TWI874545B - Curable composition, curable coating composition, curable molding material composition, curable adhesive composition, and method for producing the curable composition - Google Patents

Abstract

The present invention provides a curable composition comprising (2-oxo-1,3-dioxacyclopentane-4-yl)methyl (meth)acrylate [glycerol carbonate (meth)acrylate], and the cured product thereof has no problem of metal corrosion and excellent water resistance. The curable composition of the present invention is a composition comprising component (A), wherein component (A) comprises a compound represented by the following formula (a), and the chlorine concentration contained in component (A) is less than 100 ppm, and the sodium concentration is less than 100 ppb. [In the formula (a), ^Ra represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ^Rb represents a single bond or an oxyalkylene group].

Description

Curable composition, curable coating composition, curable molding material composition, curable adhesive composition, and method for producing the curable composition

The present invention relates to a curable composition, preferably an active energy ray curable composition, and particularly preferably a solvent-free active energy ray curable composition, and belongs to these technical fields. Furthermore, in this specification, "acrylic acid group and/or methacrylic acid group" is represented as "(meth)acrylic acid group", "acrylate and/or methacrylate" is represented as "(meth)acrylate", and "acrylic acid and/or methacrylic acid" is represented as "(meth)acrylic acid". In addition, a compound containing an ethylenic unsaturated group is represented as a "curable component" in the composition.

Curable compositions are used in a variety of applications such as coating agents, adhesives, inks, and electronic materials. Among them, active energy ray-curable compositions have the advantage of being able to cure in a very short time, and (meth)acrylates with excellent curability are often used. In the case of ultraviolet curing, an irradiation device with ultraviolet lamps such as high-pressure mercury lamps, metal halide lamps, and light emitting diodes (LEDs) is used as a light source. In the case of electron beam curing, an electron beam irradiation device is used.

On the other hand, one of the drawbacks of active energy ray-curable compositions containing (meth)acrylates is that when cured in air, curing is inhibited by the influence of oxygen in the air (hereinafter referred to as "oxygen inhibition").

In the past, in order to prevent the curing resistance caused by this oxygen barrier, there are known methods of irradiating ultraviolet rays in a nitrogen environment, or coating the composition on the substrate, laminating the coated surface, and irradiating ultraviolet rays under oxygen shielding, but there are problems such as large-scale equipment, high cost and reduced productivity, which limits the scope of application. In addition, it is known to reduce oxygen resistance by mixing additives such as amine compounds and phosphorus compounds in the composition, but such additives with relatively good effects have the problem of coloring the cured product.

In order to solve the above-mentioned problems, (meth)acrylates that are not easily blocked by oxygen have been studied in the past. Among them, according to the report of C. Decker et al., it was clarified that (2-oxo-1,3-dioxacyclopentane-4-yl) methacrylate [glycerol carbonate acrylate. hereinafter referred to as "Glycarbo-A"], which is an acrylate having a cyclic carbonate skeleton, has high curability even in air (Non-patent Document 1). However, the production method used in this document is a highly dangerous method of reacting glycerol with highly toxic phosgene and reacting the obtained chloride with acrylic acid to obtain the target product, which has a high environmental load and great problems in terms of the safety of workers.

In addition, G. Wegner et al. found that (2-oxo-1,3-dioxacyclopentane-4-yl)methyl (meth)acrylate [(meth)acrylate glycerol carbonate] was obtained by reacting glycerol carbonate with (meth)acrylic acid chloride. Hereinafter referred to as "Glycarbo-(M)A"] (Non-patent document 2). However, the production method described in the document adopts the acyl chloride method, which has problems in terms of container corrosion and environmental load. In addition, according to the research of the inventors, the compound produced by the method described in the document has high sodium and chlorine concentrations, so when used as a component of a curing composition, the cured product has problems such as metal corrosion and low water resistance.

In addition, Patent Document 1 discloses a wear-resistant coating composition containing trifunctional or higher polyacrylate and Glycarbo-(M)A, and discloses that the composition has the effects of high hardness, fast curing speed, excellent adhesion, and less coloring of the cured product (Patent Document 1). However, the method for producing Glycarbo-(M)A in Patent Document 1 also uses the acyl chloride method, and the composition has the above-mentioned problems. [Prior Art Document] [Patent Document]

[Non-patent document 1] ＜＜Radiation Curing in Polymer Science and Technology＞＞, 1993, Vol. 3, pp. 33-64 [Non-patent document 2] ＜＜Macromolecules＞＞, 2007, Vol. 40, pp. 7558-7565 [Patent document 1] Japanese Patent Publication No. 2001-19875

[Problem to be solved by the invention] The inventors of the present invention have found a hardening composition containing Glycarbo-(M)A, and the hardened product thereof does not have the problem of metal corrosion and has excellent water resistance, so they have conducted intensive research. [Means for solving the problem]

In order to solve the above-mentioned problem, the inventors of the present invention found that a hardened material of a hardening composition containing Glycarbo-(M)A as component (A) and having reduced chlorine concentration and sodium concentration in component (A) is excellent in metal corrosion resistance and water resistance, thereby completing the present invention. The present invention is described in detail below. [Effects of the invention]

According to the composition of the present invention, the hardened product can be excellent in metal corrosion resistance and water resistance.

The curable composition of the present invention is a composition containing component (A), and component (A) contains a compound represented by formula (a) described below, and the chlorine concentration contained in component (A) is less than 100 ppm, and the sodium concentration is less than 100 ppb. Component (A), the curable composition, the purpose and the method of use are described below.

1. Component (A) Component (A), which is an essential component of the present invention, includes a compound represented by the following formula (a).

[Chemistry 1]

[In the formula (a), ^Ra represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ^Rb represents a single bond or an oxyalkylene group].

^Ra in the formula (a) represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ^Ra is preferably a hydrogen atom or a methyl group.

As the oxyalkylene group in R ^b , there can be listed ethylene oxide, propylene oxide, tetramethylene oxide, and mixed units of these ethylene oxide groups, preferably ethylene oxide. As the oxyalkylene group in R ^b , it can be an ethylene oxide group having a repeating unit, preferably 1 to 20, more preferably 1 to 15.

The composition containing component (a) is not easily obstructed by oxygen and has excellent curing properties. The viscosity of the composition can be reduced without a solvent, and the hardened product has excellent hardness, abrasion resistance and substrate adhesion. As the compound of formula (a), it is preferred that ^Ra is a hydrogen atom or a methyl group and ^Rb is a single bond. That is, Glycarbo-(M)A〔(2-oxo-1,3-dioxacyclopentane-4-yl)methyl(meth)acrylate〕 is preferred. Furthermore, the compound containing a hydrogen atom as R in formula (a), namely Glycarbo-A〔(2-oxo-1,3-dioxacyclopentane-4-yl)methacrylate〕, is more preferred in terms of excellent curing properties. The compound of formula (a) is preferably a compound in which ^Ra is a hydrogen atom or a methyl group, ^Rb is an oxyalkylene group, and the number of repeating units of the oxyalkylene group is 1 to 15. Component (A) may be a mixture of these compounds.

Furthermore, in the component (A), the chlorine concentration is less than 100 ppm, and the sodium concentration is less than 100 ppb. By making the chlorine concentration less than 100 ppm and the sodium concentration less than 100 ppb, the cured product of the obtained composition can be excellent in water resistance and metal corrosion resistance. Furthermore, the chlorine concentration in the present invention refers to the value obtained by quartz tube combustion-ion chromatography. In addition, the sodium concentration in the present invention refers to the value obtained by measuring the sample with an inductively coupled plasma (ICP) mass spectrometer and quantifying the detected elements using the absolute standard curve method.

As a method for producing the component (A), it is preferred that the component (A) having the above-mentioned chlorine concentration and sodium concentration can be easily produced by subjecting glycerol carbonate, an alkylene oxide adduct of glycerol carbonate, or a mixture of these compounds (hereinafter, these compounds are also collectively referred to as "glycerol carbonate-based compounds") and a compound having one _CH2 =C(R)-(C=O)- group (hereinafter, referred to as "monofunctional (meth)acrylate"). In addition, R of the _CH2 =C(R)-(C=O)- group is a hydrogen atom or an alkyl group of 1 to 5 carbonic acids, as described above. In the production method of subjecting a glycerol carbonate-based compound to a dehydration esterification reaction with (meth)acrylic acid, there is a problem that a large amount of high molecular weight products are generated as by-products, and the viscosity of the obtained component (A) increases. In addition, the acyl chloride method of reacting a glycerol carbonate compound with (meth)acrylic chloride has the problem of difficulty in reducing the chlorine concentration and sodium concentration contained in the (A) component, and there is a problem of reduced water resistance and metal corrosion resistance of the cured product. In contrast, the ester exchange reaction of a glycerol carbonate compound with a monofunctional acrylate can produce the (A) component with good yield and reduced chlorine concentration and sodium concentration.

Hereinafter, regarding a production method by an ester exchange reaction as a preferred production method of the component (A), a method for producing a glycerol carbonate-based compound, a monofunctional (meth)acrylate, a catalyst, and the component (A) will be described.

1-1. Glyceryl carbonate compounds The glyceryl carbonate compounds used as the raw material of component (A) are glyceryl carbonate, alkylene oxide adducts of glyceryl carbonate, or mixtures of these compounds. As glyceryl carbonate (4-hydroxymethyl-1,3-dioxacyclopentane-2-one), commercially available products can be used. In addition, products produced by subjecting glycerol to an ester exchange reaction with a carbonate compound such as ethyl carbonate, dimethyl carbonate, and diethyl carbonate in the presence of a catalyst can also be used. As alkylene oxide adducts of glyceryl carbonate, products synthesized by subjecting an alkylene oxide adduct of glycerol to an ester exchange reaction with a carbonate compound such as ethyl carbonate, dimethyl carbonate, and diethyl carbonate in the presence of a catalyst can be used. As glyceryl carbonate compounds, mixtures of the above compounds can be used.

1-2. Monofunctional (meth)acrylate The monofunctional (meth)acrylate used as a raw material of the component (A) is a compound containing one CH ₂ =C(R)-(C=O)- group in the molecule, and examples thereof include compounds represented by the following general formula (1).

[Chemistry 2]

In formula (1), ^R1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ^R2 represents an organic group having 1 to 50 carbon atoms.

R ¹ in the general formula (1) is preferably a hydrogen atom or a methyl group. Preferred specific examples of R ² in the general formula (1) include alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and 2-ethylhexyl; alkoxyalkyl groups, such as 2-methoxyethyl, 2-ethoxyethyl and 2-methoxybutyl; and dialkylamino groups, such as N,N-dimethylaminoethyl, N,N-diethylaminoethyl, N,N-dimethylaminopropyl and N,N-diethylaminopropyl. Specific examples of ^R2 in the general formula (1) include, in addition to the above, functional groups listed in Japanese Patent Application Publication No. 2017-39916, Japanese Patent Application Publication No. 2017-39917, and International Publication No. 2017/033732.

In the present invention, these monofunctional (meth)acrylates can be used alone or in any combination of two or more. Among these monofunctional (meth)acrylates, preferred are (meth)acrylate alkyl esters having an alkyl group with a carbon number of 1 to 8, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, (meth)acrylate alkoxyalkyl esters such as 2-methoxyethyl (meth)acrylate, and (meth)acrylate N,N-dimethylaminoethyl ester. Particularly preferred are acrylates having an alkyl group with a carbon number of 1 to 4, which are easily available and have good reactivity with glycerol carbonate compounds, and (meth)acrylate alkoxyalkyl esters having an alkyl group with a carbon number of 1 to 2. Furthermore, more preferred is an alkoxyalkyl (meth)acrylate having an alkyl group with 1 to 2 carbon atoms, which promotes the dissolution of glycerol carbonate-based compounds and exhibits excellent reactivity, and 2-methoxyethyl (meth)acrylate is particularly preferred.

1-3. Catalyst As the catalyst for the transesterification reaction in the method for producing component (A), conventionally known catalysts such as tin-based catalysts, titanium-based catalysts, and sulfuric acid can be used. In the present invention, in order to efficiently and efficiently produce component (A), it is preferred to use the following catalyst X and catalyst Y in combination as the catalyst. Catalyst X: One or more compounds selected from the group consisting of a cyclic tertiary amine having a nitrogen-doped bicyclic structure or a salt or complex thereof (hereinafter referred to as a "nitrogen-doped bicyclic compound"), an amidine or a salt or complex thereof (hereinafter referred to as an "amidine compound"), a compound having a pyridine ring or a salt or complex thereof (hereinafter referred to as a "pyridine compound"), and a phosphine or a salt or complex thereof (hereinafter referred to as a "phosphine compound"). Catalyst Y: A zinc-containing compound. Catalyst X and catalyst Y are described below.

