably ions produced by the protonation of methylethanolamine, dimethylethanolamine or ethylethanolamine, especially the ions produced by the protonation of ethylethanolamine.

(B) The ionic group of the component is preferably bonded to the ethylenically unsaturated group through an alkyl group, an alkylphenyl group, an oxyalkylene group, or the like.

The component (B) can be exemplified by the following components (B-1) and (B-2), and any of them can be used. (B-1) Component: a compound composed of cations and anions with an ethylenically unsaturated group in one molecule. (B-2) Component: a compound composed of anions and cations having an ethylenically unsaturated group in one molecule.

(B-1) The component is a compound composed of cations and anions having an ethylenically unsaturated group in one molecule. The cationic group in the cation with ethylenically unsaturated group in 1 molecule can be exemplified by: selected from ammonium ion, imidazolium ion, pyridinium ion, pyrrolidinium ion, pyrrolinium ion, piperidinium ion Pyridine Onium ion, pyrimidinium ion, triazolium ion, three Onium ion, quinolinium ion, isoquinolinium ion, indolium ion, quino Pyridinium ion, piper Onium ion, Azolinium ion, thiazolium ion and At least one of the group consisting of porphyrinium ions.

Specific examples of cations having an ethylenically unsaturated group in 1 molecule include, for example, dimethyl mono (meth) acrylate ethylammonium ion (i.e., dimethylaminoethyl (meth) acrylate) Class 4 ammonium ions) and diethyl mono (meth) acrylate ethyl ammonium ions (that is, class 4 ammonium ions of diethylaminoethyl (meth) acrylate) and other dialkyl mono (meth) acrylic acids Alkyl ammonium ions and piperidinium ions of 1,2,2,6,6-pentamethyl-4- (meth) acrylate. In addition, in the above-mentioned ammonium ion, descriptions such as "N-" and "N, N-" indicating substituents on the nitrogen atom are omitted.

Examples of the anions constituting the component (B-1) include halogen-based anions such as sulfonic acid derivatives, bromide ions, and triflate groups, boron-based anions such as tetraphenylborate groups, and Fluorine phosphate radicals and other phosphorus-based anions. The aforementioned anion is preferably a sulfonic acid derivative. Specific examples of sulfonic acid derivatives include: anions of sulfonic acids with polyoxyalkylene units such as alkoxy polyethylene glycol sulfonic acid and anions containing alkyl aromatic sulfonic acids such as cumene sulfonic acid Wait.

The component (B-1) is preferably a compound composed of an alkylammonium ion of a dialkyl mono (meth) acrylate and an anion of a sulfonic acid having a polyoxyalkylene unit.

(B-1) As a component, a commercial item can be used. For example, the compounds having cations and anions with (meth) acryloyl and ammonium ions in the molecule can be exemplified by the trade names "IL-MA1", "IL-MA2" and "IL" manufactured by Guangrong Chemical Industry Co., Ltd. -MA3 "; compounds with cations and anions containing acryloyl groups and ammonium ions can be exemplified by the trade names" JI-62C01 "and" JI-63F01 "made by Japanese emulsifiers; and with methacrylic compounds Examples of the compound of the cation of the base and the ammonium ion and the alkyl sulfate ion of the anion include the trade name "JNA-04006" manufactured by Japan Emulsifier (Co., Ltd.).

(B-2) The component is a compound composed of anions and cations having an ethylenically unsaturated group in one molecule. Specific examples of the component (B-2) include the following examples as examples in which the anionic group is a sulfonate ion. That is, for example: polyoxyethylidene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt whose cation is ammonium ion, polyoxyethylene nonylpropenyl phenyl ether sulfate ammonium salt , Α-sulfonic acid group-ω- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt And bis (polyoxyethylene polycyclic phenyl ether) ammonium sulfate of methacrylic acid; and 2-sodium sulfonate ethyl methacrylic acid whose sodium cation is sodium ion, alkyl allyl sulfosuccinate sodium salt, (Meth) acryloyl polyoxyalkylene sulfate sodium salt and methacrylic acid bis (polyoxyethylene polycyclic phenyl ether) sodium sulfate salt, etc.

(B-2) As a component, a commercial item can be used. For example, polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate can be exemplified by the trade names "Acualon KH-10" and "Acualon KH-1025" manufactured by the First Industrial Pharmaceutical Co., Ltd. "," Acualon KH-05 "; polyoxyethylene ethyl nonyl propenyl phenyl ether ammonium sulfate can be exemplified by the trade names" Acualon HS-10 "and" Acualon HS-1025 "manufactured by the First Industrial Pharmaceutical Co., Ltd. "," Acualon BC-0515 "," Acualon BC-10 "," Acualon BC-1025 "," Acualon BC-20 "and" Acualon BC-2020 "; α-sulfonate-ω- (1- (alkane Oxygen) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt can be exemplified by the trade name "ADEKA" manufactured by ADEKA Corporation. REASOAP SR-10 "," ADEKA REASOAP SR-20 "," ADEKA REASOAP SR-1025 "and" ADEKA REASOAP SR-3025 "; methacrylic acid bis (polyoxyethylene polycyclic phenyl ether) sulfate can be exemplified The trade name "Antox MS-60" made by Japanese emulsifier (share); The alkyl allyl sulfosuccinate sodium salt can be exemplified by the trade name "Antox SAD" made by Japanese emulsifier (share); The 2-sodium methacrylic acid can be exemplified by the trade name "Antox MS-2N" manufactured by Japan Emulsifier (Share); the alkyl allyl sulfosuccinate sodium salt can be exemplified by Sanyo Chemical Industry Co., Ltd. The trade name "ELEMINOL JS-20"; and the sodium methacryloyl polyoxyalkylene sulfate sodium salt are exemplified by the trade name "ELEMINOL RS-3000" manufactured by Sanyo Chemical Industry Co., Ltd.

As for the component (B), the component (B-1) is more desirable than the component (B-2) because the anti-fogging durability is more excellent. The reason why the component (B-1) is more excellent in anti-fog durability is unknown, but it is presumably because the cation (for example, ammonium ion) that constitutes the component (B-2) and serves as a relative ion is relatively hydrophilic. The anions (for example, alkylsulfonic acid ion, alkylbenzenesulfonic acid ion, alkylnaphthalenesulfonic acid ion, and polyoxyethylethylsulfonic acid ion) that constitute the component (B-1) as relative ions are slightly hydrophobic, Therefore, there is less elution due to moisture on the surface of the cured film.

3. Curable composition The present invention is a curable composition containing the aforementioned components (A) and (B). In the method for producing the hardened composition of the present invention, it is only necessary to stir and mix the components (A) and (B) and other components described later as necessary. When the components (A) and (B) and other components described later are mixed as necessary, heating and stirring may be performed as necessary. The temperature during heating, stirring and mixing should be within the range of 40 ~ 90 ℃. However, when blending the thermal polymerization initiator described later, in order to prevent the polymerization from occurring during the production of the hardened composition, it is preferably carried out at 30 ° C or lower.

