Hardened composition

Abstract

[Problem] To provide a curable composition containing (2-oxo-1,3-dioxolane-4-yl)methyl(meth)acrylate[glycerin carbonate(meth)acrylate], wherein a cured product thereof does not have a metal corrosion problem and has excellent water resistance. [Solution] A curable composition contains a component (A), wherein: the component (A) contains a compound represented by formula (a); and the component (A) has a chlorine concentration of less than 100 ppm and a sodium concentration of less than 100 ppb. [In formula (a), Ra indicates a hydrogen atom or a C1-C5 alkyl group, and Rb indicates a single bond or an oxyalkylene group.]

Description

[Technical Field]

[0001] The present invention relates to a curable composition, preferably an active energy ray curable composition, and more preferably to a solvent-free active energy ray curable composition, and belongs to these technical fields. In this specification, "acryloyl group and / or methacryloyl group" will be expressed as "(meth)acryloyl group," "acrylate and / or methacrylate" as "(meth)acrylate," and "acrylic acid and / or methacrylic acid" as "(meth)acrylic acid." Furthermore, compounds having ethylenically unsaturated groups are referred to as "curable components" in the composition. [Background technology]

[0002] Curing-type compositions are used in a variety of applications, including coatings, adhesives, inks, and electronic materials. Among these, active energy ray curable compositions have the advantage of curing in a very short time, and (meth)acrylates with excellent curability are often used. In the case of ultraviolet curing, irradiation devices with ultraviolet lamps such as high-pressure mercury lamps, metal halide lamps, and LEDs are used as light sources, and in the case of electron beam curing, electron beam irradiation devices are used.

[0003] On the other hand, a disadvantage of active energy ray curable compositions containing (meth)acrylate is that curing in air is inhibited by the influence of oxygen in the air (hereinafter referred to as "oxygen inhibition").

[0004] Conventionally, to prevent curing inhibition due to oxygen inhibition, methods such as irradiating with ultraviolet light under a nitrogen atmosphere or laminating a film onto the coated surface after coating the composition with the substrate and then irradiating with ultraviolet light under oxygen-blocking conditions are known. However, these methods have problems such as requiring large equipment, high costs, and reduced productivity, limiting their applicability. Furthermore, it is known that oxygen inhibition can be reduced by incorporating additives such as amine compounds and phosphorus compounds into the composition. However, such relatively effective additives have the problem of causing discoloration of the cured product.

[0005] To address the above issues, (meth)acrylates that are less susceptible to oxygen inhibition have been considered in the past. In this context, C. Decker et al. have revealed that (2-oxo-1,3-dioxolan-4-yl)methyl acrylate [glycerin carbonate acrylate; hereinafter referred to as "Glycarbo-A"], which has a cyclic carbonate skeleton, exhibits high curability even under air conditions (Non-Patent Literature 1). However, the manufacturing method used in that document involves reacting glycerol with highly toxic phosgene, and then reacting the resulting chloride with acrylic acid to obtain the desired product. This method is highly dangerous and poses significant problems in terms of environmental impact and worker safety.

[0006] Furthermore, G. Wegner et al. obtained (2-oxo-1,3-dioxolan-4-yl)methyl (meth)acrylate [glycerin carbonate (meth)acrylate; hereinafter referred to as "Glycarbo-(M)A"] by the reaction of glycerol carbonate and (meth)acrylate chloride (Non-Patent Literature 2). However, the manufacturing method described in the document is an acid chloride method, which presents problems considering the issue of container corrosion and the large environmental impact. Furthermore, according to the inventors' investigation, the compounds produced by the method described in the document had high concentrations of sodium and chlorine, and when used as components of a curable composition, the cured products had problems such as metal corrosion and low water resistance.

[0007] Furthermore, Patent Document 1 discloses an abrasion-resistant coating composition containing a trifunctional or more polyacrylate and Glycarbo-(M)A, which is said to have the effects of high hardness, fast curing speed, excellent adhesion, and minimal discoloration of the cured product (Patent Document 1). However, the method for producing Glycarbo-(M)A in Patent Document 1 is also by the acid chloride method, and this composition had the aforementioned problems.

Prior Art Documents

Patent Documents

[0008]

Non-Patent Document 1

Non-Patent Document 2

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0009] The present inventors have intensively studied to find a curable composition containing Glycarbo-(M)A, the cured product of which has no problem of metal corrosion and is excellent in water resistance.

Means for Solving the Problems

[0010] In order to solve the above problems, the present inventors have found that a curable composition containing Glycarbo-(M)A as the component (A) and having a reduced chlorine concentration and sodium concentration in the component (A) has a cured product excellent in metal corrosion resistance and water resistance, and thus completed the present invention. Hereinafter, the present invention will be described in detail.

Effects of the Invention

[0011] According to the composition of the present invention, the cured product can be made excellent in metal corrosion resistance and water resistance.

Modes for Carrying Out the Invention

[0012] The present invention relates to a curable 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. The following describes (A) component, curable composition, uses, and method of use.

[0013] 1. (A) Component Component (A), which is an essential component of the present invention, includes a compound represented by the following formula (a).

[0014] [ka]

[0015] [In equation (a), R a R means a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. b This refers to a single bond or an oxyalkylene group.

[0016] R in equation (a) a R means a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. a A hydrogen atom or a methyl group is preferred as the element.

[0017] R b Examples of oxyalkylene groups in this compound include ethylene oxide groups, propylene oxide groups, tetramethylene oxide groups, and mixed units of these alkylene oxide groups, with ethylene oxide groups being preferred. R b The oxyalkylene group in may be an alkylene oxide group having repeating units, preferably 1 to 20, and more preferably 1 to 15.

[0018] (A) The composition containing component (A) is less susceptible to oxygen inhibition, has excellent curability, can be made low viscosity without solvents, and the cured product has excellent hardness, scratch resistance, and adhesion to the substrate. As for the compound of formula (a), R ais a hydrogen atom or a methyl group, and R b is a single bond is preferred. That is, Glycarbo-(M)A [(2-oxo-1,3-dioxolan-4-yl)methyl (meth)acrylate] is preferred. Furthermore, a compound having a hydrogen atom as R in the formula (a), that is, Glycarbo-A [(2-oxo-1,3-dioxolan-4-yl)methyl acrylate], is more preferred in terms of excellent curability. In addition, as the compound of the formula (a), R a is a hydrogen atom or a methyl group, and R b is an oxyalkylene group, and a compound having 1 to 15 repeating units of the oxyalkylene group is preferred. The component (A) may be a mixture of these compounds.