1-3-1. Catalyst X Catalyst X is one or more compounds selected from the group consisting of nitrogen-doped bicyclic compounds, amidine compounds, pyridine compounds and phosphine compounds. As catalyst X, among the compound group, one or more compounds selected from the group consisting of nitrogen-doped bicyclic compounds, amidine compounds and pyridine compounds are preferred. These compounds have excellent catalytic activity and can better produce component (A). In addition, after the reaction is completed, they form a complex with the catalyst Y described below, so they can be easily removed from the reaction solution after the reaction is completed by a simple method based on filtration and adsorption. In particular, the complex of the nitrogen-doped bicyclic compound and the catalyst Y is poorly soluble in the reaction solution, and can be removed more easily by filtration and adsorption. On the other hand, although the phosphine compound has excellent catalytic activity, it is difficult to form a complex with the catalyst Y, and most of it will be directly dissolved in the reaction solution after the reaction, so it is difficult to remove it from the reaction solution by a simple method based on filtration and adsorption. Therefore, the phosphine catalyst remains in the final product, which sometimes causes turbidity or catalyst precipitation during the storage of the product, or thickening or gelation over time. This storage stability problem sometimes occurs when it is used as a component of a composition.

As specific examples of the nitrogen-doped bicyclic compound, various compounds can be listed as long as they satisfy the requirement of a cyclic tertiary amine having a nitrogen-doped bicyclic structure, a salt of the amine, or a complex of the amine. As preferred compounds, the following can be listed: Quinuclidine, 3-hydroxy Pyridine, 3- 3-quinuclidinone, 1-azabicyclo[2.2.2]octane-3-carboxylic acid, and triethylenediamine (also known as 1,4-diazabicyclo[2.2.2]octane; hereinafter referred to as "DABCO"), etc. Specific examples of the azabicyclic compounds include, in addition to the above, compounds listed in Japanese Patent Laid-Open No. 2017-39916, Japanese Patent Laid-Open No. 2017-39917, International Publication No. 2016/163208, and International Publication No. 2017/033732.

Specific examples of the amidine compounds include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 1-allylimidazole, 1,8-diazabicyclo[5.4.0]undec-7-ene (hereinafter referred to as "DBU"), 1,5-diazabicyclo[4.3.0]non-5-ene (hereinafter referred to as "DBN"), N-methylimidazole hydrochloride, DBU hydrochloride, DBN hydrochloride, N-methylimidazole acetate, DBU acetate, DBN acetate, N-methylimidazole acrylate, DBU acrylate, DBN acrylate, and o-phthalimide DBU.

As main specific examples of pyridine compounds, there can be listed: pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, and N,N-dimethyl-4-aminopyridine (hereinafter referred to as "DMAP"), etc. As specific examples of pyridine compounds, in addition to the above, there can also be listed the compounds listed in Japanese Patent Laid-Open No. 2017-39916, Japanese Patent Laid-Open No. 2017-39917, International Publication No. 2016/163208 and International Publication No. 2017/033732.

Examples of the phosphine or its salt or complex include compounds having a structure represented by the following general formula (2).

[Chemistry 3]

[In formula (2), R ³ , R ⁴ and R ⁵ represent a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. R ³ , R ⁴ and R ⁵ may be the same or different.]

Specific examples of phosphine compounds include triphenylphosphine, tri(4-methoxyphenyl)phosphine, tri(p-tolyl)phosphine, tri(m-tolyl)phosphine, tri(4-methoxy-3,5-dimethylphenyl)phosphine, and tricyclohexylphosphine. Specific examples of phosphine compounds include, in addition to the above, compounds listed in Japanese Patent Laid-Open No. 2017-39916, Japanese Patent Laid-Open No. 2017-39917, International Publication No. 2016/163208, and International Publication No. 2017/033732.

In the present invention, the catalysts X can be used alone or in any combination of two or more. Pyridine, 3- Pyridone, 3-hydroxy In particular, 3-hydroxy-1-nitropropene which has good reactivity with most glycerol carbonate compounds and is easily available is more preferred. Pyridine, DABCO, N-methylimidazole, DBU and DMAP.

The ratio of the catalyst X used in the method for producing the component (A) is not particularly limited, but preferably 0.0001 to 0.5 mol of the catalyst X is used per 1 mol of the total hydroxyl groups in the glycerol carbonate-based compound, and more preferably 0.0005 to 0.2 mol. By using 0.0001 mol or more of the catalyst X, the amount of the component (A) produced can be increased, and by setting it to 0.5 mol or less, the production of by-products or the coloring of the reaction solution can be suppressed, and the purification step after the reaction is simplified.

1-3-2. Catalyst Y Catalyst Y is a compound containing zinc. As catalyst Y, various compounds can be used as long as it is a compound containing zinc. Organic zinc acid and zinc diketone enolate are preferred in terms of excellent reactivity. As organic zinc acid, zinc dibasic acid such as zinc oxalate and compounds represented by the following general formula (3) can be listed.

[Chemistry 4]

[In formula (3), ^R6 and ^R7 are linear or branched alkyl groups having 1 to 20 carbon atoms, linear or branched alkenyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 24 carbon atoms, or cycloalkyl groups having 5 to 20 carbon atoms. ^R6 and ^R7 may be the same or different.] As the compound of formula (3), preferably, ^R6 and ^R7 are linear or branched alkyl groups having 1 to 20 carbon atoms. Among ^R6 and ^R7 , the linear or branched alkyl groups having 1 to 20 carbon atoms are functional groups having no halogen atoms such as fluorine and chlorine. Catalyst Y having such functional groups is preferred because it can produce component (A) with high yield.

Examples of the zinc diketoenol include compounds represented by the following general formula (4).

[Chemistry 5]

[In formula (4), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different.]

Specific examples of the zinc-containing compound represented by the general formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octanoate, zinc neodecanoate, zinc laurate, zinc myristate, zinc stearate, zinc cyclohexanebutyrate, zinc 2-ethylhexanoate, zinc benzoate, zinc tert-butylbenzoate, zinc salicylate, zinc cycloalkanoate, zinc acrylate, and zinc methacrylate. In addition, in the presence of hydrates or solvent compounds or complexes with catalyst X, these zinc-containing compounds, solvent compounds, and complexes with catalyst X can also be used as catalyst Y in the method for producing component (A).

Specific examples of the zinc-containing compound represented by the general formula (4) include zinc acetylacetonate, zinc acetylacetonate hydrate, zinc bis(2,6-dimethyl-3,5-heptanedione), zinc bis(2,2,6,6-tetramethyl-3,5-heptanedione), and zinc bis(5,5-dimethyl-2,4-hexanedione). In addition, when these zinc-containing compounds are present as hydrates or solvent compounds or complexes with catalyst X, the hydrates, solvent compounds, and complexes with catalyst X can also be used as catalyst Y in the method for producing component (A).

As the organic acid zinc and diketoenol zinc in the catalyst Y, the compounds described above may be used directly, or these compounds may be generated in the reaction system and used. For example, there may be a method of using zinc compounds such as metallic zinc, zinc oxide, zinc hydroxide, zinc chloride and zinc nitrate (hereinafter referred to as "raw material zinc compound") as raw materials, and reacting the raw material zinc compound with an organic acid in the case of an organic acid zinc, and a method of reacting the raw material zinc compound with 1,3-diketone in the case of a diketoenol zinc.

In the present invention, the catalysts Y can be used alone or in any combination of two or more. Among the catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate and zinc acetylacetonate are preferred, and zinc acetate, zinc acrylate and zinc acetylacetonate, which have good reactivity with glycerol carbonate compounds and are easily available, are more preferred.

The ratio of catalyst Y used in the method for producing component (A) is not particularly limited, but preferably 0.0001 mol to 0.5 mol of catalyst Y is used per 1 mol of the total hydroxyl group in the glycerol carbonate-based compound, and more preferably 0.0005 mol to 0.2 mol. By using 0.0001 mol or more of catalyst Y, the amount of component (A) produced can be increased, and by setting it to 0.5 mol or less, the production of by-products or coloring of the reaction solution can be suppressed, and the purification step after the reaction is simplified.

1-4. Production method of component (A) Component (A) is preferably produced by subjecting a glycerol carbonate compound to an ester exchange reaction with a monofunctional (meth)acrylate in the presence of an ester exchange catalyst. As described above, as a production method of component (A), a production method using the catalyst X and the catalyst Y as catalysts is preferably used. The production method is described below.

The ratio of catalyst X to catalyst Y used in the method for producing component (A) is not particularly limited, but preferably 0.005 mol to 10.0 mol of catalyst X is used relative to 1 mol of catalyst Y, and more preferably 0.05 mol to 2.0 mol. By using 0.005 mol or more, the amount of the compound of formula (a) produced can be increased, and by setting it to 10.0 mol or less, the generation of by-products or the coloring of the reaction solution can be suppressed, and the purification step after the reaction is simplified.

As a combination of catalyst X and catalyst Y used in the present invention, it is preferred that catalyst X is a nitrogen-doped bicyclic compound and catalyst Y is a compound represented by the general formula (3). Furthermore, it is best that the nitrogen-doped bicyclic compound is DABCO and the compound represented by the general formula (3) is zinc acetate and/or zinc acrylate. This combination can obtain component (A) in good yield and has excellent color tone after the reaction. Therefore, it can be preferably used for various industrial uses that attach importance to color tone. Furthermore, it is a catalyst that can be obtained at a relatively low price, so it is an economically advantageous production method.

The catalyst X and catalyst Y used in the present invention can be added at the beginning of the reaction or in the middle. In addition, the desired amount can be added at once or separately.

The reaction temperature in the method for producing component (A) is preferably 40°C to 180°C, more preferably 60°C to 160°C. By setting the reaction temperature to 40°C or higher, the reaction rate can be accelerated, and by setting it to 180°C or lower, the thermal polymerization of (meth)acryloyl groups in the raw materials or products can be suppressed, the coloring of the reaction solution can be suppressed, and the purification step after the reaction can be simplified.

The reaction pressure in the method for producing the component (A) is not particularly limited as long as the predetermined reaction temperature can be maintained, and the method may be carried out under reduced pressure or under increased pressure. The reaction pressure is preferably 0.000001 MPa to 10 MPa (absolute pressure).

In the method for producing component (A), a monohydric alcohol derived from a monofunctional (meth)acrylate is produced as a by-product as the transesterification reaction proceeds. The monohydric alcohol may coexist in the reaction system, but by discharging the monohydric alcohol out of the reaction system, the transesterification reaction can be further promoted.

In the production method of component (A), the reaction can be carried out without using an organic solvent, or an organic solvent can be used as needed. Specific examples of organic solvents include: hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, pentylbenzene, dipentylbenzene, tripentylbenzene, dodecylbenzene, di-dodecylbenzene, pentyltoluene, isopropyltoluene, decahydronaphthalene and tetrahydronaphthalene; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, diethyl acetal, dihexyl acetal, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, trioxane, dioxane, anisole, diphenyl ether, dimethyl thiocyanate, , diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether; crown ethers such as 18-crown-6; esters such as methyl benzoate and γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone and benzophenone; carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene glycol carbonate, propylene glycol carbonate, 1,2-butanediol carbonate; sulfones such as cyclobutane sulfone; sulfones such as dimethyl sulfone; ureas or their derivatives; phosphine oxides such as tributylphosphine oxide; ionic liquids such as imidazolium salts, piperidinium salts and pyridinium salts; silicone oil; and water. Among these solvents, hydrocarbons, ethers, carbonate compounds and ionic liquids are preferred. These solvents can be used alone or in any combination of two or more to form a mixed solvent.

In the method for producing component (A), inert gas such as argon, helium, nitrogen and carbon dioxide may be introduced into the system for the purpose of maintaining the color tone of the reaction solution well, and oxygen-containing gas may be introduced into the system for the purpose of preventing polymerization of (meth)acrylic acid groups. Specific examples of oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium. As a method for introducing the oxygen-containing gas, a method of dissolving the oxygen-containing gas in the reaction solution or blowing the oxygen-containing gas into the reaction solution (so-called bubbling) may be cited.

In the method for producing component (A), it is preferred to add a polymerization inhibitor to the reaction solution for the purpose of preventing the polymerization of (meth)acryloyl groups. Examples of the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors. Specific examples of organic polymerization inhibitors include phenolic compounds such as hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, and 4-tert-butyl o-catechol; quinone compounds such as benzoquinone; phenothiazine; and N-nitroso-N-phenylhydroxylamine ammonium. As an organic polymerization inhibitor, an organic compound having a stable free radical may be used, and examples thereof include galvinoxyl and N-oxyl free radical compounds. As N-oxyl free radical compounds, examples thereof include 2,2,6,6-tetramethylpiperidin-1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, and 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical. As an inorganic polymerization inhibitor, examples thereof include copper chloride, copper sulfate, and iron sulfate. As organic salt-based polymerization inhibitors, copper dibutyl dithiocarbamate and aluminum N-nitroso-N-phenylhydroxylamine salt can be listed. The polymerization inhibitor can be added alone or in any combination of two or more, and can be added at the beginning of the present invention or in the middle. In addition, the desired amount can be added at one time or separately. In addition, it can also be added continuously through a refining tower. The addition ratio of the polymerization inhibitor is preferably 5 wtppm to 30,000 wtppm in the reaction solution, and more preferably 25 wtppm to 10,000 wtppm. By setting the ratio to 5 wtppm or more, the polymerization inhibition effect can be fully exerted, and by setting it to 30,000 wtppm or less, the coloring of the reaction solution can be suppressed, the purification step after the reaction can be simplified, or the curing speed of the obtained component (A) can be prevented from decreasing.