The viscosity of the hardened composition only needs to be appropriately set depending on the purpose and purpose of use. The viscosity of the hardened composition is preferably 5 to 10,000 mPa · s, more preferably 10 to 1,000 mPa · s. If the viscosity is increased, it becomes difficult to obtain a thin film and a cured film with excellent surface smoothness. Therefore, it is sufficient to adjust the desired viscosity with an appropriate solvent. In the present invention, the viscosity refers to a value measured at 25 ° C using an E-type viscometer.

The hardening type composition of the present invention can be used as an active energy ray hardening type composition or a thermosetting type composition, but it can be suitably used as an active energy ray hardening type composition. Although the hardening composition of the present invention contains the aforementioned components (A) and (B), various components may be blended depending on the purpose. Other components may specifically include compounds having an ethylenically unsaturated group (hereinafter also referred to as "(C) component") other than the aforementioned (A) and (B) components, and a photopolymerization initiator (hereinafter also referred to as "(D) component ") And thermal polymerization initiator (hereinafter also referred to as" (E) component "), etc. Hereinafter, these components will be described. In addition, other components described below may use only one of the exemplified compounds, or two or more of them may be used in combination.

1) Component (C) The component (C) is a compound having an ethylenically unsaturated group other than the components (A) and (B). (C) The component is an arbitrary component for adjusting the viscosity and other physical properties of the composition, and various substances can be used. (C) Components can be exemplified by compounds with one ethylenically unsaturated group (hereinafter also referred to as "monofunctional unsaturated compounds") and compounds with more than two ethylenically unsaturated groups (hereinafter also referred to as "multifunctional unsaturated Saturated compounds ").

(1) Monofunctional unsaturated compounds Examples of monofunctional unsaturated compounds include (meth) acrylates having one (meth) acryloyl group (hereinafter also referred to as "monofunctional (meth) acrylates") And a (meth) acrylamide compound having one (meth) acrylamide group (hereinafter also referred to as "monofunctional (meth) acrylamide"), etc.

Specific examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) ) Amyl acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate (meth) Alkyl acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Monofunctional (meth) acrylates with alicyclic groups such as amyloxyethyl and dicyclopentenyloxyethyl (meth) acrylate; (meth) glycidyl acrylate, (meth) acrylic acid Tetrahydrofurfuryl ester, (meth) acrylic acid (2-methyl-2-ethyl-1,3-di -4-yl) methyl ester, (meth) acrylic acid cyclohexanespiro-2- (1,3-di Monofunctional (meth) acrylates with cyclic ether groups such as -4-yl) methyl esters and (meth) acrylic acid 3-ethyl-3-oxeyl methyl esters; (meth) acrylic acid benzyl esters, ( Aromatic monofunctional (meth) acrylates such as phenoxyethyl methacrylate, o-phenylphenoxy (meth) acrylate and p-cumylphenol (meth) acrylate; (methyl ) Monofunctional (meth) acrylic esters with maleimide groups such as acryloxyethyl hexahydrophthalimide and maleimide; (meth) acrylamide Porphyrin; and ethyl carbitol (meth) acrylate and 2-ethylhexyl carbitol (meth) acrylate and other alkyl carbitol (meth) acrylate and other monomers with alkoxyalkyl groups Functional (meth) acrylate etc.

The monofunctional (meth) acrylamide can be specifically exemplified by: N-methyl (meth) acrylamide, N-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide Amine, N-n-butyl (meth) acrylamide, N-secondary butyl (meth) acrylamide, N-tertiary butyl (meth) acrylamide and N-n-hexyl (methyl) ) N-alkyl (meth) acrylamide such as acrylamide; N-hydroxyalkyl (meth) acrylamide such as N-hydroxyethyl (meth) acrylamide; and N, N-dimethyl Aminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-di Ethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di-n-butyl (Meth) acrylamide and N, N-dihexyl (meth) acrylamide and other N, N-dialkyl (meth) acrylamide and the like.

(2) Polyfunctional unsaturated compounds Examples of polyfunctional unsaturated compounds include: (meth) acrylates with two (meth) acryloyl groups (hereinafter also referred to as "2-functional (meth) acrylates" ) And (meth) acrylates with more than two (meth) acryloyl groups (hereinafter also referred to as "trifunctional or more (meth) acrylates"), etc. Specific examples of the 2-functional (meth) acrylates are: alkylene oxide adducts of bisphenol A (meth) acrylate, alkylene oxide adducts of bisphenol F (meth) Diol) (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate and nonanediol di (meth) acrylate and other glycol di (meth) acrylate; two new Di (meth) acrylates of polyols such as pentaerythritol di (meth) acrylates; di (meth) acrylates of these polyol alkylene oxide adducts; of isocyanuric acid Di (meth) acrylate; and di (meth) acrylate of alkylene oxide adduct of isocyanuric acid, etc. In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetrahydrofuran.

Specific examples of (meth) acrylates with more than 3 functions include: glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate , Neopentaerythritol tetra (meth) acrylate, di (trimethylol) propane tri (meth) acrylate, di (trimethylol) propane tetra (meth) acrylate, di neopentaerythritol Poly (meth) acrylates of polyhydric alcohols such as tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; Alkyl oxide adduct bis (meth) acrylate; ginseng (2- (meth) acryloyloxyethyl) trimer isocyanate, etc .; and isocyanuric acid alkylene oxide adduct The third (meth) acrylate and so on. In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetrahydrofuran.

(C) The content ratio of the components is preferably 1 to 30 parts by weight, more preferably 5 to 25 parts by weight, and more preferably 10 to 20 parts by weight relative to 100 parts by weight of the total amount of the hardenable components. If the content ratio of the component (C) is within the above range, the physical properties can be adjusted without impairing the excellent substrate adhesion characteristic of the composition of the present invention.

2) Component (D) When the hardening composition of the present invention is used as an active energy ray-curing composition (further used as an electron-beam-curing composition), the component (D) (i.e. light Polymerization initiator) and use electron wires to harden it. When the curable composition of the present invention is used as an active energy ray curable composition, especially when ultraviolet rays or visible rays are used as the active energy ray, the component (D) is preferably contained from the viewpoint of ease of curing and cost. When used as an electron wire-curing composition, although it is not necessary to contain the component (D), a small amount may be blended as necessary to improve the curability.

In the present invention, as the component (D), various conventional photopolymerization initiators can be used. In addition, the component (D) is preferably a photo radical polymerization initiator. (D) Specific examples of the component include: 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl Yl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-methyl -1- [4- (methylthio) phenyl] -2- Prolin-1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Pyridophenyl) butane-1-one, diethoxyacetophenone, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] acetone} and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropane-1-one and other acetophenone-based compounds; diphenyl Diphenyl ketone compounds such as ketone, 4-phenyl diphenyl ketone, 2,4,6-trimethyl diphenyl ketone, and 4-benzyl-4'-methyl diphenyl sulfide ; Methylbenzyl carbamate, 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester of oxyphenylacetic acid and 2- (2 of oxyphenylacetic acid -Hydroxyethoxy) ethyl esters and other α-ketoester compounds; 2,4,6-trimethylbenzyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzyl (Acyl) phenylphosphine oxide and bis (2,6-dimethoxybenzyl) -2,4,4-trimethylpentylphosphine oxide and other phosphine oxide compounds; benzoin, Benzoin-methyl compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; 1- [4- (4-benzoyl benzene Thiol) phenyl] -2-methyl-2- (4-methylphenylsulfinyl) propane-1-one and other acetophenone / diphenyl ketone hybrid (hybrid) system light start Agents; 2- (O-benzyl oxime) -1- [4- (phenylthio)]-1,2-octanedione and other oxime ester-based photopolymerization initiators; and camphorquinone.