[0019] Furthermore, the component (A) has a chlorine concentration of less than 100 ppm and a sodium concentration of less than 100 ppb. By setting the chlorine concentration to less than 100 ppm and the sodium concentration to less than 100 ppb, the cured product of the resulting composition can be made excellent in water resistance and metal corrosion resistance. In addition, the chlorine concentration in the present invention means a value determined by the quartz tube combustion-ion chromatography method. In addition, the sodium concentration in the present invention means a value obtained by measuring a sample with an ICP mass spectrometer and quantifying the detected elements by the absolute calibration curve method.

[0020] As a method for producing the component (A), in terms of easily producing the component (A) having the above-mentioned chlorine concentration and sodium concentration, glycerin carbonate, an alkylene oxide adduct of glycerin carbonate, or a mixture of these compounds [hereinafter, these are collectively referred to as "glycerin carbonate-based compounds"] and a compound having one CH2=C(R)-(C=O)- group [hereinafter, referred to as "monofunctional (meth)acrylate"] obtained by transesterification reaction is preferred. Incidentally, R of the CH2=C(R)-(C=O)- group means a hydrogen atom or an alkyl group having 1 to 5 carbon atoms as described above. In the manufacturing method involving the dehydration esterification reaction of glycerin carbonate compounds and (meth)acrylic acid, a large amount of high molecular weight by-reactants is generated, resulting in a problem where the obtained component (A) becomes highly viscous. Furthermore, the acid chloride method, which involves reacting glycerin carbonate compounds with (meth)acrylic acid chloride, has the problem that it is difficult to reduce the chlorine and sodium concentrations contained in component (A), resulting in a decrease in the water resistance and metal corrosion resistance of the cured product. In contrast, the transesterification reaction of a glycerin carbonate compound with a monofunctional acrylate makes it possible to produce component (A) in good yield while reducing the chlorine and sodium concentrations.

[0021] The following describes a preferred method for producing component (A) by transesterification, including the glycerin carbonate compound, monofunctional (meth)acrylate, catalyst, and method for producing component (A).

[0022] 1-1. Glycerin carbonate compounds (A) The glycerin carbonate compounds used as raw materials for component (A) are glycerin carbonate, alkylene oxide adducts of glycerin carbonate, or mixtures thereof. Commercially available glycerin carbonate (4-hydroxymethyl-1,3-dioxolan-2-one) can be used. Alternatively, it can be prepared by transesterifying glycerin with carbonate ester compounds such as ethylene carbonate, dimethyl carbonate, and diethyl carbonate in the presence of a catalyst. As the alkylene oxide adduct of glycerin carbonate, one can be used that has been synthesized by transesterifying a glycerin ethylene oxide adduct with a carbonate ester compound such as ethylene carbonate, dimethyl carbonate, or diethyl carbonate in the presence of a catalyst. As the glycerin carbonate-based compound, a mixture of the aforementioned compounds can also be used.

[0023] 1-2. Monofunctional (meth)acrylates (A) The monofunctional (meth)acrylate used as a raw material for component (A) is a compound having one CH2=C(R)-(C=O)- group in its molecule, and examples include the compound represented by the following general formula (1).

[0024] [ka]

[0025] In equation (1), R 1 R represents a hydrogen atom and an alkyl group with 1 to 5 carbon atoms. 2 This represents an organic group with 1 to 50 carbon atoms.

[0026] In the above general formula (1), R 1 A hydrogen atom or a methyl group is preferred as the element. In the above general formula (1), R 2 Preferred specific examples include C1-C8 alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and 2-ethylhexyl groups, alkoxyalkyl groups such as 2-methoxyethyl, 2-ethoxyethyl, and 2-methoxybutyl groups, and dialkylamino groups such as N,N-dimethylaminoethyl, N,N-diethylaminoethyl, N,N-dimethylaminopropyl, and N,N-diethylaminopropyl groups. In the above general formula (1), R 2 Specific examples include the functional groups listed in Japanese Patent Publication No. 2017-39916, Japanese Patent Publication No. 2017-39917, and International Publication No. 2017 / 033732, in addition to those mentioned above.

[0027] In this invention, these monofunctional (meth)acrylates can be used individually or in any combination of two or more types. Among these monofunctional (meth)acrylates, alkyl (meth)acrylates having C1-C8 alkyl groups such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate, and N,N-dimethylaminoethyl (meth)acrylate are preferred. In particular, acrylates having C1-C4 alkyl groups and alkoxyalkyl (meth)acrylates having C1-C2 alkyl groups are preferred as they exhibit good reactivity with glycerin carbonate compounds and are readily available. Furthermore, alkoxyalkyl (meth)acrylates having a C1-C2 alkyl group are more preferable, and 2-methoxyethyl (meth)acrylate is particularly preferable, as they promote the dissolution of glycerin carbonate compounds and exhibit excellent reactivity.

[0028] 1-3. Catalyst (A) As the transesterification reaction catalyst in the production method of component (A), conventionally known catalysts such as tin-based catalysts, titanium-based catalysts, and sulfuric acid can be used. In this invention, it is preferable to use catalysts X and Y described below in combination as catalysts, as this allows for the efficient production of component (A) in high yield. Catalyst X: One or more compounds selected from the group consisting of cyclic tertiary amines having an azabicyclo structure or their salts or complexes (hereinafter referred to as "azabicyclo compounds"), amidine or its salts or complexes (hereinafter referred to as "amidine compounds"), compounds having a pyridine ring or their salts or complexes (hereinafter referred to as "pyridine compounds"), and phosphine or its salts or complexes (hereinafter referred to as "phosphine compounds"). Catalyst Y: A compound containing zinc. The following describes catalysts X and Y.