The reaction time of the method for producing component (A) varies depending on the type and amount of the catalyst, reaction temperature, reaction pressure, etc., but is preferably 0.1 to 150 hours, more preferably 0.5 to 80 hours.

The method for producing component (A) can be implemented by any of batch, semi-batch and continuous methods. As an example of the batch method, it can be implemented by the following method: a glycerol carbonate compound, a monofunctional (meth)acrylate, a catalyst and a polymerization inhibitor are added to a reactor, and an oxygen-containing gas is bubbled in the reaction liquid while stirring at a predetermined temperature. Thereafter, the monohydric alcohol produced as a by-product of the transesterification reaction is extracted from the reactor at a predetermined pressure, thereby generating the target component (A) and the like.

It is preferable to separate and purify the reaction product obtained by the method for producing component (A) because the target component (A) can be obtained with high purity. As separation and purification operations, crystallization operation, filtration operation, distillation operation and extraction operation can be listed, and it is preferable to combine these. As crystallization operation, cooling crystallization and concentration crystallization can be listed, as filtration operation, pressure filtration, suction filtration and centrifugal filtration can be listed, as distillation operation, single distillation, separation distillation, molecular distillation and water vapor distillation can be listed, and as extraction operation, solid-liquid extraction and liquid-liquid extraction can be listed. A solvent may be used in the separation and purification operation. In addition, a neutralizer for neutralizing the catalyst and/or polymerization inhibitor used in the present invention, an adsorbent for adsorption removal, an acid and/or base for decomposing or removing by-products, activated carbon for improving color tone, diatomaceous earth for improving filtration efficiency and filtration speed, etc. may also be used.

The chlorine concentration of the component (A) thus obtained can be lowered to less than 100 ppm, preferably lower than 10 ppm, and the sodium concentration can be lowered to less than 100 ppb, preferably lower than 10 ppb, so that a hardening composition having excellent water resistance and metal corrosion resistance can be obtained.

When a compound having an ethylenically unsaturated group other than the component (A) described later is formulated (hereinafter referred to as "component D"), the content of the component (A) is preferably 5% to 100% by weight, more preferably 5% to 95% by weight, and particularly preferably 10% to 70% by weight in the total 100% by weight of the curable component. By making the content of the component (A) 5% by weight or more, the composition can be made low in viscosity. On the other hand, by making it 95% by weight or less, the crosslinking density can be increased and the heat resistance can be improved. In addition, the curable component refers to the component (A) and the component (D) as defined above.

2. Curable composition The present invention is a curable composition comprising the above-mentioned (A). As a method for producing the composition, it is preferably a method for producing the component (A), wherein the component (A) is a mixture of reaction products including (meth)acrylates obtained by subjecting a carbonate glycerol compound to an ester exchange reaction with a monofunctional (meth)acrylate in the presence of the above-mentioned catalyst X and catalyst Y. According to this production method, the component (A) can be obtained at a high yield, so the cost and productivity are excellent. In addition, the component (A) obtained by this production method has a small amount of side reaction high molecular weight products and is easy to handle due to its low viscosity, thereby reducing the chlorine concentration and sodium concentration. As this step, the production method of the component (A) can be followed. Furthermore, when preparing other components described later, it is sufficient to stir and mix the (A) component and the other components.

The viscosity of the composition may be appropriately set depending on the purpose, and is preferably 10 mPa·s to 3,000 mPa·s, more preferably 20 mPa·s to 1,500 mPa·s.

The composition of the present invention can be used as an active energy ray-curable composition or a heat-curable composition, but can be preferably used as an active energy ray-curable composition. In addition, the composition of the present invention can be used in any form of a solvent-free composition without an organic solvent, a solvent-based composition containing an organic solvent, or an aqueous composition in which the (A) component is dissolved or dispersed in water. In the aqueous composition in which the (A) component is dispersed in water, a commonly used emulsifier or a reactive emulsifier described below can be used as a dispersant.

The composition of the present invention has the aforementioned component (A) as an essential component, but various components can be formulated according to the purpose. Preferred examples of other components include: photopolymerization initiator [hereinafter referred to as "component (B)"], thermal polymerization initiator [hereinafter referred to as "component (C)"], and compounds having olefinic unsaturated groups other than the aforementioned component (A) [hereinafter referred to as "component (D)" etc. These components are described below. In addition, the other components described below may use only one of the compounds exemplified, or may use two or more of them in combination.

2-1. (B) Component When the composition of the present invention is used as an active energy ray-curable composition, especially when ultraviolet rays and visible rays are used as active energy rays, it is preferred to contain more (B) component (photopolymerization initiator) from the viewpoint of ease of curing and cost. When electron beams are used as active energy rays, it is not necessarily necessary to mix, but a small amount may be mixed as needed to improve curability.

Specific examples of the component (B) include benzyl dimethyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]propanone, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]benzene, Acetophenone compounds such as 2-(4-(methylthio)phenyl)-2-oxolinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-oxolinylphenyl)butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-oxolin-4-ylphenyl)butane-1-one, and 3,6-bis(2-methyl-2-oxolinylpropionyl)-9-n-octylcarbazole; Benzoin compounds such as benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1-[4-(4-benzoylphenylsilyl)phenyl]-2-methyl-2-(4-methylphenylsilyl)propane-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone and 4-methoxy-4'-dimethylaminobenzophenone; Bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, and bis(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide, etc.; and Thiathione compounds such as thiothione, 2-chlorothiothione, 2,4-diethylthiothione, isopropylthiothione, 1-chloro-4-propylthiothione, 3-[3,4-dimethyl-9-oxo-9H-thiothione-2-yl-oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride and fluorothiothione, etc. As compounds other than the above, there can be listed: benzyl, methyl phenylglyoxylate, ethyl (2,4,6-trimethylbenzyl) phenylphosphinate, ethyl anthraquinone, phenanthrenequinone, camphorquinone, etc.

Among these compounds, acetophenone compounds are preferred, and α-hydroxyphenyl ketone is preferred because it has good surface curability even when applied as a thin film in the atmosphere. α-hydroxyphenyl ketone is more preferred as 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propane-1-one. In addition, when the film thickness of the cured product needs to be thickened, for example, when it needs to be made 50 μm or more, in order to improve the curability of the inside of the cured product, or when a UV absorber or pigment is used in combination, it is preferred to use an acylphosphine oxide compound and a morpholine compound among acetophenone compounds in combination. As the acylphosphine oxide compound in this case, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide, ethyl-(2,4,6-trimethylbenzyl)phenylphosphinate and bis(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide can be listed. As the morpholine compound, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinepropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinephenyl)butane-1-one, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-yl-phenyl)-butane-1-one can be listed.

The content of component (B) is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the total amount of the curable components. When the content of component (B) is 0.05 parts by weight or more, the light curing property of the composition can be improved and the adhesion can be excellent. When the content is 15 parts by weight or less, the internal curing property of the cured product can be improved and the adhesion to the substrate can be improved.

2-2. Component (C) Component (C) is a thermal polymerization initiator. When the composition is used as a thermosetting composition, component (C) can be formulated. The composition of the present invention can also be formulated with a thermal polymerization initiator to make it heat-cured. As the thermal polymerization initiator, various compounds can be used, preferably organic peroxides and azo initiators.

Specific examples of organic peroxides include 1,1-bis(tert-butylperoxy)2-methylcyclohexane, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(4,4-di-butylperoxy)cyclohexane, 3-Butylperoxy)cyclohexyl)propane, 1,1-bis(tert-butylperoxy)cyclododecane, tert-butylperoxyisopropylmonocarbonate, tert-butylperoxymaleate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluylperoxy)hexane, tert-butylperoxyisopropylmonocarbonate, tert-butylperoxy-2-ethylhexylmonocarbonate, Peroxybenzoic acid tert-hexyl ester, 2,5-di-methyl-2,5-di(benzoylperoxy)hexane, peroxyacetic acid tert-butyl ester, 2,2-bis(tert-butylperoxy)butane, peroxybenzoic acid tert-butyl ester, n-butyl-4,4-bis(tert-butylperoxy)valerate, peroxyisophthalic acid di-tert-butyl ester, α,α'-bis(tert-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5- Dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, tert-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-hexyl hydroperoxide, tert-butyl hydroperoxide, etc.

Specific examples of azo compounds include 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(aminoformylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azobis-tert-octane, azobis-tert-butane, and the like.

These may be used alone or in combination of two or more. In addition, organic peroxides may also undergo redox reactions by combining with reducing agents.

The content ratio of component (C) is preferably 10 parts by weight or less relative to 100 parts by weight of the total amount of the curable component. When component (C) is used alone, it can be carried out according to the conventional method of free radical thermal polymerization. Depending on the situation, it can also be used in combination with component (B) (photopolymerization initiator) to perform thermal curing after light curing in order to further increase the reaction rate.

2-3. Component (D) Component (D) is a compound having an ethylenically unsaturated group and is a compound other than the component (A). The ethylenically unsaturated group of component (D) is preferably a (meth)acrylic group, and more preferably an acryl group, in terms of excellent curability of the composition.

The component (D) may be any compound other than the above-mentioned (A) as long as it contains one or more ethylenically unsaturated groups. Specifically, there may be mentioned compounds containing one ethylenically unsaturated group (hereinafter referred to as "monofunctional unsaturated compound"), compounds containing two ethylenically unsaturated groups (hereinafter referred to as "bifunctional unsaturated compound"), and compounds containing three or more ethylenically unsaturated groups (hereinafter referred to as "trifunctional or higher unsaturated compounds").

Specific examples of monofunctional unsaturated compounds include compounds containing a (meth)acryl group, and compounds containing a monofunctional (meth)acrylamide and a vinyl group. Examples of compounds containing a (meth)acryloyl group include: Compounds containing a carboxyl group and an ethylenically unsaturated group, such as (meth)acrylic acid, Michael addition type dimer of (meth)acrylic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, and monohydroxyethyl (meth)acrylate phthalate; (Meth)acrylates having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Carbitol (meth)acrylates, such as ethyl carbitol (meth)acrylate, butyl carbitol (meth)acrylate, and 2-ethylhexyl carbitol (meth)acrylate; Monofunctional (meth)acrylates having aromatic groups, such as benzyl (meth)acrylate, (meth)acrylates of phenol epoxide adducts, (meth)acrylates of alkylphenol epoxide adducts, (meth)acrylates of p-cumylphenol epoxide adducts, o-phenylphenol (meth)acrylate, (meth)acrylates of o-phenylphenol epoxide adducts, and 2-hydroxy-3-phenoxypropyl (meth)acrylate; Monofunctional (meth)acrylates having alicyclic groups, such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; and Monofunctional (meth)acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth)acrylate, (meth)acryloylmorpholine, N-(2-(meth)acryloyloxyethyl)hexahydroxylenedicarboximide and N-(2-(meth)acryloyloxyethyl)tetrahydroxylenedicarboximide, etc.

As monofunctional (meth)acrylamide, there can be listed: N,N-dimethyl (meth)acrylamide, (meth)acryl morpholine, N-methyl (meth)acrylamide, N-n-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-sec-butyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, and N-n-hexyl (meth)acrylamide and other N-alkyl (meth)acrylamide; N-hydroxyethyl (meth)acrylamide and other N-hydroxyalkyl (meth)acrylamide; and N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (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, etc.

Examples of the compound containing a vinyl group include N-vinylpyrrolidone and N-vinylcaprolactam.

As the bifunctional unsaturated compound, a bifunctional (meth)acrylate is preferred. Specific examples of the bifunctional (meth)acrylate include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, di(meth)acrylate of bisphenol A epoxide adduct, and di(meth)acrylate of bisphenol F epoxide adduct, etc.

As the bifunctional (meth)acrylate, in addition to the above-mentioned compounds, oligomers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate and polyether (meth)acrylate can be used.

As the trifunctional or higher unsaturated compound, the trifunctional or higher (meth)acrylate containing three or more (meth)acryloyl groups is preferred. For example, polyol poly (meth)acrylates such as glycerol tri (meth)acrylate, trihydroxymethylpropane tri (meth)acrylate, pentaerythritol tri or tetra (meth)acrylate, ditrihydroxymethylpropane tri or tetra (meth)acrylate, diglycerol tri or tetra (meth)acrylate and dipentaerythritol tri, tetra, penta or hexa (meth)acrylate can be listed; and Glycerol epoxide tri(meth)acrylate, pentaerythritol epoxide tri- or tetra(meth)acrylate, ditrihydroxymethylpropane epoxide tri- or tetra(meth)acrylate, diglycerol epoxide tri- or tetra(meth)acrylate, dipentaerythritol epoxide tri-, tetra-, penta- or hexa(meth)acrylate, poly(meth)acrylate of polyol epoxide adducts, and tri(meth)acrylate of isocyanuric acid epoxide adducts. As examples of the above-mentioned epoxide adducts, ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts can be cited.