Among these, acetophenone-based compounds, diphenyl ketone-based compounds and phosphine oxide-based compounds are preferred, and even when a cured film is applied with a film of a few μm or less, good curing can be easily obtained under air From a sexual point of view, it is particularly suitable to mention compounds such as acetophenone.

(D) The content ratio of the components is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, and particularly preferably 1 to 5 parts by weight relative to 100 parts by weight of the total amount of the curable components. (D) When the content ratio of the component is within the above range, the composition has excellent curability, and the resulting cured film has excellent scratch resistance.

3) (E) component (E) component is a thermal polymerization initiator, and when using a hardening composition as a thermosetting composition, (E) component can be blended. The hardening type composition of the present invention may be blended with a thermal polymerization initiator and hardened by heating. Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.

Specific examples of organic peroxides include 1,1-bis (tertiary butylperoxy) 2-methylcyclohexane, 1,1-bis (tertiary hexylperoxy) -3,3,5- Trimethylcyclohexane, 1,1-bis (tertiary hexylperoxy) cyclohexane, 1,1-bis (tertiary butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tertiary butylperoxy) cyclohexane, 2,2-bis (4,4-dibutylperoxycyclohexyl) propane, 1,1-bis (tertiary butylperoxy) Cyclododecane maleic acid, tertiary hexylperoxyisopropyl monocarbonate, tertiary butylperoxy, tertiary butylperoxy-3,5,5-trimethylhexanoate, tertiary Grade butyl peroxylaurate, 2,5-dimethyl-2,5-bis (m-toluenemethyl peroxy) hexane, tertiary butyl peroxyisopropyl monocarbonate, tertiary butyl 2-ethylhexyl monocarbonate, tertiary hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis (benzyl peroxy) hexane, tertiary butyl Peroxyacetate, 2,2-bis (tertiary butylperoxy) butane, tertiary butylperoxybenzoate, n-butyl-4,4-bis (tertiary butylperoxy) Valerate, di (tertiary butyl) peroxyisophthalate, α, α'-bis (tertiary butylperoxy) dicumyl, dicumyl peroxide, 2,5-dimethyl Yl-2,5-di (tertiary butylperoxy) hexane, tertiary butylcumyl peroxide, di (tertiary butyl) peroxide, p-menthane hydroperoxide, 2,5 -Dimethyl-2,5-di (tertiary butylperoxy) hexyne-3, dicumyl hydroperoxide, tertiary butyltrimethylsilyl peroxide, 1,1,3 , 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tertiary hexyl hydroperoxide, tertiary butyl hydroperoxide, etc.

Specific examples of azo compounds include 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (aminomethylazo) isobutyronitrile, and 2-phenylazo- 4-Methoxy-2,4-dimethylvaleronitrile, azobis (tertiary octane) and azobis (tertiary butane), etc. The organic peroxide and the azo-based compound may be used alone or in combination of two or more. In addition, organic peroxides can also be combined with reducing agents to form redox reactions.

(E) The content ratio of the components is preferably 10 parts by weight or less based on 100 parts by weight of the total amount of the curable components. When the thermal polymerization initiator is used alone, it only needs to be carried out according to the conventional method of free radical thermal polymerization, and depending on the situation, it can also be used together with the component (D) (ie, photopolymerization initiator), which is further improved after photohardening Thermal hardening for the purpose of reaction rate.

4) Other components other than the foregoing For the other components other than the foregoing, conventional additives can be used, and examples thereof include organic solvents, ultraviolet absorbers, light stabilizers, acidic substances, inorganic particles, antioxidants, silane coupling agents, and surfaces Modifiers, polymers, acid generators, pigments, dyes, adhesion-imparting agents, polymerization inhibitors, etc.

<Organic solvent> Although the composition of the present invention can be used without an organic solvent, various organic solvents can be used for the purpose of adjusting the coating viscosity and film thickness. Specific examples include: alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohol such as diacetone alcohol; benzene and toluene And aromatic compounds such as xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N- Methylpyrrolidone, etc.

The content ratio of the organic solvent is preferably 0.01 to 200 parts by weight, more preferably 10 to 150 parts by weight, and more preferably 20 to 100 parts by weight relative to 100 parts by weight of the total composition.

<Anti-fog modifier> Although the cured composition of the present invention has a cured film with excellent anti-fogging properties, in particular when used as an active energy ray curing composition, the irradiation condition of the active energy ray is set to At high exposures, the anti-fog performance may be insufficient. In addition, although the cured film of the present invention has excellent repetitive anti-fogging properties, it varies depending on the intended use, and it may be necessary to further improve the initial anti-fogging properties. For these purposes, anti-fogging modifiers can be added within a range that does not adversely affect other properties of the present invention. Examples of anti-fogging modifiers include ionic surfactants without ethylenic unsaturated groups. Conventional substances can be used for the ionic surfactant not having an ethylenic unsaturated group, and examples include anionic surfactants, cationic surfactants, and zwitterionic surfactants.

Anionic surfactants can be used: dialkyl sulfosuccinates such as sulfosuccinate bis (2-ethylhexyl) sodium salt and sulfosuccinate bis (2-ethylhexyl) ammonium salt; Fatty acid salts such as sodium oleate and potassium oleate; higher alcohol sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; alkyls such as sodium alkylnaphthalenesulfonate Naphthalene sulfonate; naphthalene sulfonate formaldehyde condensate; dialkyl phosphate; and polyoxyethylene ethyl sulfate such as polyoxyethyl ethyl alkyl phenyl ether sulfate. Among these compounds, dialkyl sulfosuccinate is preferred from the viewpoint that the initial antifogging properties are more excellent. Dialkyl sulfosuccinates are commercially available, and commercially available products can be used. The sodium salt of bis (2-ethylhexyl) sulfosuccinate can be exemplified by RIKASURF P-10 (solution of the compound), M-30 (solution of the compound) and G-30 (manufactured by New Japan Physical and Chemical Co., Ltd.) Propylene glycol / water mixed solution of this compound) and RAPISOL A30, RAPISOL A70, RAPISOL A80, RAPISOL A90 manufactured by NOF Corporation. The sulfosuccinic acid bis (2-ethylhexyl) ammonium salt can be exemplified by RIKASURF G-600 [propylene glycol / water mixed solution of the compound] manufactured by New Japan Physical and Chemical Corporation.

Examples of the cationic surfactants include ethanolamines, laurylamine acetate, triethanolamine monoformate, stearylamine ethyldiethylamine acetate and other amine salts, lauryltrimethylammonium chloride, chloride Stearyl trimethyl ammonium, dilauryl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, and stearyl dimethyl benzyl chloride Grade 4 ammonium salts, etc.

Zwitterionic surfactants include fatty acid zwitterionic surfactants such as dimethylalkyl lauryl betaine and dimethyl alkyl stearyl betaine, dimethyl alkyl sulfonate betaine, etc. Sulfonic acid-based zwitterionic surfactant and alkylglycine.