[0029] 1-3-1. Catalyst X Catalyst X is one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, pyridine compounds, and phosphine compounds. As catalyst X, one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, and pyridine compounds are preferred from the aforementioned group of compounds. These compounds have excellent catalytic activity and can readily produce component (A). Furthermore, they form complexes with catalyst Y, described below, after the reaction is complete, and can be easily removed from the reaction solution by simple methods such as filtration and adsorption. In particular, azabicyclo compounds can be removed even more easily by filtration and adsorption because their complexes with catalyst Y are poorly soluble in the reaction solution. On the other hand, while phosphine compounds exhibit excellent catalytic activity, they do not readily form complexes with catalyst Y and remain largely dissolved in the reaction solution after the reaction is complete. Therefore, they are difficult to remove from the reaction solution by simple methods such as filtration and adsorption. Consequently, phosphine catalysts may remain in the final product, leading to storage stability problems such as turbidity, catalyst precipitation, or thickening or gelling over time. Similar problems can also occur when used as components in compositions.

[0030] Specific examples of azabicyclo compounds include various compounds that satisfy the requirements of a cyclic tertiary amine having an azabicyclo structure, a salt of said amine, or a complex of said amine. Preferred compounds include quinuclidine, 3-hydroxyquinuclidine, 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"). Specific examples of azabicyclo compounds include those listed in Japanese Patent Publication No. 2017-39916, Japanese Patent Publication No. 2017-39917, International Publication No. 2016 / 163208, and International Publication No. 2017 / 033732, in addition to those mentioned above.

[0031] Specific examples of amidine compounds include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 1-alliimidazole, 1,8-diazabicyclo[5.4.0]undeca-7-ene (hereinafter referred to as "DBU"), 1,5-diazabicyclo[4.3.0]nona-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 phthalimide DBU.

[0032] Main examples of pyridine compounds include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, and N,N-dimethyl-4-aminopyridine (hereinafter referred to as "DMAP"). Specific examples of pyridine compounds include those listed in Japanese Patent Publication No. 2017-39916, Japanese Patent Publication No. 2017-39917, International Publication No. 2016 / 163208, and International Publication No. 2017 / 033732, in addition to those mentioned above.

[0033] Examples of phosphines or their salts or complexes include compounds containing the structure shown in the following general formula (2).

[0034] [ka]

[0035] [In equation (2), R 3 , R 4 and R 5 This refers to 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. 3 , R 4 and R 5They can be the same or different.

[0036] Specific examples of phosphine compounds include triphenylphosphine, tris(4-methoxyphenyl)phosphine, tri(p-tolyl)phosphine, tri(m-tolyl)phosphine, tris(4-methoxy-3,5-dimethylphenyl)phosphine, and tricyclohexylphosphine. Specific examples of phosphine compounds include those listed in Japanese Patent Publication No. 2017-39916, Japanese Patent Publication No. 2017-39917, International Publication No. 2016 / 163208, and International Publication No. 2017 / 033732, in addition to those mentioned above.

[0037] In the present invention, these catalysts X can be used individually or in any combination of two or more. Among these catalysts X, quinuclidine, 3-quinuclidinone, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, DBN, and DMAP are preferred, and 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, and DMAP are more preferred because they show good reactivity with most glycerin carbonate compounds and are readily available.

[0038] There are no particular restrictions on the proportion of catalyst X used in the production method of component (A), but it is preferable to use 0.0001 to 0.5 moles of catalyst X per 1 mole of total hydroxyl groups in the glycerin carbonate compound, and more preferably 0.0005 to 0.2 moles. Using 0.0001 moles or more of catalyst X increases the amount of component (A) produced, while using 0.5 moles or less suppresses the formation of by-products and discoloration of the reaction solution, and simplifies the purification process after the reaction is complete.

[0039] 1-3-2. Catalyst Y Catalyst Y is a zinc-containing compound. Various compounds containing zinc can be used as catalyst Y, but zinc organic acids and zinc diketone enolates are preferred due to their excellent reactivity. Examples of zinc organic acids include zinc dibasic acids such as zinc oxalate and compounds represented by the following general formula (3).

[0040] [ka]

[0041] [In equation (3), R 6 and R 7 This refers to 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. 6 and R 7 They can be the same or different. The compound of formula (3) is R 6 and R 7 However, compounds that are linear or branched alkyl groups having 1 to 20 carbon atoms are preferred. 6 and R 7 In this case, the linear or branched alkyl group having 1 to 20 carbon atoms is a functional group that does not have halogen atoms such as fluorine and chlorine, and catalyst Y having such a functional group is preferred because it can produce component (A) in high yield.

[0042] Examples of zinc diketone enolates include compounds represented by the following general formula (4).

[0043] [ka]

[0044] [In equation (4), R 8 , R 9 , R 10 , R 11 , R 12 and R 13 R means 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. 8, R 9 , R 10 , R 11 , R 12 and R 13 They can be the same or different.

[0045] Specific examples of zinc-containing compounds represented by the above general formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octoate, zinc neodecanoate, zinc laurate, zinc myristate, zinc stearate, zinc cyclohexanebutyrate, zinc 2-ethylhexanoate, zinc benzoate, zinc t-butylbenzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and zinc methacrylate. Furthermore, if a hydrate, solvate, or complex with catalyst X exists for these zinc-containing compounds, the hydrate, solvate, and complex with catalyst X can also be used as catalyst Y in the production method for component (A).

[0046] Specific examples of zinc-containing compounds represented by the above general formula (4) include zinc acetylacetonate, zinc acetylacetonate hydrate, bis(2,6-dimethyl-3,5-heptanedionato)zinc, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)zinc, and bis(5,5-dimethyl-2,4-hexanedionato)zinc. Furthermore, if a hydrate, solvate, or complex with catalyst X exists for these zinc-containing compounds, the hydrate, solvate, and / or complex with catalyst X can also be used as catalyst Y in the production method for component (A).

[0047] In catalyst Y, the aforementioned compounds can be used directly as the zinc organic acid and zinc diketone enolate, but these compounds can also be generated and used within the reaction system. For example, zinc compounds such as metallic zinc, zinc oxide, zinc hydroxide, zinc chloride, and zinc nitrate (hereinafter referred to as "raw material zinc compounds") can be used as raw materials, and in the case of zinc organic acid, a method of reacting the raw material zinc compound with an organic acid can be used, and in the case of zinc diketone enolate, a method of reacting the raw material zinc compound with a 1,3-diketone can be used.

[0048] In the present invention, these catalysts Y can be used individually or in any combination of two or more. Among these catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, and zinc acetylacetonate are preferred, and zinc acetate, zinc acrylate, and zinc acetylacetonate are particularly preferred because they show good reactivity with glycerin carbonate compounds and are readily available.