As the trifunctional or higher functional (meth)acrylate, in addition to the above compounds, urethane (meth)acrylate and the like can also be used.

Among these compounds, tri- or tetra-(meth)acrylate of pentaerythritol, tri-, tetra-, penta- or hexa-(meth)acrylate of dipentaerythritol, and tri- or higher-functional urethane (meth)acrylate are preferred because the hardened products of the obtained compositions have high hardness and excellent substrate adhesion. The tri- or higher-functional urethane (meth)acrylate is described in detail below.

Examples of the trifunctional or higher-functional urethane (meth)acrylate include reaction products of a polyol, a polyisocyanate, and a hydroxyl-containing (meth)acrylate, and reaction products of an organic polyisocyanate and a hydroxyl-containing (meth)acrylate compound.

Examples of the polyol include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by reacting the polyols with the polyacids, caprolactone polyols obtained by reacting the polyols, the polyacids, and ε-caprolactone, and polycarbonate polyols (for example, polycarbonate polyols obtained by reacting 1,6-hexanediol with diphenyl carbonate).

Examples of organic polyisocyanates include diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and dicyclopentyl diisocyanate; and organic polyisocyanates having three or more isocyanate groups such as hexamethylene diisocyanate trimer and isophorone diisocyanate trimer.

Examples of hydroxyl-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, trihydroxymethylpropane mono(meth)acrylate, and pentaerythritol mono(meth)acrylate, etc.; and hydroxyl-containing polyfunctional (meth)acrylates such as trihydroxymethylpropane di(meth)acrylate, pentaerythritol di- or tri(meth)acrylate, ditrihydroxymethylpropane di- or tri(meth)acrylate, and dipentaerythritol di-, tri-, tetra- or penta(meth)acrylate, and glycerol di(meth)acrylate.

Preferred trifunctional or higher urethane (meth)acrylates include the reaction products of organic polyisocyanates containing two isocyanate groups and polyfunctional (meth)acrylates containing hydroxyl groups. Among them, in terms of low viscosity, high hardness of the cured product, and low coloring, preferred organic polyisocyanates having two isocyanate groups are isophorone diisocyanate or hexamethylene diisocyanate, and preferred polyfunctional (meth)acrylates containing hydroxyl groups are pentaerythritol di- or tri-(meth)acrylate, dipentaerythritol di-, tri-, tetra- or penta-(meth)acrylate, and glycerol di-(meth)acrylate.

Urethane (meth)acrylates can be obtained by conventional methods. For example, there are methods such as the following, namely, in the presence of an addition catalyst such as dibutyltin dilaurate, an organic polyisocyanate and a polyol are heated and stirred to cause an addition reaction to produce an isocyanate group-containing compound, and a hydroxyl group-containing (meth)acrylate is further added to the compound and heated and stirred to cause an addition reaction. In the case of a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth)acrylate, there is a method such as heating and stirring the organic polyisocyanate and the hydroxyl group-containing (meth)acrylate in the presence of an addition catalyst to cause an addition reaction.

Examples of urethane poly(meth)acrylates other than these include compounds described in the document "UV·EB Curable Materials" [CMC Co., Ltd., published in 1992], pages 70 to 74.

The content of component (D) is preferably 0% to 80% by weight, and more preferably 10% to 50% by weight, in the total amount of curable components (100% by weight). By setting the content of component (D) to 80% by weight or less, the composition can be prevented from becoming highly viscous, and when used as a coating agent, the adhesion to the substrate is excellent. By setting the content of component (D) to 10% by weight or more, when used as a coating agent, the adhesion to the plastic can be excellent.

2-4. Other components other than those mentioned above Preferred other components include surface modifiers, antistatic agents, polymerization inhibitors, organic solvents, antioxidants, ultraviolet absorbers, and silane coupling agents. These components are described below.

2-4-1. Surface modifier A surface modifier may be added to the composition of the present invention in order to improve the leveling property during coating, to improve the smoothness of the cured product and thus improve the scratch resistance. As the surface modifier, surface conditioners, surfactants, leveling agents, defoaming agents, slip agents, and antifouling agents may be listed, and these known surface modifiers may be used. Among these, silicone-based surface modifiers and fluorine-based surface modifiers may be suitably listed. As specific examples, organic polysiloxanes having a polyoxyalkylene skeleton in the molecular structure, organic polysiloxanes having a polyester skeleton, fluorine-based polymers and oligomers having perfluoroalkyl and polyepoxy chains, and fluorine-based polymers and oligomers having perfluoroalkyl ether chains and polyepoxy chains can be cited. In addition, in order to improve the durability of smoothness, etc., a surface modifier having an olefinic unsaturated group, preferably a (meth)acrylic group, in the molecule can also be used.

Among these, in order to achieve excellent surface smoothness and significantly improve the antistatic function described later, it is preferred to use an organic polysiloxane having a polyoxyalkylene skeleton (hereinafter referred to as "(E) component"). Examples of the oxyalkylene groups constituting the polyoxyalkylene skeleton include oxyethylene, oxypropylene, oxybutylene, and combinations of these oxyalkylene groups. As the bonding form of the polyoxyalkylene skeleton, it may be any of a single end, both ends, and a side chain of the polysiloxane chain. As specific examples of the (E) component, polyoxyethylene-methyl polysiloxane copolymers, poly(oxyethylene-oxypropylene)methyl polysiloxane copolymers, etc. may be listed. (E) The ingredients are commercially available, for example: 71 ADDITIVE, 74 ADDITIVE, 57 ADDITIVE, 8029 ADDITIVE, 8054 ADDITIVE, 8211 ADDITIVE, 8019 ADDITIVE, 8526 ADDITIVE, FZ-2123, FZ-2191 (manufactured by Toray Dow Corning Co., Ltd.); TSF4440, TSF4441, TSF4445, TSF4446, TSF4450, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Co., Ltd.); SILFACE SAG002, SILFACE SAG003, SILFACE SAG005, SILFACE SAG503A, SILFACE SAG008, SILFACE SJM003 (manufactured by Nissin Chemical Industry Co., Ltd.); TEGO Wet KL245, TEGO Wet 250, TEGO Wet 260, TEGO Wet 265, TEGO Wet 270, TEGO Wet 280 (manufactured by Evonik); and BYK-345, BYK-347, BYK-348, BYK-375, BYK-377 (manufactured by BYK-Chemie Japan Co., Ltd.), etc.

The content of the surface modifier is preferably 0.01 to 5.0 parts by weight relative to 100 parts by weight of the total amount of the curable component.

2-4-2. Antistatic agent In order to impart antistatic function, an antistatic agent may be added to the composition of the present invention. Examples of antistatic agents include: various cationic antistatic agents having cationic groups such as quaternary ammonium salts, pyridinium salts, primary to tertiary amine groups, anionic antistatic agents having cationic groups such as sulfonic acid bases, sulfate bases, phosphate bases, and phosphonic acid bases, amphoteric antistatic agents such as amino acid series and aminosulfate series, nonionic antistatic agents such as amino alcohol series, glycerol series, and polyethylene glycol series, and polymer antistatic agents obtained by increasing the molecular weight of the above antistatic agents. In addition, ionic liquids and metal salts can also be used as antistatic agents. There is no particular limitation on the ionic liquid and the metal salt, and various commonly used ionic liquids and metal salts can be used. The metal salt has high ion dissociation even in a trace amount, so it can show excellent antistatic ability, which is useful. On the other hand, the ionic liquid itself shows excellent conductivity, so it can provide sufficient antistatic ability even in a trace amount, which is useful.

Among these, metal salts having anions with fluorine and sulfonyl groups are preferred from the perspective of excellent antistatic ability and optical properties (hereinafter referred to as "(F) component"). Among the (F) component, trifluoromethanesulfonyl group is preferred as anion having fluorine and sulfonyl groups. In addition, as a metal forming a metal salt, alkali metals, 2A group elements, transition metals and amphoteric metals are preferred, and alkali metals are more preferred.

As a specific compound of the component (F), a metal salt of bis(trifluoromethanesulfonyl)imide, an alkali metal salt of tri(trifluoromethanesulfonyl)methide, and an alkali metal salt of trifluoromethanesulfonic acid ion are preferred. That is, any one of the compounds represented by the following general formulas (D1) to (D3) is preferred. M(CF ₃ SO ₂ ) ₂ N ·······(D1) M(CF ₃ SO ₂ ) ₃ C ·······(D2) M(CF ₃ SO ₃ ) ······(D3) In the general formulas (D1) to (D3), M represents an alkali metal. As the alkali metal salt, lithium, sodium and potassium are preferred, and lithium is more preferred.

Specific examples of the above-mentioned component include: bis(fluoroalkylsulfonyl)imide ions, tri(fluoroalkylsulfonyl)methide ions, and fluoroalkylsulfonic acid ions, specifically, lithium bis(trifluoromethanesulfonyl)imide [Li(CF ₃ SO ₂ ) ₂ N], potassium bis(trifluoromethanesulfonyl)imide [K(CF ₃ SO ₂ ) ₂ N], sodium bis(trifluoromethanesulfonyl)imide [Na(CF ₃ SO ₂ ) ₂ N], lithium tris(trifluoromethanesulfonyl)methylate [Li(CF ₃ SO ₂ ) ₃ C], potassium tris(trifluoromethanesulfonyl)methylate [K(CF ₃ SO ₂ ) ₃ C〕, sodium tris(trifluoromethanesulfonyl) methylate〔Na(CF ₃ SO ₂ ) ₃ C〕, lithium trifluoromethanesulfonate〔Li(CF ₃ SO ₃ )〕, potassium trifluoromethanesulfonate〔K(CF ₃ SO ₃ )〕, sodium trifluoromethanesulfonate〔Na(CF ₃ SO ₃ )〕, etc. Among these compounds, lithium bis(trifluoromethanesulfonyl) imide, lithium tris(trifluoromethanesulfonyl) methylate and lithium trifluoromethanesulfonate are preferred, and lithium bis(trifluoromethanesulfonyl) imide and lithium trifluoromethanesulfonate are particularly preferred.

The content ratio of the antistatic agent is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the solid component in the composition. By setting the content ratio of the antistatic agent to 0.1 parts by weight or more, the effect of reducing the surface resistivity can be exerted. On the other hand, by setting it to 20 parts by weight or less, the water resistance of the cured product can be excellent.

In the present invention, in order to more effectively reduce the surface resistivity, it is preferred to use the component (E) and the component (F) together.

2-4-3. Polymerization inhibitor In order to improve the storage stability of the composition such as preventing gelation, a polymerization inhibitor may be formulated in the composition of the present invention. As the polymerization inhibitor, the organic polymerization inhibitor, inorganic polymerization inhibitor and organic salt polymerization inhibitor exemplified in the method for producing the component (A) are listed, and the same compounds as those mentioned are listed. As the polymerization inhibitor, among these compounds, organic compounds having stable free radicals are preferred for the reason of improving the storage stability and not reducing the hardness of the cured product. As the organic compound having stable free radicals, galvinoxyl and N-oxy free radical compounds are listed, and N-oxy free radical compounds are more preferred for the following reasons. That is, when the composition is used for coating, the work is often carried out under a fluorescent lamp that removes ultraviolet light (ultraviolet cutoff fluorescent lamp) for the reason of excellent work efficiency, but even when the composition is stored under such fluorescent lamp, the storage stability of the composition containing N-oxyl radical compounds is excellent. Specific examples of N-oxyl radical compounds include 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl radical, 2,2,6,6-tetramethylpiperidin-1-oxyl radical, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl radical, and 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl radical. A polymerization inhibitor can be added to the composition, and can be used directly when it is included in component (A). In addition, even when component (A) contains a polymerization inhibitor, a polymerization inhibitor can be further added. The content of the polymerization inhibitor in the composition is preferably 0.0005 wt% to 1 wt%, and more preferably 0.005 wt% to 0.1 wt%. By setting the content of the polymerization inhibitor to 0.0005 wt% or more, the polymerization inhibition effect can be fully exerted, and by setting it to 1 wt% or less, the hardness of the cured product can be avoided from being reduced.

2-4-4. Organic solvent The composition of the present invention does not substantially require an organic solvent, but may contain an organic solvent as needed for the purpose of viscosity adjustment, etc. As the organic solvent, the same compounds as the organic solvents listed in the method for producing the component (A) can be cited. As for the content ratio of the organic solvent, it is preferably 0.1 parts by weight to 1000 parts by weight, and more preferably 5 parts by weight to 500 parts by weight relative to 100 parts by weight of the total amount of the curable component. If it is within the above range, the composition can have a viscosity suitable for coating, and the composition can be easily coated by the known coating method described later.