Among these ionic surfactants that do not have an ethylenically unsaturated group, from the viewpoint of more excellent initial antifogging properties, anionic surfactants are preferred, as described above for dialkylsulfonic acid succinic acid Salt is better.

Regarding the content of the anti-fog modifier, the composition of the present invention preferably contains 0.1 to 10% by weight of the total 100% by weight. If it is within the above range, it can be made into an excellent initial anti-fogging property without compromising the repeated anti-fogging properties of the cured film.

<Ultraviolet absorber> Specific examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6 -Bis (2,4-dimethylphenyl) -1,3,5-tris , 2- [4-[(2-Hydroxy-3-tridecynyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-three , 2- [4-[(2-Hydroxy-3- (2-ethylhexyloxy) propyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl Phenyl) -1,3,5-tri , 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-bisbutoxyphenyl) -1,3,5-tri And 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-tri Wait three UV absorber; 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2-hydroxy-5-tris Grade butylphenyl) -2H-benzotriazole and 2- [2-hydroxy-5- (2- (methyl) acryloyloxyethyl) phenyl] -2H-benzotriazole and other benzo Triazole ultraviolet absorber; 2,4-dihydroxydiphenyl ketone and 2-hydroxy-4-methoxydiphenyl ketone and other diphenyl ketone ultraviolet absorber; ethyl-2-cyano-3 , 3-diphenyl acrylate and octyl-2-cyano-3,3-diphenyl acrylate and other cyanoacrylate-based ultraviolet absorbers; and, titanium oxide particles, zinc oxide particles and tin oxide particles, etc. Inorganic particles that absorb ultraviolet rays, etc. Among the aforementioned compounds, benzotriazole ultraviolet absorbers are particularly preferred.

The above-mentioned ultraviolet absorber is used for the purpose of preventing the plastic substrate which is easily yellowed by the irradiation of active energy rays from discoloring, and for the purpose of preventing the deterioration of the article caused by sunlight when using the article with the cured film formed outdoors use. The content ratio of the ultraviolet absorber is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 2 parts by weight relative to 100 parts by weight of the total amount of the hardenable components.

<Light stabilizers> Conventional light stabilizers can be used as light stabilizers, but among them, hindered amine light stabilizers (HALS) are preferred. Specific examples of hindered amine-based light stabilizers include bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis (N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiper Pyridin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-tri , Bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidyl) sebacate, etc. Examples of commercially available products of hindered amine-based light stabilizers include TINUVIN 111FDL, TINUVIN123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 and the like manufactured by BASF.

The content ratio of the light stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, and more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the total amount of the hardening component.

<Acid Substance> Although the composition of the present invention is an excellent adhesion material to base materials such as plastics, the adhesion can be further improved by adding an acid substance. Examples of acidic substances include photo-acid generators that generate acids by irradiating active energy rays, inorganic acids, and organic acids. Among these, inorganic acids or organic acids are suitable. As far as inorganic acids are concerned, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, etc. are better. For organic acids, organic sulfonic acid compounds such as p-toluenesulfonic acid and methanesulfonic acid are preferred, aromatic sulfonic acid compounds are more preferred, and p-toluenesulfonic acid is particularly preferred. The content ratio of the acidic substance is preferably 0.0001 to 5 parts by weight, more preferably 0.0001 to 1 part by weight, and more preferably 0.0005 to 0.5 part by weight with respect to 100 parts by weight of the total amount of the hardenable component. If the content ratio of the acidic substance is within the above range, the adhesion between the composition and the substrate is more excellent, and problems such as corrosion of the substrate and decomposition of other components can be prevented.

<Antioxidant> The composition of the present invention may further contain an antioxidant for the purpose of improving the heat resistance and weather resistance of the cured film. Examples of the antioxidant used in the present invention include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Phenolic antioxidants are suitably exemplified by hindered phenols such as bis (tertiary butyl) hydroxytoluene. Examples of commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70 and AO-80 manufactured by ADEKA Corporation. Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphite, and triaryl phosphite. Examples of commercially available products of these derivatives include ADEKA STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, and 135A manufactured by ADEKA Corporation. , 3010, etc. Examples of the sulfur-based antioxidants include thioether-based compounds, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by ADEKA Corporation.

The content ratio of the antioxidant is preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 1 part by weight, relative to 100 parts by weight of the total composition of the present invention. If the content of the antioxidant is within the above range, the composition has excellent stability, and also has good curability and adhesion.

<Surface modifier> The composition of the present invention can be added with a surface modifier for the purpose of improving the leveling property during coating and for improving the smoothness of the cured film to improve the scratch resistance. Examples of surface modifiers include surface modifiers, surfactants, leveling agents, defoamers, smoothness-imparting agents, and antifouling-imparting agents. These conventional surface modifiers can be used. Among them, polysiloxane-based surface modifiers and fluorine-based surface modifiers are suitable. Specific examples include polysiloxane-based polymers and oligomers with polysiloxane chains and polyalkylene oxide chains, polysiloxane-based polymers and oligomers with polysiloxane chains and polyester chains Substances, fluoropolymers and oligomers with perfluoroalkyl and polyalkylene oxide chains, and fluoropolymers and oligomers with perfluoroalkyl ether chains and polyalkylene oxide chains, etc. . In addition, it is also possible to use surface modifiers having an ethylenically unsaturated group in the molecule (preferably (meth) acryloyl group) for the purpose of improving smoothness sustainability.

The content ratio of the surface modifier is preferably 0.01 to 1.0 part by weight relative to 100 parts by weight of the total composition of the present invention. When the content ratio of the surface modifier is within the above range, the surface smoothness of the cured film is excellent.

<Hydrophilic polymer> When applying the hardening composition of the present invention to a substrate, it varies depending on the type of substrate to be applied and the coating method, and the coating film after the composition is applied to the substrate and dried There may be cases in which the cured film finally obtained becomes poor in appearance. At this time, for the purpose of preventing the coating film from collapsing and the like, it is suitable to add a hydrophilic polymer to the curable composition.

Examples of the hydrophilic polymer include polymers having a hydrophilic group. Examples of the hydrophilic group include acidic groups and hydroxyl groups, and acidic groups are preferred. Examples of the acidic group include a carboxyl group, a sulfonic acid group and a phosphine group, and the carboxyl group and the sulfonic acid group are preferred, and the carboxyl group is more preferred. For the hydrophilic polymer to be a polymer having an acid group (hereinafter referred to as "acid group-containing polymer"), it is preferred that a part or all of the acid group is neutralized and neutralized. The method for producing the neutralizing salt of the acid group-containing polymer can be exemplified by the method of producing the raw material vinyl monomer using the neutralizing salt; Methods, etc.

The hydrophilic polymer is preferably a polymer having a vinyl monomer having a hydrophilic group as an essential structural monomer unit. Examples of the vinyl monomer having a hydrophilic group include a vinyl monomer having an acid group and a vinyl monomer having a hydroxyl group.