[0049] There are no particular restrictions on the proportion of catalyst Y used in the production method of component (A), but it is preferable to use 0.0001 to 0.5 moles of catalyst Y per 1 mole of total hydroxyl groups in the glycerin carbonate compound, and more preferably 0.0005 to 0.2 moles. Using 0.0001 moles or more of catalyst Y increases the amount of component (A) produced, while using 0.5 moles or less suppresses the formation of by-products and discoloration of the reaction solution, and simplifies the purification process after the reaction is complete.

[0050] 1-4. Method for producing component (A) Component (A) is preferably produced by transesterifying a glycerin carbonate compound with a monofunctional (meth)acrylate in the presence of a transesterification catalyst. As stated above, a preferred method for producing component (A) is one in which catalysts X and Y are used in combination, and this method will be described below.

[0051] (A) There are no particular restrictions on the ratio of catalyst X and catalyst Y used in the method for producing component (A), but it is preferable to use 0.005 to 10.0 moles of catalyst X per mole of catalyst Y, and more preferably 0.05 to 2.0 moles. Using 0.005 moles or more increases the amount of the target compound of formula (a) produced, while using 10.0 moles or less suppresses the formation of by-products and discoloration of the reaction solution, and simplifies the purification step after the reaction is complete.

[0052] In the present invention, the preferred combination of catalyst X and catalyst Y is one in which catalyst X is an azabicyclo compound and catalyst Y is a compound represented by the general formula (3). More preferably, the preferred combination is one in which the azabicyclo compound is DABCO and the compound represented by the general formula (3) is zinc acetate and / or zinc acrylate. This combination yields component (A) in good yield and exhibits excellent color after the reaction, making it suitable for various industrial applications where color is important. Furthermore, since the catalyst is relatively inexpensive and readily available, it represents an economically advantageous manufacturing method.

[0053] The catalysts X and Y used in this invention may be added from the beginning of the reaction or midway through. Furthermore, the desired amount may be added all at once or in installments.

[0054] (A) The reaction temperature in the method for producing component is preferably 40 to 180°C, and more preferably 60 to 160°C. By raising the reaction temperature to 40°C or higher, the reaction rate can be increased, and by raising it to 180°C or lower, the thermal polymerization of (meth)acryloyl groups in the raw materials and products can be suppressed, the discoloration of the reaction solution can be suppressed, and the purification process after the reaction can be simplified.

[0055] (A) The reaction pressure in the method for producing 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 to 10 MPa (absolute pressure).

[0056] In the method for producing component (A), a monohydric alcohol derived from a monofunctional (meth)acrylate is produced as a by-product during the transesterification reaction. While this monohydric alcohol may be left in the reaction system, removing it from the reaction system can further accelerate the progress of the transesterification reaction.

[0057] (A) In the method for producing component (A), the reaction can be carried out without using an organic solvent, but an organic solvent may be used if necessary. 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, amylbenzene, diamylbenzene, triamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, isopropyltoluene, decalin, and tetralin; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diethyl acetal, dihexyl acetal, t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, trioxane, dioxane, anisole, and diphenyl ether. Examples include ethers such as dimethyl cellosolve, diglyme, triglyme, and tetraglyme; 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 carbonate, propylene carbonate, and 1,2-butylene carbonate; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; 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 may be used individually, or two or more may be combined as a mixed solvent.

[0058] (A) In the method for producing component (A), an inert gas such as argon, helium, nitrogen, and carbon dioxide may be introduced into the system to maintain a good color of the reaction solution, or an oxygen-containing gas may be introduced into the system to prevent polymerization of the acryloyl group. Specific examples of oxygen-containing gases include air, a mixture of oxygen and nitrogen, and a mixture of oxygen and helium. Methods for introducing the oxygen-containing gas include dissolving it in the reaction solution or blowing it into the reaction solution (so-called bubbling).

[0059] In the method for producing component (A), it is preferable to add a polymerization inhibitor to the reaction solution in order to prevent polymerization of the (meth)acryloyl group. Examples of polymerization inhibitors 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-butylcatechol, quinone compounds such as benzoquinone, phenothiazines, and N-nitroso-N-phenylhydroxylamine ammonium. Organic polymerization inhibitors can also be organic compounds that have stable radicals, such as carbinoxyl and N-oxyl compounds. Examples of N-oxyl compounds include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl. Examples of inorganic polymerization inhibitors include copper chloride, copper sulfate, and iron sulfate. Examples of organic salt polymerization inhibitors include copper dibutyldithiocarbamate and N-nitroso-N-phenylhydroxylamine aluminum salt. Polymerization inhibitors may be added individually or in any combination of two or more types. They may be added from the beginning of the process or midway through. The desired amount may be added all at once or in installments. They may also be added continuously via a rectification column. The polymerization inhibitor is preferably added in an amount of 5 to 30,000 wtppm in the reaction solution, and more preferably 25 to 10,000 wtppm. By setting this amount to 5 wtppm or more, the polymerization inhibitory effect can be sufficiently exerted, and by setting it to 30,000 wtppm or less, discoloration of the reaction solution can be suppressed, the purification process after the reaction can be simplified, and a decrease in the curing rate of the obtained component (A) can be prevented.

[0060] The reaction time in the method for producing component (A) varies depending on the type and amount of catalyst used, reaction temperature, reaction pressure, etc., but is preferably 0.1 to 150 hours, and more preferably 0.5 to 80 hours.

[0061] The method for producing component (A) can be carried out by batch, semi-batch, or continuous methods. In one example of a batch method, a glycerin carbonate compound, a monofunctional (meth)acrylate, a catalyst, and a polymerization inhibitor are charged into a reactor, and the mixture is stirred at a predetermined temperature while bubbling oxygen-containing gas into the reaction solution. Subsequently, the monohydric alcohol produced as a by-product during the transesterification reaction is removed from the reactor at a predetermined pressure to produce the desired component (A).

[0062] The reaction product obtained by the method for producing component (A) is preferable because it allows for separation and purification operations to be performed on the reaction product, thereby obtaining component (A) with high purity. Separation and purification operations include crystallization, filtration, distillation, and extraction, and it is preferable to combine these operations. Examples of crystallization operations include cold crystallization and concentration crystallization; examples of filtration operations include pressure filtration, suction filtration, and centrifugal filtration; examples of distillation operations include single distillation, fractional distillation, molecular distillation, and steam distillation; and examples of extraction operations include solid-liquid extraction and liquid-liquid extraction. A solvent may be used in the separation and purification operation. Furthermore, neutralizing agents for neutralizing the catalyst and / or polymerization inhibitor used in the present invention, adsorbents for adsorption and removal, acids and / or alkalis for decomposing or removing by-products, activated carbon for improving color tone, diatomaceous earth for improving filtration efficiency and filtration rate, etc., may also be used.