2-4-5. Antioxidants Antioxidants are formulated to improve the durability of cured products, such as heat resistance and weather resistance. Examples of antioxidants include phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants. Examples of phenolic antioxidants include hindered phenols such as di-tert-butylhydroxytoluene. Examples of commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by ADEKA Co., Ltd. Examples of phosphorus antioxidants include phosphines such as trialkylphosphines and triarylphosphines; trialkylphosphites, triarylphosphites, and the like. Among these derivatives, commercial products include ADEKASTAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010, etc. manufactured by ADEKA Co., Ltd. As sulfur-based antioxidants, sulfide-based compounds can be listed, and commercial products include AO-23, AO-412S, AO-503A, etc. manufactured by ADEKA Co., Ltd. These can be used alone or in combination. As a preferred combination of these antioxidants, a phenolic antioxidant and a phosphorus antioxidant, and a phenolic antioxidant and a sulfur antioxidant can be listed. The content ratio of the antioxidant can be appropriately set according to the purpose, 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 amount of the curing component. By setting the content ratio of the antioxidant to 0.1 parts by weight or more, the durability of the composition can be improved. On the other hand, by setting it to 5 parts by weight or less, the curability and adhesion can be improved.

2-4-6. Ultraviolet absorber Ultraviolet absorber is formulated to improve the light resistance of the cured product. As ultraviolet absorber, there are triazine ultraviolet absorbers such as TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 manufactured by BASF; and benzotriazole ultraviolet absorbers such as TINUVIN 900, TINUVIN 928, TINUVIN 1130. The content ratio of the ultraviolet absorber can be appropriately set according to the purpose. It 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 amount of the curable component. By setting the content ratio of the ultraviolet absorber to 0.01% by weight or more, the light resistance of the cured product can be kept good. On the other hand, by setting it to 5% by weight or less, the composition can be made with excellent curability.

2-4-7. Silane coupling agent Silane coupling agent is formulated to improve the interface bonding strength between the cured product and the substrate. As for the silane coupling agent, there is no particular limitation as long as it can help improve the bonding with the substrate.

As the silane coupling agent, specifically, there can be mentioned 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl Propyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyl trimethoxysilane, 3-butylene methyl dimethoxysilane, 3-butylene propyl trimethoxysilane, etc.

The content ratio of the silane coupling agent can be appropriately set according to the purpose, and is preferably 0.1 to 10 parts by weight, and more preferably 1 to 5 parts by weight, relative to 100 parts by weight of the total amount of the curing component. By setting the mixing ratio of the silane coupling agent to 0.1 parts by weight or more, the adhesion of the composition can be improved. On the other hand, by setting it to 10 parts by weight or less, the change in adhesion over time can be prevented.

3. Applications The curability of component (A) in the present invention is excellent, and Glycarbo-A〔(2-oxo-1,3-dioxacyclopentane-4-yl) methacrylate〕is excellent, and the viscosity of the composition can be reduced, so it can be preferably used in a composition containing component (A) as a reactive diluent. The present invention relates to a curable composition, preferably an active energy ray curable composition, and more preferably a solvent-free active energy ray curable composition, which can be used for various purposes. For example, coating agents such as coatings, adhesives, adhesives, inks, forming agents for forming shaping materials, and pattern forming agents such as anti-corrosion agents can be cited. The composition of the present invention can also be preferably used in coating compositions, adhesive compositions, and shaping material compositions in these applications, and can be more preferably used in active energy ray-curable coating compositions, adhesive compositions, and shaping material compositions. The following describes preferred applications. In addition, the other components listed below may be used in combination of only one of the compounds listed as examples, or two or more thereof.

3-1. Coating composition The composition of the present invention is preferably used as a coating composition because of its excellent film curing property and high hardness of the cured product. Component (A) is more preferably used as a solvent-free coating composition because of its low viscosity. Furthermore, as mentioned above, component (A) has a low chlorine concentration, thereby forming a cured film with excellent corrosion resistance, and has a low sodium concentration, thereby forming a cured film with excellent water resistance.

Furthermore, the composition of the present invention can be preferably used as a coating agent for various plastics, i.e., a hard coating agent, because the surface hardness and abrasion resistance of the obtained cured film are excellent, and can be preferably used as a solvent-free hard coating agent. As substrates for applying hard coating agents, plastic films used in polarizer protective films and anti-reflection films, and resin molded products used in home appliances and automobile interior and exterior parts can be listed.

The coating composition has the aforementioned (A) as an essential component, but various components can be formulated according to the purpose. As other components, specifically, the aforementioned (B), (C), and (D) components, surface modifiers, ultraviolet absorbers, antistatic agents, polymerization inhibitors, organic solvents, antioxidants, and silane coupling agents can be listed. In addition, pigments, dyes, and polymers can also be listed. As specific examples of pigments, dyes, and polymers, the same compounds as those listed in paragraphs [0088] and [0094] of the international publication WO2017/002964 can be cited.

As another use of the coating composition, it can be preferably used as a coating agent for metal substrates. As described above, the chlorine concentration of the component (A) used in the present invention is low, thereby forming a cured film of a curable composition with excellent corrosion resistance on the surface of the metal substrate. As a method for manufacturing a metal substrate having a cured film using the composition of the present invention, it is preferred to include: a step of coating a curable composition on a part or all of the metal substrate, and a step of curing the coated composition by irradiating it with active energy rays or heating it. The metal substrate having the cured film obtained from the composition of the present invention has excellent water resistance and corrosion resistance, and therefore can be suitably used as an electrode protective coating used in electrode protective materials, substrate circuit protective materials, and lithium ion batteries.

3-2. Adhesive composition The composition of the present invention can be preferably used as an adhesive composition because of its low viscosity and excellent curability. Furthermore, as mentioned above, the cured product has excellent corrosion resistance and water resistance, so it can be preferably used for applications requiring these physical properties.

The adhesive composition has the aforementioned (A) as an essential component, but various components can be formulated according to the purpose. As other components, specifically, in addition to the aforementioned (B), (C) and (D) components, surface modifiers, ultraviolet absorbers, polymerization inhibitors, organic solvents, antioxidants, silane coupling agents, pigments, dyes, and polymers can also be cited.

3-3. Forming material composition The composition of the present invention has low viscosity and high hardness of the cured product, so it can be preferably used as a forming material composition used in mold transfer or nanoimprinting, etc., and can be particularly preferably used as a shaping material used in micro-processing applications such as nanoimprinting. In addition, in the present invention, for convenience, the shaping material is also included in the concept of the forming material.

As a shaping material, it can be used in the production of shaping films with fine concave-convex structures on the surface, such as lenses, nano-imprinted films, anti-reflective films with moth-eye shapes, polarizing films, anti-glare films, light extraction films for organic electroluminescence (EL) and light emitting diodes (LED), light limiting films for solar cells, and heat-transmitting reflective films.

The molding material composition has the aforementioned (A) as an essential component, but various components can be formulated according to the purpose. As other components, specifically, in addition to the aforementioned (B), (C) and (D) components, surface modifiers, ultraviolet absorbers, polymerization inhibitors, organic solvents, antioxidants, silane coupling agents, pigments, dyes and polymers can also be cited.

3-4. Ink composition The film curing property of the composition of the present invention is excellent, so it can be preferably used as a transparent overprint varnish ink for further printing with a printing press after single-color printing or multi-color printing; and ink for color printing such as yellow, red, blue, and black.

As printing methods, various printing methods can be listed, such as lithographic printing (normal lithographic printing using moistening water and waterless printing without moistening water), letterpress printing (flat plate letterpress, semi-rotary letterpress, rotary, intermittent rotary, flexographic), gravure printing (gravure), screen printing, and inkjet printing. Since the emulsion stability is excellent, it can be preferably used for lithographic printing using moistening water. In addition, since the viscosity is low, it can also be preferably used for inkjet printing.

The composition for ink has the aforementioned (A) as an essential component, and various components can be formulated according to the purpose. As other components, specifically, binders, pigments, plasticizers, and anti-friction agents other than the aforementioned (B), (C), and (D) components can be listed. As specific examples of binders, pigments, plasticizers, and anti-friction agents, the same compounds as those listed in paragraphs [0101] to [0107] of the International Publication No. WO2017/002964 can be listed.

The method for producing the ink composition may be based on existing methods for producing ink compositions, and examples thereof include: preparing component (A), component (B) (when the active energy ray is ultraviolet ray), a binder, a pigment, a polymerization inhibitor, and other additives such as wax, and then adding the pigment and dispersing the mixture using a disperser such as a three-roll mill or a bead mill.

3-5. Pattern-forming composition The composition of the present invention has high exposure sensitivity and excellent developability, and can form precise and accurate patterns, so it can be preferably used as a pattern-forming composition.

The pattern forming composition has the aforementioned (A) as an essential component, and various components can be formulated according to the purpose. As other components, specifically, alkali-soluble resins other than the aforementioned (B), (D), organic solvents, antioxidants, ultraviolet absorbers, silane coupling agents, surface modifiers, and polymerization inhibitors can be listed. As specific examples of alkali-soluble resins, the same compounds as those listed in paragraphs [0110] to [0122] of the International Publication No. WO2017/002964 can be listed.

Method of use The method of using the composition of the present invention may be in accordance with conventional methods. For example, a method of applying the composition to an applied substrate by a conventional coating method, and then irradiating the substrate with active energy rays or heating the substrate to cure the composition, etc. may be cited. The method of irradiating the active energy rays may be a general method known as an existing curing method. In addition, the following method may be used: a method of using component (B) (photopolymerization initiator) and component (C) (thermal polymerization initiator) in the composition, irradiating the composition with active energy rays, and then curing the composition by heating the composition to improve adhesion to the substrate.

As a substrate to which the composition of the present invention can be applied, various materials can be listed, including plastics, metals, wood, inorganic materials and paper. Specific examples of plastics include polyolefins such as polyethylene and polypropylene, cellulose acetate resins such as acrylonitrile-butadiene-styrene (ABS) resin, polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose; acrylic resins; cyclic polyolefin resins using cyclic olefins such as polyethylene terephthalate, polycarbonate, polyarylate, polyether sulfone and norbornene as monomers; polyvinyl chloride, epoxy resins and polyurethane resins, etc. Examples of metals include steel plates, aluminum, and chromium; metal oxides include zinc oxide (ZnO) and indium tin oxide (ITO), etc. Examples of wood include natural wood and synthetic wood, etc. Examples of inorganic materials include glass, mortar, concrete, and stone, etc.

As a method for applying the composition of the present invention to a substrate, it can be appropriately set according to the purpose, and there can be listed methods of applying using a rod coater, a coater, a scraper, a dip coater, a roller coater, a spin coater, a flow coater, a scraper coater, a comma coater, a reverse roll coater, a die coater, a lip coater, a spray coater, a gravure coater, and a micro gravure coater.

When the composition of the present invention is used as an active energy ray-curable composition, examples of active energy rays used to cure the composition of the present invention include ultraviolet rays, visible light rays, and electron beams, preferably ultraviolet rays or visible light rays, and particularly preferably ultraviolet rays. Examples of ultraviolet irradiation devices include high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, and light-emitting diodes (LEDs). The irradiation energy may be appropriately set according to the type and composition of the active energy line. For example, when a high-pressure mercury lamp is used, the irradiation energy is preferably 50 mJ/cm ² to 5,000 mJ/cm ² , more preferably 100 mJ/cm ² to 1,000 mJ/cm ² .

When the composition of the present invention is used as a thermosetting composition, a cured film can be obtained by placing the cured film in a heatable dryer or the like. The heating temperature can be appropriately set according to the substrate used and the purpose, and is preferably 40°C to 180°C. When the substrate is plastic, the substrate may be deformed when the temperature is too high, so it is preferably below 120°C. The heating time can be appropriately set according to the applicable substrate and the heating temperature, and is preferably 0.5 minutes to 60 minutes.

As described above, the composition of the present invention can be preferably used as a coating composition, an adhesive composition, a molding material composition, an ink composition, and a pattern forming composition, and specific examples thereof will be described.

4-1. Method of using the coating composition The coating composition can be used in any conventional manner. For example, a method of applying the composition to a substrate and then curing the composition by irradiating the substrate with active energy rays or heating the composition can be cited. Specifically, a method of applying the composition to an applied substrate by a conventional coating method and then curing the composition by irradiating the substrate with active energy rays in the case of an active energy ray curing composition or a method of curing the composition by heating the composition in the case of a thermosetting composition can be cited. In addition, a method of using a component (C) (photopolymerization initiator) and a component (D) (thermal polymerization initiator) in the composition, irradiating the substrate with active energy rays, and then curing the composition by heating the composition can be cited.

As a substrate to which the composition of the present invention can be applied, various materials can be used, including plastics, metals, wood, inorganic materials and paper, and the specific examples are as listed above.

The thickness of the cured film of the composition relative to the substrate may be appropriately set according to the purpose. The thickness of the cured film may be selected according to the substrate used and the purpose of the substrate having the cured film to be produced, and is preferably 1 μm to 5 mm, more preferably 3 μm to 3 mm.