Examples of the vinyl monomer having an acid group include an ethylenically unsaturated compound having a carboxyl group, an ethylenically unsaturated compound having a sulfonic acid group, and an ethylenically unsaturated compound having a phosphoric acid group. Examples of the ethylenically unsaturated compound having a carboxyl group include (meth) acrylic acid, maleic acid, itaconic acid, crotonic acid, and salts of these compounds. Examples of the ethylenically unsaturated compound having a sulfonic acid group include acrylamide 2-methylpropanesulfonic acid, styrenesulfonic acid and (meth) allylsulfonic acid. Examples of the ethylenically unsaturated compound having a phosphoric acid group include phosphoric acid-containing (meth) acrylates such as esters of phosphoric acid and (meth) acrylic acid. When the acid group-containing polymer is a part or all of the acid group undergoing neutralization and neutralization, the vinyl monomer with acid group is preferably neutralized. Examples of basic compounds used to form neutralizing salts of vinyl monomers with acidic groups include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; ammonia; and triethylamine and triethanolamine Such as amine compounds.

Examples of the vinyl monomer having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.

The hydrophilic polymer may be obtained by copolymerizing vinyl monomers other than vinyl monomers having hydrophilic groups (hereinafter referred to as "other monomers"). Other monomers include alkyl (meth) acrylate, alkylamino (meth) acrylate, styrene, alkyl vinyl ether, polyvinylidene chloride, (meth) acrylamide, N- Vinylformamide, N-vinylacetamide, vinyl acetate, vinylpyrrolidone, (meth) acrylonitrile and (meth) acryloyl Porphyrin etc. Examples of alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and ethyl 2- (meth) acrylate Hexyl ester, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, etc. Examples of dialkylaminoalkyl (meth) acrylates include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.

The weight average molecular weight of the hydrophilic polymer (hereinafter referred to as "Mw") is preferably 5,000 to 100,000, more preferably 7,000 to 30,000. In addition, the Mw of the hydrophilic polymer in the present invention means a value obtained by gel permeation chromatography (hereinafter referred to as "GPC") using a standard polystyrene calibration line, which uses acidic groups such as carboxylic acid as The acid component is measured before neutralization. In addition, when amine monomers are included as other monomers, GPC measurement cannot be performed, which means that ordinary alkyl (meth) acrylates are used to replace these components and the same polymerization temperature, initiator concentration, monomer The GPC measurement result of the polymer polymerized under conditions such as concentration and solvent concentration is regarded as the value of the estimated value.

Hydrophilic polymers can be used: those made using the aforementioned monomers and in accordance with general polymerization methods. For example, a radical polymerization method, an anion living polymerization method, a radical living polymerization method, etc. are mentioned. In addition, the polymerization form includes, for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method. If it is desired to manufacture the aforementioned low molecular weight polymer by a general polymerization method, it is generally necessary to add a chain transfer agent and a polymerization initiator. If a polymer that uses a large amount of a chain transfer agent is used, the cured film is easily colored by irradiation with active energy rays. In addition, if a polymer that uses a large amount of a polymerization initiator is used, the storage stability of the composition tends to decrease. Therefore, a polymer prepared by high-temperature polymerization without a large amount of chain transfer agent and polymerization initiator is preferred. The temperature of high temperature polymerization is preferably 160 ~ 350 ℃, preferably 180 ~ 300 ℃.

The form of the hydrophilic polymer only needs to be selected according to the purpose, and examples include a solution of the hydrophilic polymer, a dispersion liquid of the hydrophilic polymer, and a powder. Specifically, examples include organic solvent solutions of hydrophilic polymers, aqueous solutions or aqueous dispersions of hydrophilic polymers, mixed solutions of organic solvents and water of hydrophilic polymers, aqueous dispersions, and powders. Among these, the aqueous solution or aqueous dispersion of the hydrophilic polymer, the organic solvent solution, and the mixed solution or aqueous dispersion of the organic solvent and water of the hydrophilic polymer are ideal because of their excellent solubility in the composition. The solid content of the solution and dispersion of the hydrophilic polymer is preferably 3 to 70% by weight. In addition, the viscosity of the solution and dispersion of the hydrophilic polymer is preferably 5 to 20,000 mPa · s.

Whether the content of the hydrophilic polymer is in either aqueous solution or aqueous dispersion, based on the solid content, based on 100 parts by weight of the total composition, it is preferably 0.5 to 50 parts by weight, more preferably 2 ~ 30 weight parts. If the content of the hydrophilic polymer is more than 0.5 parts by weight, while preventing the collapse of the cured film and improving the adhesion to various substrates, if the composition of the present invention is coated like a film The thin film thickness of the substrate can prevent the substrate from deforming and warping during curing. It can be set at less than 50 parts by weight to prevent the cured film from becoming cloudy, stains, and orange peel.

4. Application method The application method of the hardened composition of the present invention only needs to be in accordance with conventional methods. For example, a method in which the composition is applied to the applied substrate by a general coating method and then irradiated with active energy rays or heated to harden it. The method of irradiating active energy rays only needs to use a general method known as a conventional hardening method. In addition, it is also possible to use (D) component (photopolymerization initiator) and (E) component (thermal polymerization initiator) in combination with the composition and irradiate it with active energy rays to heat-harden it to improve the density with the substrate The sex method.

The substrate to which the composition of the present invention can be applied can be applied to various materials, such as inorganic materials, plastics, and paper. Examples of the inorganic material include glass, metal, plaster, concrete, and stone. Metals include steel plate, metal such as aluminum and chromium, metal oxide such as zinc oxide (ZnO), and indium tin oxide (ITO). Specific examples of plastics include polyolefins such as polyethylene and polypropylene, ABS resins, polyvinyl alcohol, triethyl acetyl cellulose, and cellulose acetate resins such as diethyl acetyl cellulose, acrylic resins, and polypyrrole Ethylene phthalate, polycarbonate, polyallyl ester, polyether sulfone, cyclic polyolefin resin made from norbornene and other cyclic olefins into monomers, polyvinyl chloride, epoxy resin and polyurethane Ester resin, etc.

Among these substrates, the composition of the present invention has excellent adhesion to plastic substrates and is suitable for use with plastic substrates. Furthermore, inorganic materials are suitable for glass and metals. As far as plastic substrates are concerned, they are suitable for polyethylene terephthalate, carbonates, poly (meth) methacrylates and copolymers containing it as a main component. The shape of the plastic substrate can be suitable for application whether it is a film or a plate.

The coating method of the composition of the present invention on the substrate only needs to be appropriately set according to the purpose, such as bar coater, applicator, blade, dip coater, roll coater, spin coater, flow coating Coating method, such as machine, knife coater, corner wheel coater, reverse roll coater, die coater, lip coater, sprayer, gravure coater and micro gravure coater.

The thickness of the cured film of the cured composition only needs to be set appropriately according to the purpose. Although the thickness of the cured film can be selected according to the substrate to be used and the application of the substrate with the resulting cured film, it is preferably 1 to 100 μm, more preferably 2 to 40 μm.

When the curable composition contains an organic solvent, it is preferable to heat and dry it after applying it to the substrate to evaporate the organic solvent. The drying temperature is not particularly limited as long as the temperature of the applied base material does not cause problems such as deformation. The preferred heating temperature is 40 ~ 100 ℃. The drying time can be set appropriately according to the applied substrate and heating temperature, preferably 0.5 ~ 3 minutes.