[0063] The component (A) obtained in this manner has a chlorine concentration of less than 100 ppm, preferably less than 10 ppm, and a sodium concentration of less than 100 ppb, preferably less than 10 ppb, and the cured product can be a curable composition with excellent water resistance and metal corrosion resistance.

[0064] When compound having an ethylenically unsaturated group other than component (A) described below [hereinafter referred to as "component (D)"] is incorporated, the content of component (A) is preferably 5 to 100% by weight, more preferably 5 to 95% by weight, and particularly preferably 10 to 70% by weight, out of 100% by weight of the total curable components. (A) By setting the content of component 5% by weight or more, the composition can be made low viscosity. On the other hand, by setting it to 95% by weight or less, the crosslinking density can be increased and the heat resistance can be improved. Furthermore, the curing components are as defined above and refer to components (A) and (D).

[0065] 2.Curing composition The present invention is a curable composition comprising (A) above. A preferred method for producing the composition includes a step of producing component (A), which is a mixture of reaction products containing (meth)acrylate obtained by transesterifying a glycerin carbonate compound and a monofunctional (meth)acrylate in the presence of catalysts X and Y. According to this manufacturing method, component (A) can be obtained in high yield, resulting in excellent cost-effectiveness and productivity. Furthermore, component (A) obtained by this manufacturing method has low viscosity and is easy to handle due to the low amount of high molecular weight by-reaction products, and the chlorine and sodium concentrations can be reduced. The process in question can be carried out according to the manufacturing method of component (A) described above. Furthermore, if you wish to include the other ingredients listed below, simply stir and mix ingredient (A) with the other ingredients.

[0066] The viscosity of the composition can be set appropriately depending on the purpose, preferably between 10 and 3,000 mPa·s, and more preferably between 20 and 1,500 mPa·s.

[0067] The composition of the present invention can be used as an active energy ray curable composition or as a thermosetting composition, but it is preferably used as an active energy ray curable composition. Furthermore, the composition of the present invention can be used in any of the following forms: a solvent-free composition that does not contain an organic solvent, a solvent-type composition that contains an organic solvent, or an aqueous composition in which component (A) is dissolved or dispersed in water. In the aqueous composition in which component (A) is dispersed in water, commonly used emulsifiers or the reactive emulsifiers described below can be used as dispersants.

[0068] The composition of the present invention has component (A) as an essential component, but various components can be blended depending on the purpose. Preferred examples of other components include, specifically, photopolymerization initiators (hereinafter referred to as "component (B)"), thermal polymerization initiators (hereinafter referred to as "component (C)"), and compounds having ethylenically unsaturated groups other than component (A) (hereinafter referred to as "component (D)"). The following explains these ingredients. Furthermore, the other components listed below may be one of the exemplified compounds used, or two or more may be used in combination.

[0069] 2-1.(B) Component When the composition of the present invention is used as an active energy ray curable composition, it is particularly preferable to further include component (B) (photopolymerization initiator) when ultraviolet light and visible light are used as the active energy rays, from the viewpoint of ease of curing and cost. When using electron beams as the active energy source, it is not always necessary to include this ingredient, but a small amount can be added as needed to improve curing properties.

[0070] (B)Specific examples of components include benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]propanone, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropionyl)benzyl] Acetophenone compounds such as [phenyl]-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)butan-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-octylcarbazole; Benzoin compounds such as benzoin, 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-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone; Acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; and Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl-oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride, and fluorothioxanthone. Other compounds include benzyl, methyl phenylglyoxyate, ethyl (2,4,6-trimethylbenzoyl)phenyl phosphinate, ethylanthraquinone, phenanthrenequinone, and camphorquinone.

[0071] Among these compounds, acetophenone compounds are preferred, and α-hydroxyphenyl ketones are even more preferred because they exhibit good surface hardening properties even when used as a thin film coating in the atmosphere. As α-hydroxyphenyl ketones, 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one are more preferred. Furthermore, if it is necessary to increase the thickness of the cured product, for example, to 50 μm or more, it is preferable to use an acylphosphine oxide compound and a morpholine compound from the acetophenone system in combination, either to improve the curability inside the cured product or when using ultraviolet absorbers or pigments in combination. In this case, the acylphosphine oxide compound is: Examples of morpholin compounds include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphineate, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. Examples of morpholin compounds include 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one.

[0072] The content ratio of component (B) is preferably 0.05 to 15 parts by weight, and more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the total amount of curable components. By setting the ratio of component (B) to 0.05 parts by weight or more, the photocurability of the composition can be improved and the adhesion can be made excellent, and by setting it to 15 parts by weight or less, the internal curability of the cured product can be improved and the adhesion to the substrate can be made good.

[0073] 2-2.(C) Component Component (C) is a thermal polymerization initiator, and when the composition is used as a thermosetting composition, component (C) may be incorporated. The composition of the present invention can also be cured by heat after incorporating a thermal polymerization initiator. Various compounds can be used as thermal polymerization initiators, with organic peroxides and azo-based initiators being preferred.

[0074] Specific examples of organic peroxides include 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-butylperoxycyclohexyl)propane, 1, 1-Bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexyl monocarbonate, t-hexylperoxybenzoate 2,5-Dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane Examples include t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide.

[0075] Specific examples of azo compounds include 1,1'-azobis(cyclohexane-1-carbonitride), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, and azodi-t-butane.

[0076] These can be used individually or in combination of two or more. Furthermore, organic peroxides can be combined with reducing agents to produce redox reactions.

[0077] (C) The content ratio of component is preferably 10 parts by weight or less per 100 parts by weight of the total amount of curable components. When using component (C) alone, the process should be carried out according to the usual procedures for radical thermal polymerization. In some cases, it may be used in combination with component (B) (photopolymerization initiator), and after photocuring, thermal curing may be performed to further improve the reaction rate.

[0078] 2-3.(D) Component Component (D) is a compound having an ethylenically unsaturated group, and is a compound other than component (A). As for the ethylenically unsaturated group of component (D), a (meth)acryloyl group is preferred, and an acryloyl group is even more preferred, because it exhibits excellent curability of the composition.