The method for applying the composition of the present invention to a substrate may be appropriately set according to the purpose, and the methods described in detail above may be cited.

When used as an active energy ray-curing coating composition, the active energy ray used for curing can include ultraviolet rays, visible light rays, and electron beams, and ultraviolet rays are preferred. As the ultraviolet ray irradiation device, the same device as described above can be cited. As the irradiation energy, it can be appropriately set according to the type of active energy ray or the formulation composition, and the same irradiation energy as described above can be cited.

4-2. Method of using adhesive composition The method of using the adhesive composition may be in accordance with conventional methods. For example, a method of applying the composition on a substrate, bonding the applied surface to another substrate, and then curing the composition by irradiating active energy rays or heating the surface. Specifically, a method of applying the composition on an applicable substrate by conventional coating methods, and then curing the composition by irradiating active energy rays in the case of an active energy ray curing composition, or curing the composition by heating the composition in the case of a thermosetting composition, etc. may be cited. Furthermore, in the case of an active energy ray curing adhesive composition, a light-transmitting substrate is used as at least one of the above substrates. Alternatively, the following method may be used: by using component (C) (photopolymerization initiator) and component (D) (thermal polymerization initiator) in the composition, irradiating it with active energy rays, and then heating and curing it to improve its adhesion to the substrate.

As a substrate to which the composition of the present invention can be applied, various materials can be used, including plastics, metals, wood, inorganic materials and paper, and the specific examples are as listed above.

The thickness of the cured film of the composition relative to the substrate may be appropriately set according to the purpose. The thickness of the cured film may be selected according to the substrate used and the purpose of the substrate having the cured film to be produced, and is preferably 0.1 μm to 500 μm, more preferably 1 μm to 200 μm.

The method for applying the composition of the present invention to a substrate may be appropriately set according to the purpose, and the methods described in detail above may be cited.

When used as an active energy ray curing adhesive composition, the active energy ray used for curing can include ultraviolet rays, visible light rays, and electron beams, and ultraviolet rays are preferred. As the ultraviolet ray irradiation device, the same device as described above can be cited. As the irradiation energy, it can be appropriately set according to the type of active energy ray or the formulation composition, and the same irradiation energy as described above can be cited.

4-3. Method of using the composition for forming materials The method of using the composition of the present invention for forming materials can be done according to conventional methods. Specifically, the following methods can be listed: a method of applying the composition to a mold called a press mold having a target shape, laminating it with a film or sheet substrate (hereinafter collectively referred to as a "film substrate"), and then irradiating it with active energy rays to cure it; a method of injecting the composition into a predetermined mold frame, and then irradiating it with active energy rays in the case of an active energy ray-curing composition; or a method of heating it in the case of a thermosetting composition, etc.

As the film substrate that can be used in the present invention, preferred are plastic films such as polymethyl methacrylate, polymethyl methacrylate-styrene copolymer film, polyethylene terephthalate, polyethylene naphthalate, polyarylate, polyacrylonitrile, polycarbonate, polysulfone, polyethersulfone, polyetherimide, polyetherketone, polyimide, polymethylpentene, etc., and glass-based substrates can be used if necessary.

The film substrate is preferably transparent or translucent (eg, milky white). The thickness of the film substrate is preferably 20 μm to 500 μm.

The thickness of the cured film of the composition relative to the substrate can be appropriately set according to the purpose. The thickness of the cured film can be selected according to the substrate used and the purpose of the substrate having the cured film to be produced, and is preferably 10 nm to 100 μm, more preferably 50 nm to 50 μm.

As active energy rays used to cure the composition of the present invention, ultraviolet rays, visible light rays, and electron beams can be listed, and ultraviolet rays are preferred. As ultraviolet irradiation devices, the same devices as described above can be listed. As irradiation energy, it can be appropriately set according to the type and blending composition of the active energy rays, and the same irradiation energy as described above can be listed.

An example of manufacturing a lens using the composition of the present invention is described. When manufacturing a thin lens, the composition of the present invention is applied to a transparent substrate and then brought into close contact with a mold called a die having the target lens shape. Then, active energy rays are irradiated from the transparent substrate side to cure the composition, and then it is peeled off from the mold.

On the other hand, when manufacturing a lens with a thicker film thickness, the composition of the present invention is poured between a mold having a target lens shape and a transparent substrate. Then, active energy rays are irradiated from the transparent substrate side to cure the composition, and then the mold is demolded.

The material of the mold is not particularly limited, and examples thereof include metals such as brass and nickel, and resins such as epoxy resin. In terms of the long life of the mold, it is preferably made of metal.

When the composition of the present invention is used for nanoimprinting, conventional methods can be used. For example, the following method can be used: after applying the composition to a substrate, it is pressed using a transparent mold having a finely processed pattern. Then, the composition is cured by irradiating active energy rays from the transparent mold, and then the mold is demolded.

4-4. Method of using the ink composition The printing substrate used in the printed matter of the present invention is not particularly limited, and examples thereof include high-grade paper, coated paper, art paper, molded paper, thin paper, thick paper, and various synthetic papers; films or sheets of polyester resins, acrylic resins, vinyl chloride resins, vinylidene chloride resins, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymers, ethylene vinyl alcohol copolymers, ethylene methacrylic acid copolymers, nylon, polylactic acid, polycarbonate, etc., cellophane, aluminum foil, and other various substrates that have been used as printing substrates.

The thickness of the cured film of the composition relative to the substrate may be appropriately set according to the purpose. The thickness of the cured film may be selected according to the substrate used and the purpose of the substrate having the cured film to be produced, and is preferably 1 μm to 20 μm, more preferably 1 μm to 10 μm.

When the composition of the present invention is used as a flatbed ink, it can be applied to a substrate using a flatbed printing press that continuously supplies water to the plate. It can also be used in a single-sheet flatbed printing press using sheet-shaped printing paper, a flatbed rotary printing press using roll-shaped printing paper, or any other paper supply method.

When the composition of the present invention is used as an inkjet ink, it can be applied to a substrate by using a known inkjet recording device that forms an image by ejecting ink by an inkjet method.

In the ink jet method, in consideration of the jetting properties, the viscosity of the composition is preferably 7 mPa·s to 30 mPa·s at a jetting temperature (e.g., 40°C to 80°C, preferably 25°C to 30°C), and more preferably 7 mPa·s to 20 mPa·s.

As active energy rays used to cure the composition of the present invention, ultraviolet rays, visible light rays, and electron beams can be listed, and ultraviolet rays are preferred. As ultraviolet irradiation devices, the same devices as described above can be listed. As irradiation energy, it can be appropriately set according to the type and blending composition of the active energy rays, and the same irradiation energy as described above can be listed.

4-5. Usage of pattern forming composition As pattern forming composition, there can be listed photosensitive lithographic printing plates, anti-etching agents such as etch resists and solder resists; columnar spacers in liquid crystal panel manufacturing, coloring compositions for forming pixels or black matrix in color filters, and color filter protective films, etc.

Among these uses, the composition of the present invention can be preferably used for columnar spacers in the manufacture of liquid crystal panels, color filter coloring compositions, and protective films for color filters. When used for columnar spacers and color filter protective films, in order to improve coating and developing properties, non-ionic surfactants such as polyoxyethylene lauryl ether and fluorine-based surfactants can also be added to the composition. In addition, bonding aids, storage stabilizers, and defoaming agents can also be appropriately added as needed. Example

The following shows a production example, an embodiment and a comparative example to more specifically illustrate the present invention. In addition, "parts" in the following are parts by weight. High performance liquid chromatography (hereinafter referred to as "high performance liquid chromatography, HPLC"), viscosity, gel permeation chromatography (hereinafter referred to as "gel permeation chromatography, GPC"), gas chromatography (hereinafter referred to as "Gas Chromatography, GC"), APHA, chlorine content and sodium content were measured under the following conditions.

◆HPLC measurement conditions · Apparatus: ACQUITY ultra-high performance liquid chromatograph (UPLC) manufactured by Waters Corporation · Detector: UV detector · Detection wavelength: 210 nm · Column: ACQUITY UPLC BEH C18 manufactured by Waters Corporation (Part No. 186002350, column inner diameter 2.1 mm, column length 50 mm) · Column temperature: 40°C · Eluent composition: a mixed solution of 0.03 wt% trifluoroacetic acid aqueous solution and methanol · Eluent flow rate: 0.3 mL/min

◆Viscosity measurement conditions Use an E-type viscometer (cone plate type viscometer) to measure the viscosity at 25°C.

◆GPC measurement conditions · Apparatus: GPC system name 1515 2414 717P RI manufactured by Waters · Detector: Refractive index (RI) detector · Column: Guard column, Showa Denko Co., Ltd., Showa KFG (8 μm 4.6×10 mm), main column, Styragel HR 4E THF (7.8×300 mm) + Styragel HR 1THF (7.8×300 mm) manufactured by Waters · Column temperature: 40°C · Eluent composition: THF (containing 0.03% sulfur as an internal standard), flow rate 0.75 mL/min · Detection line: A calibration curve was prepared using standard polystyrene. · Method for calculating the purity (%) Among the peaks detected by GPC measurement, the total area of all peaks from the purified product was set to 100%, and the area of the peak containing glycerol carbonate acrylate and/or glycerol carbonate ethylene oxide adduct acrylate was calculated based on the following formula (1). In addition, when each peak is not completely separated, vertical division processing is performed to obtain the area of each peak. Purity of purified product (%) = (I/S) × 100  ···(1) The symbols and terms in formula (1) are as shown above. S: Total area of detection peaks derived from purified products I: Area of detection peaks of acrylate containing glycerol carbonate acrylate and/or glycerol carbonate ethylene oxide adduct

◆GC measurement conditions · Apparatus: GC-14B manufactured by Shimadzu Corporation · Detector: Flame ionization detector (FID) detector · Column: ZB-1 (length 60 m, inner diameter 0.32 mm, film thickness 3 μm) · Injection temperature: 230℃ or 270℃ · Detector temperature: 330℃ · Column temperature: After maintaining at 125℃ for 5 minutes, increase the temperature at a rate of 10℃/min. After reaching 325°C, hold for 20 minutes ·Carrier gas: nitrogen ·Injection volume: dilute with methanol or acetone to 10 wt% and inject 0.4 μL ·Calculation method of purity (%) Among the peaks detected by GC measurement, peaks derived from the dilution solvent are not considered, and the area of all peaks derived from the sample before dilution is set to 100%, and the peak area of the target object is calculated based on the following formula (2). In addition, when each peak is not completely separated, vertical division processing is performed to obtain the area of each peak. Purity of target object (%) = (I/S) × 100 ···(2) The symbols and terms in formula (2) are as described above. ·S: Total area of the detection peaks from the sample before solvent dilution ·I: Peak area of the target substance

◆APHA APHA was measured using a colorimeter [Petroleum product color tester OME-2000 manufactured by Nippon Denshoku Industries Co., Ltd.].

◆Chlorine content Collect 30 mg of sample on the quartz boat of the trace chlorine and sulfur analyzer, burn it under an argon/oxygen flow, and finally burn it under a pure oxygen flow. The generated combustion gas passes through 10 ml of absorption liquid (0.3% hydrogen peroxide water), and the chlorine component is collected in the form of Cl ions. Repeat this operation 3 times, collect the chlorine component in the same absorption liquid as the test solution. Measure the test solution with an ion chromatograph, and quantify the Cl ion using the standard curve method. ·Trace chlorine and sulfur analyzer: TOX-100 manufactured by Mitsubishi Chemical Analytical Technology (analytech) ·Ion chromatograph: DIONEX ICS-3000 manufactured by Thermo Fisher Scientific (column: IonPac AG20/AS20)

◆Sodium content Collect 1 g of the sample into a 20 ml PFA bottle (fluororesin bottle), dilute it with NMP (N-methylpyrrolidone) to a total of 10 g, and use it as the test solution. Measure the test solution using an inductively coupled plasma (ICP) mass spectrometer. Quantify the detected elements using the absolute standard curve method. · Pretreatment environment: Clean room G (Class 1000) and clean draft room (clean draft) (Class 100) · NMP: for electronics industry [manufactured by Fuji Film & Wako Pure Chemicals Co., Ltd.] · Mixed standard solution: XSTC-622B (manufactured by SPEX) · ICP mass spectrometer: Agilent Technologies (Agilent) 7700s (organic solvent measurement mode: He/H2),

1. Production Example In addition, the abbreviations in the examples refer to the following. ·MCA: 2-methoxyethyl acrylate ·MEL: 2-methoxyethanol ·DABCO: triethylenediamine ·MEHQ: hydroquinone monomethyl ether ·TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical ·DEHA: N,N-diethylhydroxylamine

1) Production Example 1 In a 3-liter flask equipped with a stirrer, a thermometer, a gas inlet pipe, a distillation tower, and a cooling tube, 660.00 parts (5.59 mol) of glycerol carbonate, 1891.10 parts (14.53 mol) of MCA, 1.22 parts (0.011 mol) of DABCO (triethylenediamine) as catalyst X, 4.52 parts (0.022 mol) of zinc acrylate as catalyst Y, 1.02 parts (474 ppm relative to the total weight of the raw materials added) of MEHQ, and 0.74 parts (288 ppm relative to the total weight of the raw materials added) of TEMPOL were added, and oxygen-containing gas (5 volume % of oxygen and 95 volume % of nitrogen) was bubbled into the liquid. While the reaction liquid is heated and stirred at a temperature of 110°C to 120°C, the pressure in the reaction system is adjusted in the range of 140 mmHg to 180 mmHg, and a mixed liquid of MEL and MCA produced as by-products during the ester exchange reaction is extracted from the reaction system through a distillation tower and a cooling tube. In addition, MCA of the same weight as the extract is added to the reaction system at any time. In addition, MCA containing MEHQ and TEMPOL is added to the reaction system at any time through a distillation tower. The heating is terminated 17 hours after the start of the heating and stirring, and the pressure in the reaction system is returned to normal pressure to terminate the extraction. A portion of the reaction solution was collected and analyzed by HPLC. The results confirmed that it contained the target substance Glycarbo-A〔(2-oxo-1,3-dioxacyclopentane-4-yl) methacrylate〕.