When the hardening type composition of the present invention is used as an active energy ray hardening type composition, the active energy ray used to harden it can be exemplified by electron rays, ultraviolet rays, and visible rays, but ultraviolet rays or visible rays are particularly preferred. For ultraviolet light. Examples of the ultraviolet irradiation device include high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, and light-emitting diodes (LEDs). Although the irradiation energy should be appropriately set according to the type of active energy line and the blending composition, if the high-pressure mercury lamp is used as an example, the irradiation energy meter in the UV-A area should be 100 ~ 8,000mJ / cm ² , more preferably 200 ~ 3,000mJ / cm ² . In addition, when the irradiation energy is 1,000 mJ / cm ² or more, the anti-fog performance of the cured film may be insufficient. At this time, it is advisable to blend the aforementioned anti-fog modifier.

When the hardening type composition of the present invention is thermally hardened, the hardened film can be placed in a drier or the like which can be heated to obtain a hardened film. The drying time only needs to be properly set according to the applied substrate and heating temperature, preferably 0.5 to 60 minutes.

5. Use The hardened composition of the present invention can be used for various purposes, can be used as a coating agent, printing ink, etc., and can be suitably used as a coating agent.

Specific examples of the coating agent include anti-fog coating agents and coating agents that prevent dust from adhering to them. Examples of application of the anti-fog coating agent include protective glasses, goggles, bathroom inner walls, kitchen peripheral components, and glass and plastic used for headlight covers and taillight covers of automobiles and motorcycles. Examples of applications to prevent dust from adhering to the coating agent include plastic substrates and floors. Examples

The following shows examples and comparative examples to more specifically explain the present invention. In addition, the present invention is not limited to these embodiments. In addition, in the following, unless otherwise stated, "parts" means parts by weight, and "%" means% by weight.

1. Production Example 1-1) Production Example 1 [Production of Acrylate Containing (A) Component] 302.75 parts were fed into a 3-liter flask equipped with a stirrer, thermometer, gas introduction pipe, rectification tower, and cooling pipe (3.29 mol) glycerol (manufactured by Sakamoto Pharmaceutical Co., Ltd., purified glycerol (trade name). Hereinafter also referred to as "GLY"), 2312.84 parts (17.77 mol) 2-methoxyethyl acrylate (Hereinafter also referred to as "MCA"), 6.51 parts (0.06 mol) of DABCO used as catalyst X, 24.07 parts (0.12 mol) of zinc acrylate used as catalyst Y, 1.19 parts (0.01 mol) of hydroquinone monomethyl ether ( (Hereinafter also referred to as "MEHQ") and 0.21 serving (0.002 mol) phenothiazine , And make oxygen-containing gas (oxygen 5 volume%, nitrogen 95 volume%) bubble in the liquid. Heat and stir within the range of the reaction liquid temperature 100 ~ 130 ℃, adjust the pressure in the reaction system within the range of 110 ~ 760mmHg, and make 2-methoxyethanol by-produced along with the transesterification reaction with MCA (the following also The mixture called "MEL" is discharged from the reaction system through the rectification tower and cooling pipe. In addition, the same weight of MCA as the discharged liquid is added to the reaction system at any time. After 18 hours from the start of heating and stirring, the pressure in the reaction system was returned to normal pressure, and the discharge was ended. The acrylated rate of the hydroxyl group of GLY was calculated from the amount of MEL produced, and the result was 58 mol%. After the reaction liquid was cooled to room temperature and the precipitate was separated by filtration, 58.7 parts of aluminum silicate (KYOWAAD 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred to adsorb and remove the catalyst X and catalyst Y contained in the filtrate. It is heated and stirred for 1 hour at 70 ~ 100 ℃. After filtering and separating the aluminum silicate after adsorption treatment, the filtrate is charged into a flask connected to a stirrer, thermometer, glass introduction tube, cooling tube for distillation and decompression tube, at a temperature of 70 ~ 100 ° C and a pressure of 0.001 ~ 100mmHg Within the range, vacuum distillation was performed for 10 hours while bubbling dry air, and a distillate containing unreacted MCA was separated. 5.0 parts of diatomaceous earth (made by Showa Chemical Industry Co., Ltd., Radiolite (trade name)) was added to the kettle liquid and subjected to pressure filtration to make the resulting filtrate the component (A). (A) The output of the component is 651 parts. This is hereinafter referred to as A-1. The total yield of 302.75 parts of GLY fed into glycerol diacrylate (hereinafter also referred to as "GLY-DA") was 658 parts, and the yield of the above A-1 calculated on this basis was 99% . Using HPLC equipped with a UV detector, the purity of each component contained in A-1 was calculated according to the following formula (3). As a result, GLY-DA was 62%, and glycerin triacrylate (hereinafter also referred to as "GLY-TA") was 33%, glycerol monoacrylate (hereinafter also referred to as "GLY-MA") is 5%. The viscosity of the obtained component (A) was 43 mPa · s (25 ° C), and the hydroxyl value was 238 mgKOH / g. The Mw (Molecular weight) measured by GPC (Gel Permeation Chromatography) was 314.

In addition, HPLC, viscosity, hydroxyl value, GPC and GC (Gas Chromatography) were measured under the following conditions. ◆ HPLC measurement conditions ・ Apparatus: ACQUITY UPLC manufactured by Waters Corporation ・ Detector: UV detector ・ Detection wavelength: 210nm ・ Column: ACQUITY UPLC BEH C18 manufactured by Waters Corporation (Part No. 186002350, column inner diameter 2.1 mm, column length 50mm) • Column temperature: 40 ° C • Dissolved liquid composition: 0.03% by weight of a mixed solution of trifluoroacetic acid aqueous solution and methanol • Dissolved liquid flow rate: 0.3 mL / min

◆ (A) The method of calculating the purity of GLY-DA contained in the component The purity of GLY-DA (%) = [(D × 1.27) / (M × 1.74 + D × 1.27 + T)] × 100… Formula (3) Formula (3) In 3), D, M, and T are the following values obtained by analyzing (A) component using HPLC equipped with an ultraviolet (UV) detector.・ D: GLY-DA peak area at 210nm ・ M: GLY-MA peak area at 210nm ・ T: GLY-TA peak area at 210nm

◆ Viscosity measurement conditions Use E-type viscometer to measure the viscosity at 25 ℃.

◆ Conditions for measuring hydroxyl value Add acetylation reagent to the sample and heat-treat it in a temperature bath of 92 ℃ for 1 hour. After cooling, a small amount of water was added and heat treatment was carried out in a 92 ° C warm bath for 10 minutes. After cooling, the phenolphthalein solution is used as an indicator, and the acid is titrated in the potassium hydroxide solution to determine the hydroxyl value.

◆ GPC measurement conditions ・ Apparatus: GPC made by Waters Corporation, system name 1515 2414 717P RI ・ Detector: RI detector ・ Column: protection column, Shodex KFG (8μm 4.6 × 10mm) manufactured by Showa Denko Corporation, Two types of body columns, styragel HR 4E THF (7.8 × 300mm) and styragel HR 1THF (7.8 × 300mm) made by Waters Co., Ltd. • Column temperature: 40 ℃ • Composition of dissolution solution: THF (0.03% sulfur content as internal standard) ), Flow rate 0.75mL / min. • Calibration line: use standard polystyrene to make a calibration curve.・ In the detection peak derived from the component (A), the retention time is slower than the detection peak derived from the monofunctional (meth) acrylate, solvent, and water-derived detection peak. The calculation of the Mw is not considered, and the Multiple other detection spikes are regarded as one spike to calculate Mw.