[0079] Component (D) can be any compound having one or more ethylenically unsaturated groups, other than those in (A), and specifically include compounds having one ethylenically unsaturated group (hereinafter referred to as "monofunctional unsaturated compounds"), compounds having two ethylenically unsaturated groups (hereinafter referred to as "bifunctional unsaturated compounds"), and compounds having three or more ethylenically unsaturated groups (hereinafter referred to as "trifunctional or more functional unsaturated compounds").

[0080] Specific examples of monofunctional unsaturated compounds include compounds having a (meth)acryloyl group, monofunctional (meth)acrylamides, and compounds having a vinyl group. Examples of compounds having a (meth)acryloyl group include: Compounds having a carboxyl group and an ethylenically unsaturated group, such as (meth)acrylic acid, Michael addition dimers 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 alkylene oxide adducts of phenols, (meth)acrylates of alkylphenols, (meth)acrylates of paracumylphenols, orthophenylphenol (meth)acrylate, (meth)acrylates of orthophenylphenols, 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 Examples include tetrahydrofurfuryl (meth)acrylate, (meth)acryloylmorpholine, N-(2-(meth)acryloxyethyl)hexahydrophthalimide, and monofunctional (meth)acrylates having heterocyclic rings such as N-(2-(meth)acryloxyethyl)tetrahydrophthalimide.

[0081] Examples of monofunctional (meth)acrylamides include N-alkyl (meth)acrylamides such as N,N-dimethyl(meth)acrylamide, (meth)acryloylmorpholine, N-methyl(meth)acrylamide, Nn-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nn-butyl(meth)acrylamide, N-sec-butyl(meth)acrylamide, Nt-butyl(meth)acrylamide, and Nn-hexyl(meth)acrylamide; N-hydroxyalkyl(meth)acrylamides such as N-hydroxyethyl(meth)acrylamide; and Examples include 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, as well as other N,N-dialkyl(meth)acrylamides.

[0082] Examples of compounds containing a vinyl group include N-vinylpyrrolidone and N-vinylcaprolactam.

[0083] As the bifunctional unsaturated compound, a bifunctional (meth)acrylate is preferred. Examples of bifunctional (meth)acrylates 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, tetramethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, di(meth)acrylate of alkylene oxide adducts of bisphenol A, and di(meth)acrylate of alkylene oxide adducts of bisphenol F.

[0084] In addition to the compounds mentioned above, other oligomers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate can be used as bifunctional (meth)acrylates.

[0085] As for trifunctional or more unsaturated compounds, trifunctional or more (meth)acrylates having three or more (meth)acryloyl groups are preferred. For example, polyol poly(meth)acrylates such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri or tetra(meth)acrylate, ditrimethylolpropane tri or tetra(meth)acrylate, diglycerin tri or tetra(meth)acrylate, and dipentaerythritol tri, tetra, penta or hexa(meth)acrylate; and Examples include poly(meth)acrylates of polyol alkylene oxide adducts such as tri(meth)acrylate of glycerin alkylene oxide adducts, tri or tetra(meth)acrylate of pentaerythritol alkylene oxide adducts, tri or tetra(meth)acrylate of ditrimethylolpropane alkylene oxide adducts, tri or tetra(meth)acrylate of diglycerin alkylene oxide adducts, and tri, tetra, penta, or hexa(meth)acrylate of dipentaerythritol alkylene oxide adducts; as well as tri(meth)acrylate of isocyanuric acid alkylene oxide adducts. Examples of the alkylene oxide adducts mentioned above include ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts.

[0086] In addition to the compounds mentioned above, other types of (meth)acrylates with three or more functionalities can also be used as urethane (meth)acrylates.

[0087] Among these compounds, tri- or tetra(meth)acrylate of pentaerythritol, tri, tetra, penta, or hexa(meth)acrylate of dipentaerythritol, and trifunctional or higher urethane(meth)acrylates are preferred because the cured products of the resulting compositions have high hardness and excellent adhesion to the substrate. The following describes trifunctional or higher urethane(meth)acrylates in detail.

[0088] Examples of trifunctional or more urethane (meth)acrylates include reaction products of polyhydric alcohols, polyhydric isocyanates, and hydroxyl group-containing (meth)acrylates, as well as reaction products of organic polyhydric isocyanates and hydroxyl group-containing (meth)acrylate compounds.

[0089] Examples of polyhydric alcohols include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by the reaction of the polyhydric alcohol with the polybasic acid, caprolactone polyols obtained by the reaction of the polyhydric alcohol with the polybasic acid with ε-caprolactone, and polycarbonate polyols (for example, polycarbonate polyols obtained by the reaction of 1,6-hexanediol with diphenyl carbonate).

[0090] Examples of organic polyvalent isocyanates include diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and dicyclopentanyl diisocyanate; Examples include organic polyisocyanates having three or more isocyanate groups, such as hexamethylene diisocyanate trimers and isophorone diisocyanate trimers.

[0091] Examples of hydroxyl group-containing (meth)acrylates include hydroxyl group-containing mono(meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, hydroxyhexyl (meth)acrylate, and hydroxyoctyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, and pentaerythritol mono(meth)acrylate; Other examples include trimethylolpropane di(meth)acrylate, pentaerythritol di or tri(meth)acrylate, di or tri(meth)acrylate of ditrimethylolpropane and di, tri, tetra or penta(meth)acrylate of dipentaerythritol, hydroxyl group-containing polyfunctional (meth)acrylates such as glycerin di(meth)acrylate.

[0092] Preferred trifunctional or more urethane (meth)acrylates include reaction products of an organic polyisocyanate having two isocyanate groups and a hydroxyl group-containing polyfunctional (meth)acrylate. Among these, isophorone diisocyanate and hexamethylene diisocyanate are preferred as organic polyisocyanates having two isocyanate groups due to their low viscosity, high cured product hardness, and low coloration, while pentaerythritol di or tri(meth)acrylate, di, tri, tetra or penta(meth)acrylate of dipentaerythritol, and glycerin di(meth)acrylate are preferred as hydroxyl group-containing polyfunctional (meth)acrylates.