54 parts of aluminum silicate (Kyoward 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.) were added to the filtrate as an adsorbent, and the mixture was heated and stirred at an internal temperature of 80°C to 105°C for 1 hour at normal pressure for contact treatment. Then, 3.0 parts of calcium hydroxide were added at an internal temperature of 20°C to 40°C and stirred at normal pressure for 1 hour. After the insoluble matter was separated by pressure filtration, dry air was bubbled into the filtrate while reduced pressure distillation was performed at a temperature of 70°C to 90°C and a pressure of 0.001 mmHg to 100 mmHg for 16 hours to separate the distillate containing unreacted MCA.

0.87 parts (900 ppm relative to the second step treated product) of DEHA were added to the obtained kettle liquid, and stirred at an internal temperature range of 70°C to 90°C at normal pressure for 3 hours. Thereafter, 4.50 parts of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd. (trade name omitted below)] were added to the kettle liquid, and pressure filtration was performed, and the obtained filtrate was used as a purified product. The weight of the filtrate was 945.75 parts, and the composition was analyzed using HPLC, and the result confirmed that Glycarbo-A, which was the target product, was contained. The various analysis results of the obtained purified product are shown in Table 1.

2) Production Example 2 (1) Production of ethylene oxide adduct of glycerol carbonate First, ethylene oxide adduct of glycerol, which is the raw material of ethylene oxide adduct of glycerol carbonate, is purified. In a 3-liter flask equipped with a stirrer, a thermometer, and a cooling tube, 1,722 parts of ethylene oxide adduct of glycerol [Emalgen GE-1 (trade name), hydroxyl value 1,190 mgKOH/g, manufactured by Kao Corporation] are added, and reduced pressure distillation is performed for 43 hours at a kettle liquid temperature of 125°C to 140°C and a system internal pressure range of 70 Pa to 7 Pa. First, 475 parts (hereinafter referred to as "primary distillate") are taken out, and then 508 parts (hereinafter referred to as "main distillate") are taken out. According to the results of GC analysis, the main distillate contains 6% glycerol, 72% of compounds with only one ethylene oxide added to the first hydroxyl group of glycerol, and 10% of compounds with only two ethylene oxides added to the first hydroxyl group of glycerol.

504 parts of the main distillation solution obtained above, 411 parts of ethyl carbonate, and 0.9 parts of activated alumina as a catalyst were added to a 3-liter flask equipped with a stirrer, a thermometer, and a cooling tube. The reaction solution was heated and stirred at a temperature of 130°C to 150°C, and the pressure in the reaction system was adjusted to a range of 4700 Pa to 30 Pa. The mixed solution of ethylene glycol and ethyl carbonate produced as a by-product during the ester exchange reaction was taken out from the reaction system through a cooling tube. After 15 hours from the start of heating and stirring, the heating was stopped, the pressure in the reaction system was restored to normal pressure, and the removal was stopped. Then, the kettle liquid was filtered under pressure to remove the activated aluminum oxide added as a catalyst, and the filtrate was obtained. The weight of the filtrate was 560 parts. According to the results of GC analysis, it contained: 5% of glycerol carbonate, 68% of a compound in which only one ethylene oxide was added to the first hydroxyl group of glycerol, and the second and third hydroxyl groups were carbonated to form a cyclic carbonate structure in the molecule, and 4% of a compound in which only two ethylene oxides were added to the first hydroxyl group of glycerol, and the second and third hydroxyl groups were carbonated to form a cyclic carbonate structure in the molecule.

(2) Production of acrylic acid ester of ethylene oxide adduct of glycerol carbonate In a 3-liter flask equipped with a stirrer, a thermometer, a gas inlet pipe, a distillation tower and a cooling tube, 450 parts of the filtrate obtained above, 1553 parts (11.93 mol) of MCA, 0.31 parts (0.028 mol) of DABCO as catalyst X, 1.15 parts (0.056 mol) of zinc acrylate as catalyst Y, 2.09 parts of pure water, 0.78 parts (464 ppm relative to the total weight of the raw materials added) of MEHQ, and 0.56 parts (279 pm relative to the total weight of the raw materials added) of TEMPOL were added, and oxygen-containing gas (5 volume % of oxygen and 95 volume % of nitrogen) was bubbled into the liquid. While heating and stirring the reaction liquid at a temperature of 110°C to 120°C, the pressure in the reaction system is adjusted in the range of 120 mmHg to 160 mmHg, and the mixed liquid of MEL and MCA produced as by-products during the ester exchange reaction is taken out from the reaction system through the distillation tower and the cooling tube. In addition, MCA of the same weight as the taken out liquid is added to the reaction system at any time. In addition, MCA containing MEHQ and TEMPOL is added to the reaction system at any time through the distillation tower. After 40 hours from the start of heating and stirring, the heating is stopped, and the pressure in the reaction system is restored to normal pressure, and the removal is stopped. 18 parts of aluminum silicate as an adsorbent were added to the reaction reactor liquid at the end of the reaction, and the mixture was heated and stirred at an internal temperature of 80°C to 105°C for 1 hour under normal pressure for contact treatment. Then, 0.9 parts of calcium hydroxide were added at an internal temperature of 20°C to 40°C and stirred at normal pressure for 1 hour. After separating the insoluble matter by pressure filtration, dry air was bubbled in the filtrate while the reduced pressure distillation was performed at a temperature of 70°C to 90°C and a pressure of 0.001 mmHg to 100 mmHg for 16 hours to separate the distillate containing unreacted MCA.

0.75 parts of DEHA were added to the obtained kettle liquid, and the mixture was stirred at normal pressure for 3 hours at an internal temperature of 70°C to 90°C. Thereafter, 4.5 parts of diatomaceous earth were added to the kettle liquid for pressure filtration, and the obtained filtrate was used as a purified product. The weight of the filtrate was 630 parts, and according to the results of GC analysis, it contained: 7% of glyceryl carbonate acrylate, 59% of glyceryl carbonate 1 mol ethylene oxide adduct acrylate, and 4% of glyceryl carbonate 2 mol ethylene oxide adduct acrylate. The various analysis results of the obtained purified product are shown in Table 1.

3) Production Example 3 200 parts of the purified product obtained in Production Example 2 and 1525 parts of n-hexane were added to a 3-liter separatory funnel, and the separatory funnel was vigorously shaken for extraction. The liquid was allowed to stand for double-layer separation, and components with a carbonate structure such as glycerol carbonate acrylate were mainly distributed in the lower layer. The upper layer with n-hexane as the main component contained a large number of glycerol triacrylates or compounds triacrylated by adding only one ethylene oxide to the second hydroxyl group of glycerol, that is, acrylate compounds without a carbonate structure. The upper layer was taken out from the separatory funnel, reduced pressure and concentrated in an evaporator, and most of the n-hexane was recovered as a distillate. The recovered n-hexane and new n-hexane were added to the separatory funnel where the lower layer remained, and the extraction operation was performed again. After repeating the extraction operation and the recovery operation of n-hexane for a total of 8 times, the lower layer of the separatory funnel was taken out, 0.105 parts of MEHQ and 0.001 parts of TEMPOL were added, and while bubbling dry air, reduced pressure distillation was performed for 5 hours at a temperature of 60°C and a pressure range of 3 mmHg to 100 mmHg. The small amount of n-hexane contained in the lower layer was distilled off, and the obtained kettle liquid was used as a purified product. The weight of the kettle liquid was 155 parts. According to the results of GC analysis, it contained: 9% of glycerol carbonate acrylate, 77% of glycerol carbonate ethylene oxide 1 mole adduct acrylate, and 5% of glycerol carbonate ethylene oxide 2 mole adduct acrylate. The various analysis results of the obtained purified product are shown in Table 1.

4) Comparative Production Example 1〔Production based on ester exchange reaction using titanium catalyst〕 Into a 20 ml test tube equipped with a rotor, a thermometer, a gas inlet tube, and a cooling tube, 2.502 parts (0.212 mol) of glycerol carbonate, 4.958 parts (0.0381 mol) of MCA, 0.003 parts of MEHQ, and 0.001 parts of phenothiazine were added, and oxygen-containing gas (5 volume % of oxygen and 95 volume % of nitrogen) was bubbled into the liquid, and the reaction liquid was heated at a temperature range of 105°C to 120°C for 0.5 hours. Then, 0.245 parts (0.0007 mol) of titanium tetra-n-butoxide was added as a catalyst, and the reaction solution was heated at a temperature of 105°C to 120°C for 6 hours. A portion of the reaction solution was collected and analyzed by HPLC, but the formation of the target Glycarbo-A was not confirmed.

5) Comparative Production Example 2〔Production by Dehydration Esterification Reaction〕 Into a flask equipped with a stirrer, a thermometer, a gas inlet tube, a cooling tube, and a water distribution tube, 213.46 parts (1.81 mol) of glycerol carbonate, 169.90 parts (2.36 mol) of acrylic acid, 6.15 parts of methanesulfonic acid, 0.60 parts of copper sulfate, 0.61 parts of MEHQ, and 210.95 parts of toluene were added, and an oxygen-containing gas (5% by volume of oxygen and 95% by volume of nitrogen) was bubbled into the liquid. The reaction solution was heated and stirred for 7 hours at a reaction pressure of 370 Torr and a reaction liquid temperature of 86°C to 90°C, while the water generated in the dehydration reaction was taken out from the water distribution tube. A portion of the reaction solution was collected and analyzed by HPLC. The result confirmed that the target Glycarbo-A was contained. After cooling the reaction solution to room temperature, 274.34 parts of toluene and 87.50 parts of water were added and stirred. Stirring was stopped and the solution was allowed to stand for separation into three layers. The upper layer contained almost no target and toluene was the main component. The middle layer was a water layer. The lower layer was a layer containing the target. After the upper and middle layers were discharged, 250.00 parts of tetrahydrofuran and 55.48 parts of a 20% sodium hydroxide aqueous solution were added to the lower layer and stirred. Stirring was stopped and the solution was allowed to stand for separation into two layers. The lower layer is the water layer, and the upper layer is the layer containing the target. After draining the lower layer, add 87.50 parts of water to the upper layer and stir. Stop stirring and let it stand, then separate into two layers. The lower layer is the water layer, and the upper layer is the layer containing the target. After draining the lower layer, transfer the upper layer to a flask, add 0.14 parts of MEHQ, and while bubbling dry air, perform reduced pressure distillation for 6 hours at a temperature of 40°C to 80°C and a pressure of 0.01 mmHg to 600 mmHg to remove low-boiling components such as tetrahydrofuran, toluene, and water. 1.40 parts of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.] was added to the kettle liquid, and pressure filtration was performed, and the obtained filtrate was used as a purified product. The weight of the filtrate was 147.19 parts, and the composition was analyzed using HPLC, and the result confirmed that Glycarbo-A, which was the target product, was contained. The various analysis results of the obtained purified product are shown in Table 1.

6) Comparative Preparation Example 3 [Preparation by the Acyl Chloride Method] The method described in the non-patent document (Gerhard Wegner et al., Macromolecules, 2007, Vol. 40, pp. 7558-7565) was used for implementation. 130.00 parts (1.10 mol) of glycerol carbonate, 111.40 parts (1.10 mol) of triethylamine, and 700 mL of tetrahydrofuran were added to a 2-liter flask equipped with a stirrer, a thermometer, a dropping funnel, and a gas inlet tube. Nitrogen was introduced into the gas phase, and the internal temperature was cooled to a range of 0°C to 5°C. Add 99.64 parts (1.10 mol) of acryloyl chloride and 260 mL of tetrahydrofuran to the dropping funnel, and slowly add dropwise for about 3 hours while stirring, so that the internal temperature reaches the range of 0-5°C. After the addition is completed, stir for 1 hour, transfer the supernatant to the separatory funnel, add 50 mL of tetrahydrofuran to wash the residual precipitate in the flask, and wash the organic solvent layer with 150 mL of saturated saline. 0.047 parts of MEHQ and 0.0047 parts of TEMPOL were added to the organic solvent layer, and the mixture was distilled under reduced pressure for 10 hours at a temperature of 50°C to 70°C and a pressure of 20 mmHg to 100 mmHg while bubbling dry air, to separate the distillate containing tetrahydrofuran. The solid matter was separated by pressure filtration, and the obtained filtrate was used as a purified product. The weight of the filtrate was 59.72 parts, and the composition was analyzed using HPLC, and it was confirmed that the target Glycarbo-A was contained. The various analysis results of the obtained purified product are shown in Table 1.