1-2) Production Example 2 [Production of acrylates other than (A) components] 30.71 parts (3.29 moles) was fed into a 3-liter flask equipped with a stirrer, thermometer, gas introduction tube, rectification tower, and cooling tube ) GLY, 2312.76 parts (17.77 moles) MCA, 9.76 parts (0.087 moles) used as catalyst X DABCO, 36.10 parts (0.17 moles) used as catalyst Y zinc acrylate, 1.60 parts MEHQ, 0.074 parts 4-hydroxyl -2,2,6,6-tetramethylpiperidine-1-oxide (hereinafter also referred to as "TEMPOL") and 5.00 parts of pure water (0.28 mole), and make oxygen-containing gas (oxygen 5 volume%, nitrogen 95% by volume) foaming in the liquid. Heat and stir the reaction liquid at a temperature in the range of 105 to 130 ° C, adjust the pressure in the reaction system in the range of 150 to 760 mmHg, and make the by-produced mixed liquid with MEL accompanying the transesterification reaction with MCA pass through The distillation tower and cooling pipe are discharged from the reaction system. In addition, the same weight of MCA as the discharged liquid is added to the reaction system at any time. In addition, the MCA containing MEHQ and TEMPOL is added to the reaction system via the rectification tower at any time. After 40 hours from the start of heating and stirring, the pressure in the reaction system was returned to normal pressure, and the discharge was ended. The acrylated rate of the hydroxyl group of GLY was calculated from the amount of MEL produced, and the result was 91 mol%. The resulting reaction product was cooled to room temperature, and the precipitate was separated by pressure filtration. Put 14 parts of aluminum silicate (KYOWAAD 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.) into the filtrate, heat and stir at normal pressure for 1 hour under normal pressure in the range of internal temperature 80 ~ 105 ℃, then contact inside. Add 27 parts of calcium hydroxide at a temperature in the range of 20-40 ° C and stir for 1 hour at normal pressure. After separating insolubles by pressure filtration, while making dry air bubbling in the filtrate, while performing vacuum distillation at a temperature of 70 to 98 ° C and a pressure of 0.001 to 100 mmHg for 16 hours, a distillate containing unreacted MCA was separated liquid. The resulting kettle liquid was cooled to room temperature, 0.16 parts (0.0018 mol) of N, N-diethylhydroxylamine was added, and stirred at normal pressure for 1 hour. Thereafter, 8.0 parts of activated carbon (manufactured by FUTAMURA CHEMICAL CO., LTD., Taihe S (trade name)) was added and stirred at room temperature for 1 hour for contact treatment, and the solid matter containing activated carbon was separated by pressure filtration Get fluid. Hereinafter, this filtrate is referred to as A'-1. Using HPLC equipped with a UV detector, the purity of each component contained in A'-1 was calculated according to the aforementioned formula (3). As a result, GLY-DA was 8% and GLY-TA was 92%. The viscosity of the obtained component (A) was 26 mPa · s (25 ° C), and the hydroxyl value was 16 mgKOH / g. The Mw measured by GPC was 338.

2. Example 1 to Example 11 and Comparative Example 1 to Comparative Example 5 (Preparation of Hardened Composition) The components shown in Tables 1 to 3 described later were stirred and mixed at 40 ° C to obtain a hardened composition. The viscosity of the resulting hardened composition was measured at 25 ° C with an E-type viscometer. In addition, the curable composition of Example 7 was prepared by stirring and mixing components other than the component (E) at 40 ° C, cooling to 30 ° C, and dissolving the component (E).

3. Evaluation of plastic substrates The obtained hardening compositions of Examples 1 to 11 and Comparative Examples 1 to 5 were applied to the cut polycarbonate made by Mitsubishi Engineering-Plastics Corporation using a bar coater Iupilon NF2000 (150 mm × 70 mm × 1 mm) was made to have a film thickness of 10 μm, and a test body was produced. In addition, the compositions of Examples 10 and 11 were applied to the substrate and dried at 80 ° C for 90 seconds. Next, using a high-pressure mercury lamp equipped with a conveyor (EYE GRAPHICS CO., LTD. H06-L 41), the UV-A lamp output illuminance 80W / cm, each pass (pass) irradiation intensity 250mW / cm ² and irradiation The test body was irradiated with ultraviolet rays at an energy of 400 mJ / cm ² . The number of times until the surface viscosity of the cured film disappeared was evaluated as an index of active energy ray curability. The lower the number of passes, the better the hardenability. The hardening composition of Example 7 was heated in a 80 ° C dryer at 5 mL / min with nitrogen flowing for 60 minutes. The obtained cured film was evaluated according to the following method. The results are shown in Table 4 to Table 6.

1) Adhesiveness: Use a cutting knife to draw a cut with a 1mm vertical and horizontal interval on the resulting hardened film to form 100 square eyes with a size of 1mm × 1mm, and attach Nichiban Co., Ltd. to the checkerboard # After 405 of celluloid tape, peel it off firmly. The number of remaining films after peeling was evaluated. The greater the number of residual films, the better the adhesion.

2) Pencil hardness In accordance with JIS K5600-5-4, the pencil hardness of the obtained cured film was measured under a load of 750 g.

3) Persistence of anti-fogging The hardened film was exposed to steam at 80 ° C for 1 minute, and evaluation was made based on whether the hardened film was fogged. In addition, the anti-fogging continuity was evaluated by repeating the operation of exposing the cured film to steam at 80 ° C. for 1 minute after wiping the water adhered to the surface of the cured film with paper. In addition, A, B, and C in Table 3 and Table 4 mean as follows. A: No fog, B: Slight fog, C: Fog.

4) Surface resistivity was measured with a surface resistance meter (manufactured by Dia Instruments Co., Ltd., Loresta-GP MCP-T600) formed on a PET film (A-4300 manufactured by Toyobo Co., Ltd.) with a film thickness of 188 μm under the above coating and curing conditions. The surface resistance of the cured film is set to the surface resistivity immediately after patterning. The results are shown in Table 1. In addition, (Ω / □): Ohm / square is the unit of surface resistivity. The smaller the value, the smaller the surface resistivity. The measurement was carried out in two modes of the cured film immediately after curing and the cured film after the above anti-fogging durability test.