[0093] Urethane (meth)acrylate manufactured by conventional methods can be used. For example, one method involves heating and stirring an organic polyvalent isocyanate and a polyvalent ol in the presence of an addition catalyst such as dibutyltin dilaurate to produce an isocyanate group-containing compound, and then adding a hydroxyl group-containing (meth)acrylate to the compound and heating and stirring to carry out an addition reaction. In the case of a reaction product between an organic polyvalent isocyanate and a hydroxyl group-containing (meth)acrylate, one method is to heat and stir the organic polyvalent isocyanate and the hydroxyl group-containing (meth)acrylate in the presence of an addition catalyst to carry out the addition reaction.

[0094] Other examples of urethane poly(meth)acrylates include compounds described on pages 70-74 of the literature "UV / EB Curing Materials" [CMC Co., Ltd., published in 1992].

[0095] The content of component (D) is preferably 0 to 80% by weight, and more preferably 10 to 50% by weight, of the total amount of curing components by 100% by weight. (D) By limiting the content of component to 80% by weight or less, it is possible to prevent the composition from becoming highly viscous and to achieve excellent adhesion to the substrate when used as a coating agent. (D) By making the content of component 10% by weight or more, when used as a coating agent, it is possible to achieve excellent adhesion to plastics.

[0096] 2-4. Other components not mentioned above Other preferred components include surface modifiers, antistatic agents, polymerization inhibitors, organic solvents, antioxidants, ultraviolet absorbers, and silane coupling agents. The following explains these ingredients.

[0097] 2-4-1. Surface Modifiers The composition of the present invention may contain a surface modifier for purposes such as improving leveling properties during application or enhancing scratch resistance by increasing the slipperiness of the cured product. Examples of surface modifiers include surface modifiers, surfactants, leveling agents, defoaming agents, lubricity-imparting agents, and antifouling agents, and these known surface modifiers can be used. Among these, silicone-based surface modifiers and fluorine-based surface modifiers are particularly preferred. Specific examples include organopolysiloxanes having a polyoxyalkylene skeleton in their molecular structure, organopolysiloxanes having a polyester skeleton, fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, and fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain. Furthermore, a surface modifier having an ethylenically unsaturated group, preferably a (meth)acryloyl group, in its molecule may be used for purposes such as increasing the durability of the lubricity.

[0098] Among these, it is preferable to use an organopolysiloxane having a polyoxyalkylene skeleton (hereinafter referred to as "component (E)") because it has excellent surface smoothness and can significantly improve the antistatic function described later. Examples of oxyalkylenes that constitute the polyoxyalkylene skeleton include oxyethylene, oxypropylene, oxybutylene, and combinations of these oxyalkylenes. The polyoxyalkylene skeleton can be attached to one end, both ends, or side chains of the polysiloxane chain. Specific examples of component (E) include polyoxyethylene-methylpolysiloxane copolymer and poly(oxyethylene-oxypropylene)methylpolysiloxane copolymer. (E) The component is commercially available, for example, 71ADDITIVE, 74ADDITIVE, 57ADDITIVE, 8029ADDITIVE, 8054ADDITIVE, 8211ADDITIVE, 8019ADDITIVE, 8526ADDITIVE, FZ-2123, FZ-2191 [manufactured by Toray Dow Corning Co., Ltd.]; TSF4440, TSF4441, TSF4445, TSF4446, TSF4450, TSF4452, TSF4460 (manufactured by Momentive Performance Materials); Silface SAG002, Silface SAG003, Silface SAG005, Silface SAG503A, Silface SAG008, Silface SJM003 [manufactured by Nisshin 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 Examples include BYK-345, BYK-347, BYK-348, BYK-375, and BYK-377 (manufactured by BYK Chemie Japan).

[0099] The surface modifier content is preferably 0.01 to 5.0 parts by weight per 100 parts by weight of the total amount of curable components.

[0100] 2-4-2. Antistatic agents The composition of the present invention may contain an antistatic agent for the purpose of providing an antistatic function. Examples of antistatic agents include cationic antistatic agents having cationic groups such as quaternary ammonium salts, pyridinium salts, and primary to tertiary amino groups; anionic antistatic agents having anionic groups such as sulfonic acid bases, sulfate ester bases, phosphate ester bases, and phosphonic acid bases; amphoteric antistatic agents such as amino acid-based and aminosulfate ester-based agents; nonionic antistatic agents such as amino alcohol-based, glycerin-based, and polyethylene glycol-based agents; and polymeric antistatic agents that are high molecular weight versions of the above-mentioned antistatic agents. Furthermore, ionic liquids and metal salts can also be used as antistatic agents. The ionic liquids and metal salts are not particularly limited, and various commonly used ionic liquids and metal salts can be used. The metal salts are useful because, even in trace amounts, they exhibit high ionic dissociation properties, thus exhibiting excellent antistatic performance. On the other hand, the ionic liquids are useful because, even in trace amounts, they can impart sufficient antistatic performance due to their excellent conductivity.

[0101] Among these, metal salts of anions having fluoro and sulfonyl groups [hereinafter referred to as "component (F)"] are preferred because they have excellent antistatic properties and optical properties. In component (F), the anion having a fluoro group and a sulfonyl group is preferably a trifluoromethanesulfonyl group. Furthermore, the metal forming the metal salt is preferably an alkali metal, a group 2A element, a transition metal, or an amphoteric metal, with alkali metal being more preferred.

[0102] (F) Specific compounds that are preferred include metal salts of bis(trifluoromethanesulfonyl)imide, alkali metal salts of tris(trifluoromethanesulfonyl)methide, and alkali metal salts of trifluoromethanesulfonate ions. In other words, one of the compounds represented by the following general formulas (D1) to (D3) is preferred. M(CF3SO2)2N ······(D1) M(CF3SO2)3C ······(D2) M(CF3SO3) ······(D3) In general formulas (D1) to (D3), M represents an alkali metal. Lithium, sodium, and potassium are preferred alkali metal salts, with lithium being more preferred.