[Table 1] Viscosity (mPa·s/25℃) GPC purity (%) APHA Chlorine content (ppm) Na content (ppb) Manufacturing Example 1 59 87 106 2.9 ＜10 Manufacturing Example 2 68 80 96 1.2 78 Manufacturing Example 3 85 82 50 0.9 130 Comparative Manufacturing Example 2 449 49 ＞1000 6.6 8,600 Comparative Manufacturing Example 3 72 94 ＞1000 1,900 930

2. Examples 1) Preparation of active energy ray-hardening composition The compounds shown in Tables 2 to 4 below were stirred, mixed, and dissolved in a stainless steel container in the proportions shown in Table 2 to prepare an active energy ray-hardening composition. The numbers in Tables 2 to 4 refer to parts, and the abbreviations refer to the following contents. ·M1200: Urethane acrylate [manufactured by Toa Gosei Co., Ltd., trade name: Aronix M-1200] ·M402: Dipentaerythritol penta/hexaacrylate mixture [manufactured by Toa Gosei Co., Ltd., trade name: Aronix M-402] ·Om907: 2-methyl-1-(4-methylthiophenyl)-2-oxopropane-1-one [manufactured by IGM Resins Co., Ltd., trade name: Omnirad 907] ·DETX: 2,4-diethylthiodone [manufactured by Nippon Kayaku Co., Ltd., trade name: Kayacure DETX-S] ·TPO: Phosphorus-based photopolymerization initiator (2,4,6-trimethylbenzoyl-diphenylphosphine oxide) [manufactured by IGM Resin Co., Ltd., trade name: Omnirad TPO]

2) Evaluation method The obtained composition was used to perform the following evaluation. The results are shown in Tables 2 to 4.

(1) Viscosity The viscosity of the obtained composition was measured using an E-type viscometer (cone plate type viscometer) (25°C).

(2) Wet heat test The composition obtained in Table 2 was applied to a 100 μm thick easy-adhesive polyethylene terephthalate (hereinafter referred to as "PET") film [Cosmoshine A4300 manufactured by Toyobo Co., Ltd.] using a rod coater to a thickness of 10 μm, and then irradiated with ultraviolet light to cure the composition. The ultraviolet irradiation device used was a metal halide lamp manufactured by Eye Graphics Co., Ltd., and ultraviolet irradiation was performed under the conditions of an irradiation intensity of 200 mW/ ^cm2 and a cumulative light quantity of 2,000 mJ/ ^cm2 in the ultraviolet region (UV-A) centered at 365 nm. After UV irradiation, the obtained samples were kept in an environment of 85°C and 85% RH for 100 hours for a wet heat test. The appearance changes of the cured film after the wet heat test were visually observed and evaluated according to the following three levels. ○: No change, Δ: Partially bubbling, peeling and other defects occurred, ×: The entire surface of the cured film peeled off

(3) Insulation reliability On a substrate with a comb-shaped pattern of line/space = 100/100 formed by photolithography on a polyimide/copper laminate film (hereinafter referred to as a "comb-shaped substrate"), the composition obtained in Table 2 was applied to a thickness of 10 μm using a bar coater, and then irradiated with ultraviolet light under the same conditions as the wet heat test to cure the composition. Using the evaluation sample obtained by the above method, the insulation reliability test was evaluated in an environment of 85°C and 85%RH, under a continuous application of 20 V, and the time it takes for the resistance value to reach less than 100 MΩ was measured.

(4) Adhesion (initial) The composition obtained in Table 3 was coated with a rod coater on a 100 μm thick easy-adhesion polyethylene terephthalate (hereinafter referred to as "easy-adhesion PET") film [Cosmoshine A4300 manufactured by Toyobo Co., Ltd.] to a thickness of 10 μm, and then laminated with another easy-adhesion PET. The composition was cured by irradiating with ultraviolet light under the same conditions as the wet heat test. The above laminate was subjected to a T-peel test in accordance with Japanese industrial standard (JIS) K-6854 at a peel width of 25 mm and 25°C, and the peel strength was measured.

(5) Adhesion strength (after wet heat test) The laminate obtained in (4) was kept in an environment of 85°C and 85% RH for 100 hours, and a T-peel test was performed in accordance with JIS K-6854 under the conditions of a peel width of 25 mm and 25°C. The peel strength after the wet heat test was taken as the peel strength.

(6) Shape reproducibility The composition obtained in Table 4 was applied to a transfer mold (hereinafter referred to as "nickel mold") on a nickel-plated stainless steel plate with a fine process (semicircular pattern with a diameter of 3 μm and a film thickness of 5 μm) using a rod coater to a thickness of 10 μm, and then laminated with easy-to-bond PET. The composition was cured by irradiating with ultraviolet rays under the same conditions as the wet heat test. Thereafter, the pattern shape of the cured film was observed under a microscope after peeling off from the nickel mold, and the shape size was measured and compared with the size of the nickel mold. The shape reproducibility was evaluated at the following two levels. ○: The dimensional change of the pattern shape between the nickel mold and the hardened resin is less than 5%, ×: The dimensional change is more than 5%, or there is a gap in the pattern

(7) Mold corrosion On a transfer mold (hereinafter referred to as "nickel mold") with a fine process (bowl-shaped pattern with a diameter of 10 μm and a film thickness of 5 μm) formed on a nickel-plated stainless steel plate, the composition obtained in Table 4 was applied to a thickness of 10 μm using a bar coater, and then laminated with PET, and irradiated with ultraviolet light under the same conditions as the wet heat test to cure the composition. Thereafter, the metal corrosion test was performed in an environment of 40°C and 80% RH for 24 hours. The appearance changes of the nickel mold after the metal corrosion test were visually observed and evaluated according to the following three levels. ○: No change, Δ: Part of the nickel mold changed color, ×: The entire surface of the nickel mold changed color

[Table 2] Embodiment Ingredients (parts) Viscosity (mPa·s) Wet heat test Insulation reliability (hr) (A) (A)' (B) (C) Manufacturing Example 1 Comparative Manufacturing Example 2 Comparative Manufacturing Example 3 without Om907 DETX Embodiment 1 100 5 0.2 70 ○ >100 Comparison Example 1 100 5 0.2 460 × ＜10 Comparison Example 2 100 5 0.2 80 × ＜10

[Table 3] Embodiment Ingredients (parts) Viscosity (mPa·s) Adhesion force (N/25 mm) (A) (A)' (B) (C) Early days After wet heat test Manufacturing Example 1 Comparative Manufacturing Example 2 Comparative Manufacturing Example 3 M1200 Om907 DETX Embodiment 2 50 50 5 0.2 7,200 10.5 9.4 Comparison Example 3 50 50 5 0.2 18,300 9.8 0.4 Comparison Example 4 50 50 5 0.2 7,680 10.2 0.1

[Table 4] Embodiment Ingredients (parts) Viscosity (mPa·s) Shape reproducibility Mold Corrosion (A) (A)' (B) (C) Manufacturing Example 1 Comparative Manufacturing Example 2 Comparative Manufacturing Example 3 M402 TPO Embodiment 3 70 30 4 270 ○ ○ Comparison Example 5 70 30 4 1,020 × (gap) × Comparison Example 6 70 30 4 300 ○ ×

According to Table 2, the composition of Example 1 containing the component (A) obtained in Production Example 1 has low viscosity, good wet heat test and insulation reliability, and has excellent performance as an active energy ray-curable coating composition. In contrast, the compositions of Comparative Example 1 and Comparative Example 2 containing the component (A)' obtained in Comparative Production Example 2 and Comparative Production Example 3, respectively, have large changes in appearance in the wet heat test and low insulation reliability. In addition, according to Table 3, the composition of Example 2 containing the component (A) obtained in Production Example 1 has excellent adhesion and wet heat test, and has excellent performance as an active energy ray-curable adhesive composition. In contrast, the compositions of Comparative Examples 3 and 4, which contain the component (A) obtained in Comparative Examples 2 and 3, respectively, show a significant decrease in adhesion in the wet heat test. In addition, according to Table 4, the composition of Example 3 containing the component (A) obtained in Production Example 1 has excellent shape reproducibility and good mold corrosion resistance when used as an active energy ray-curable molding material composition, and is therefore suitable as a composition for an active energy ray-curable molding material composition. In contrast, in the compositions of Comparative Examples 5 and 6, which respectively contain the component (A)' obtained in Comparative Examples 2 and 3, Comparative Example 5 has problems with shape reproducibility due to its high viscosity, and Comparative Examples 5 and 6 have problems with mold corrosion, and are compositions not suitable for this purpose. [Industrial Applicability]

The curable composition of the present invention can be preferably used as an active energy ray curable composition, and further can be preferably used as a solvent-free active energy ray curable composition. The curable composition of the present invention can be used for various purposes, including coating agents such as coatings, adhesives, adhesives, inks, forming agents for forming shaping materials, and pattern forming agents such as anti-corrosion agents, etc., and can be preferably used for coating agents, adhesives, and shaping materials.

Claims (15)

A curable composition comprises a component (A), wherein the component (A) contains a compound represented by the following formula (a), the chlorine concentration in the component (A) is less than 100 ppm, and the sodium concentration is less than 100 ppb,

In formula (a), ^Ra represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ^Rb represents an oxyalkylene group having 1 to 20 repeating units. The curable composition according to claim 1, wherein the component (A) is a mixture of compounds obtained by subjecting an alkylene oxide adduct of glycerol carbonate to an ester exchange reaction with a compound having one _CH2 =C(R)-(C=O)- group in its molecule in the presence of the following catalysts X and Y, wherein the catalyst X is one or more compounds selected from the group consisting of a cyclic tertiary amine having a nitrogen-heterobicyclic structure or a salt or complex thereof, an amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof, and a phosphine or a salt or complex thereof; and the catalyst Y is a zinc-containing compound. The hardening composition as described in claim 2, wherein the compound having one CH ₂ =C(R)-(C=O)- group in its molecule is an alkoxyalkyl (meth)acrylate. The curable composition as described in claim 2 or claim 3, wherein the catalyst X is one or more compounds selected from the group consisting of a cyclic tertiary amine having a nitrogen-doped bicyclic structure or its salt or complex, an amidine or its salt or complex, and a compound having a pyridine ring or its salt or complex. The curable composition as described in claim 2 or claim 3, wherein the catalyst Y is at least one of an organic acid zinc and a diketo enol zinc. A curable composition as described in any one of claims 1 to 3, wherein the component (A) further comprises a component (B): a photopolymerization initiator. A curable composition as described in any one of claims 1 to 3, wherein the component (A) further comprises a component (C): a thermal polymerization initiator. A curable composition as described in any one of claims 1 to 3, wherein the component (A) further comprises a component (D): a compound containing an olefinic unsaturated group other than the component (A). A hardening coating composition comprising a hardening composition as described in any one of claims 1 to 8. A hardening molding material composition, comprising a hardening composition as described in any one of claims 1 to 8. A hardening adhesive composition comprising a hardening composition as described in any one of claims 1 to 8. A method for producing a curable composition comprises the step of producing a component (A), wherein the component (A) contains a compound represented by the following formula (a):

In formula (a), ^Ra is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ^Rb is an alkylene oxide group having 1 to 20 repeating units. The component (A) is prepared by reacting an alkylene oxide adduct of glycerol carbonate with a alkylene oxide adduct having a CH ₂ =C(R)-(C=O)- group by transesterification of a compound, wherein the chlorine concentration in the mixture is less than 100 ppm, and the sodium concentration is less than 100 ppb; catalyst X: one or more compounds selected from the group consisting of a cyclic tertiary amine having a nitrogen-heterobicyclic structure or a salt or complex thereof, an amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof, and a phosphine or a salt or complex thereof; catalyst Y: a zinc-containing compound. The method for producing a curable composition as described in claim 12, wherein the compound having one CH ₂ =C(R)-(C=O)- group in its molecule is an alkoxyalkyl (meth)acrylate. A method for producing a curable composition as described in claim 12 or 13, wherein the catalyst X is one or more compounds selected from the group consisting of a cyclic tertiary amine having a nitrogen-doped bicyclic structure or its salt or complex, an amidine or its salt or complex, and a compound having a pyridine ring or its salt or complex. A method for producing a curable composition as described in claim 12 or 13, wherein the catalyst Y is at least one of an organic acid zinc and a diketo enol zinc.