[Table 1]

[Table 2]

[table 3]

The meanings of the abbreviations in Tables 1 to 3 are as follows. The numerical value in parentheses in Table 1 to Table 3 means the number of parts of each component, "-" means not included. (A) Component · A-1: Glycerin acrylate mixture obtained in Production Example 1 (hydroxyl value: 238 mgKOH / g) (A) 'Component · A'-1: Glycerin acrylate mixture obtained in Production Example 2 (hydroxyl Value: 16mgKOH / g) (B) Ingredients: JI-62C01: A 50% solution of propylene glycol monomethyl ether having a compound having a cation and anion with an acryloyl group and ammonium ions (made by Japan Emulsifier Co., Ltd., JI-62C01)・ IL-MA2: Compounds with cations and anions with methacryl amide group and ammonium ion (manufactured by Guangrong Chemical Industry Co., Ltd., IL-MA2) ・ RS-3000: methacryl amide polyoxyalkylene Sodium sulfate (made by Sanyo Chemical Industry Co., Ltd., ELEMINOL RS-3000) ・ KH-10: polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt (Daiichi Pharmaceutical Co., Ltd. ), Acualon KH-10) SR-10: It has a SO ₃ NH ₄ group (anionic) at one end of polyethylene glycol (addition mole number 10) and an alkyl group and an alkene at the other end Propyl compound [ADEKA Co., Ltd., ADEKA REASOAP SR-10] (B) 'component · 2F-30: 30% aqueous solution of sodium lauryl sulfate (manufactured by Kao Corporation, EMAL 2F-30) (C) component・ M-240: Polyethylene glycol diacrylate (average ethylene oxide addition mole number 4) (ARONIX M-240 manufactured by East Asia Synthetic Co., Ltd.) ・ M-305: Neopentaerythritol triacrylate Mixture product with neopentaerythritol tetraacrylate (manufactured by East Asia Synthetic Co., Ltd., ARONIX M-305) ・ DMAA: dimethylacrylamide (manufactured by KJ Chemical Co., Ltd., DMAA) ・ M-402: Erxin A mixture of pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (ARONIX M-402 manufactured by East Asia Synthetic Co., Ltd.) ・ M-313: Heterocyanuric acid ethylene oxide adduct II And triacrylate mixture products (ARONIX M-313, manufactured by East Asia Synthetic Co., Ltd.) (D) Ingredients • HCPK: 1-hydroxy-alkylhexyl-phenyl-one (BASF Corporation, IRGACURE184) • TPO: 2, 4,6-Trimethylbenzyl-diphenyl-phosphine oxide (made by BASF, DAROCUR TPO) (E) Ingredients PERBUTYL O: tertiary butyl peroxy-2-ethylhexanoate ( Nippon Oil Co., Ltd., PERBUTYL O) Other ingredients. G-30: Propylene glycol / water mixed solution of sulfosuccinic acid di (2-ethylhexyl) sodium, RIKASURF G-30 made by Nippon Kogyo Co., Ltd. AT- 210: Aqueous solution containing acid-based polymer, AT-210 manufactured by East Asia Synthetic Co., Ltd. (aqueous solution containing carboxyl group-containing polymer neutralizing salt, solid content: 30%, viscosity: 9,000 mPa · s, pH = 8, M w: 10,000) ET-410: Aqueous dispersion containing an acid-based polymer, ET-410 (aqueous dispersion containing a carboxyl group-containing polymer neutralizing salt, solid content: 30%, viscosity) : 40mPa · s, pH = 8, Mw: 10,000) ・ PGM: propylene glycol monomethyl ether

[Table 4]

[table 5]

[Table 6]

4. Evaluation results From the results of Examples 1 to 11 in Tables 4 and 6, it is obvious that the adhesiveness, surface hardness, and antifogging properties of the cured film surface of the hardening composition of the present invention to the plastic substrate And its sustainability is excellent. Furthermore, the surface resistivity of the resulting cured film is low. In contrast, from the results in Table 5, it is clear that the hardened composition of Comparative Example 1 has a hydroxyl value of the blended glycerol acrylate mixture of less than 80 mgKOH / g of the lower limit of the component (A), although it is The acrylate of the glycerin skeleton failed to obtain sufficient hydrophilicity, and even if the (B) component was added, the anti-fogging property could not be obtained. In addition, when using an acrylate which is considered to have high hydrophilicity as shown in Comparative Examples 2 and 3 and has a structure different from the component (A), anti-fogging properties cannot be obtained. Although the curable composition of Comparative Example 4 is a curable composition that does not contain the component (B), it has no anti-fogging properties at all. Although the hardening composition of Comparative Example 5 uses a surfactant having no ethylenic unsaturated group at all in place of the component (B), the hardening composition still cannot achieve good antifogging properties. In addition, for the compositions of Examples 1 to 11, except that the test object was irradiated with ultraviolet light under the condition of irradiation energy of 1000 mJ / cm ² , a cured film was formed by the same method as described above, and the anti-fog was evaluated in the same manner as described above Persistent. As a result, although the compositions of Examples 1 to 7 have a reduced anti-fog durability of the cured film, the compositions of Examples 8 to 11 containing G-30 do not have the durability of the anti-fog of the cured film The change is excellent. Industrial availability

The hardening type composition of the present invention can be suitably used as an active energy ray hardening type composition, and the resulting cured film has excellent adhesion to various substrates and excellent scratch resistance, and also has excellent anti-tank properties and dust adhesion prevention properties. . The hardening composition of the present invention can be suitably used as a coating agent, and more specifically, can be used as a headlight cover and a taillight cover for protecting glasses, goggles, bathroom inner walls, automobiles and motorcycles, and anti-theft cameras Anti-fog coating agent for lens or plastic substrate to prevent dust adhesion.

no

Claims (17)

A hardening composition comprising the following components (A) and (B); (A) component: selected from the group consisting of glycerin (meth) acrylate and polyglycerin (meth) acrylate A mixture of at least one compound of which has a hydroxyl value of 80 mgKOH / g or more; (B) Component: a compound having an ethylenically unsaturated group and an ionic group. The hardening composition according to claim 1, wherein the aforementioned (A) component is a mixture of glycerin (meth) acrylate. The hardening type composition according to claim 2, wherein the aforementioned component (A) is calculated based on the peak area calculated using a high-speed liquid chromatograph equipped with an ultraviolet detector, and contains 30% or more of glycerol A mixture of meth) acrylates. The hardening composition according to claim 1, wherein the component (B) is a compound composed of a cation and an anion, and the cation has the aforementioned ethylenic unsaturated group in one molecule. The hardening composition according to claim 1, wherein the component (B) is a compound having a (meth) acryloyl group as the ethylenically unsaturated group. The hardening composition according to claim 1, which contains 0.01 to 20 parts by weight of the component (B) relative to 100 parts by weight of the total of the component (A). The hardening composition according to claim 1 further includes a compound (C) having an ethylenically unsaturated group other than the aforementioned (A) component and (B) component. The hardening composition according to claim 7, which contains 0.01 to 20 parts by weight of the component (B) relative to 100 parts by weight of the total of the components (A) and (C). The hardening composition according to claim 1, further contains an ionic surfactant having no ethylenic unsaturated group. The hardening composition according to any one of claims 1 to 9, which further contains a photopolymerization initiator (D). The hardening composition according to claim 10 is an active energy ray-curable coating agent composition. The hardening composition according to claim 10 is an active energy ray-curable anti-fog coating agent composition. The hardening composition according to any one of claims 1 to 9, which further contains a thermal polymerization initiator (E). The hardening type composition according to claim 13 is a thermosetting coating agent composition. The hardening composition according to claim 13 is a thermosetting anti-fog coating agent composition. The hardening composition according to any one of claims 1 to 9, which further contains a photopolymerization initiator (D) and a thermal polymerization initiator (E). The hardening type composition according to claim 16, which is an active energy ray hardening and thermosetting coating agent composition.