[0103] Specific examples of the above components include bis(fluoroalkylsulfonyl)imide ions, tris(fluoroalkylsulfonyl)methide ions, and fluoroalkylsulfonate ions. Specifically, these include bis(trifluoromethanesulfonyl)imidolithium [Li(CF3SO2)2N], bis(trifluoromethanesulfonyl)imidolithium [K(CF3SO2)2N], bis(trifluoromethanesulfonyl)imidolithium [Li(CF3SO2)3C], tris(trifluoromethanesulfonyl)methidepotassium [K(CF3SO2)3C], tris(trifluoromethanesulfonyl)methidesodium [Na(CF3SO2)3C], tris(trifluoromethanesulfonyl)methidesodium [Na(CF3SO2)3C], trifluoromethanesulfonate lithium [Li(CF3SO3)], trifluoromethanesulfonate potassium [K(CF3SO3)], and trifluoromethanesulfonate sodium [Na(CF3SO3)]. Among these compounds, bis(trifluoromethanesulfonyl)imidolithium, tris(trifluoromethanesulfonyl)methidolithium, and lithium trifluoromethanesulfonate are preferred, with bis(trifluoromethanesulfonyl)imidolithium and lithium trifluoromethanesulfonate being particularly preferred.

[0104] The amount of antistatic agent is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of solids in the composition. By including 0.1 parts by weight or more of the antistatic agent, the effect of reducing surface resistivity is achieved, while by including 20 parts by weight or less, the water resistance of the cured product can be improved.

[0105] In this invention, it is preferable to use components (E) and (F) in combination in order to more effectively reduce surface resistivity.

[0106] 2-4-3. Polymerization Inhibitors The composition of the present invention may contain polymerization inhibitors for the purpose of improving storage stability, such as preventing gelation of the composition. Examples of polymerization inhibitors include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors exemplified in the method for producing component (A) described above, and the same compounds as described above are exemplified. Among these compounds, organic compounds having stable radicals are preferred as polymerization inhibitors because they improve storage stability without reducing the hardness of the cured product. Examples of organic compounds having stable radicals include garbinoxyl and N-oxyl compounds, with N-oxyl compounds being more preferred for the following reasons. Specifically, when coating using the composition, work is often performed under fluorescent lights that exclude ultraviolet light (UV-cut fluorescent lights) for better work efficiency. Even when storing the composition under such fluorescent lights, compositions containing N-oxyl compounds exhibit excellent storage stability. Specific examples of N-oxyl compounds include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl. Polymerization inhibitors can be added to the composition, or if they are included in component (A), they can be used as is. Furthermore, even if component (A) already contains a polymerization inhibitor, additional polymerization inhibitors may be added. The polymerization inhibitor content is preferably 0.0005 to 1% by weight, and more preferably 0.005 to 0.1% by weight, in the composition. By setting the polymerization inhibitor content to 0.0005% by weight or more, the polymerization inhibiting effect can be sufficiently exhibited, and by setting it to 1% by weight or less, a decrease in the hardness of the cured product can be avoided.

[0107] 2-4-4. Organic Solvents The composition of the present invention does not substantially require an organic solvent, but may contain an organic solvent as needed for purposes such as viscosity adjustment. Examples of organic solvents include the same organic solvents listed in the method for producing component (A) described above. The organic solvent content is preferably 0.1 to 1000 parts by weight, and more preferably 5 to 500 parts by weight, per 100 parts by weight of the total amount of curable components. Within this range, the composition can be made to have a viscosity suitable for coating, and the composition can be easily applied by the known coating method described later.

[0108] 2-4-5. Antioxidants Antioxidants are added to improve the durability of the cured product, such as its heat resistance and weather resistance. Examples of antioxidants include phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. Commercially available examples include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by ADEKA Corporation. Examples of phosphorus-based antioxidants include phosphines such as trialkylphosphines and triarylphosphines, as well as trialkyl phosphites and triaryl phosphites. Commercially available derivatives of these include, for example, Adeka Stub PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, and 3010, all manufactured by Adeka Corporation. Examples of sulfur-based antioxidants include thioether compounds, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by ADEKA Corporation. These can be used individually or in combination of two or more types. Preferred combinations of these antioxidants include the combined use of a phenolic antioxidant and a phosphorus-based antioxidant, and the combined use of a phenolic antioxidant and a sulfur-based antioxidant. The antioxidant content can be set appropriately depending on the purpose, but is preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 1 part by weight, per 100 parts by weight of the total amount of curable components. By including 0.1 parts by weight or more of antioxidant, the durability of the composition can be improved, while by including 5 parts by weight or less, good curability and adhesion can be achieved.

[0109] 2-4-6. UV absorbers UV absorbers are added to improve the light resistance of the cured product. Examples of UV absorbers include triazine-based UV absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole-based UV absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130. The content ratio of the UV absorber can be set appropriately depending on the purpose, but it is preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 1 part by weight, per 100 parts by weight of the total amount of curable components. By setting the UV absorber content ratio to 0.01% by weight or more, good light resistance of the cured product can be achieved, while by setting it to 5% by weight or less, excellent curability of the composition can be achieved.

[0110] 2-4-7. Silane coupling agents Silane coupling agents are added to improve the interfacial adhesion strength between the cured product and the substrate. The silane coupling agent is not particularly limited as long as it can contribute to improving adhesion to the substrate.

[0111] Examples of silane coupling agents include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

[0112] The content ratio of the silane coupling agent can be set appropriately depending on the purpose, and is preferably 0.1 to 10 parts by weight, and more preferably 1 to 5 parts by weight, per 100 parts by weight of the total amount of curable components. By increasing the content of the silane coupling agent to 0.1 parts by weight or more, the adhesive strength of the composition can be improved, while by keeping it at 10 parts by weight or less, changes in adhesive strength over time can be prevented.

[0113] 3.Applications Component (A) in the present invention exhibits excellent curability, and Glycarbo-A [(2-oxo-1,3-dioxolan-4-yl)methyl acrylate] in particular exhibits excellent curability and can reduce the viscosity of the composition, making it preferable to use in compositions 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, and can be used for a variety of applications. Examples include coating agents such as paints, adhesives, sealants, inks, molding agents for forming excipients, and pattern-forming agents such as resists. The compositions of the present invention can be preferably used in coating compositions, adhesive compositions, and excipient compositions among these applications, and more preferably in active energy ray curable coating compositions, adhesive compositions, and excipient compositions. The following describes preferred uses. Furthermore, for the other components listed below, only one of the exemplified compounds may be used, or two or more may be used in combination.

[0114] 3-1. Coating composition The composition of the present invention has excellent thin-film curability and high hardness of the cured product, making it suitable for use as a coating agent composition. Furthermore, since component (A) has low viscosity, it is more suitable for use as a solvent-free coating agent composition. Furthermore, as mentioned above, component (A) has a low chlorine concentration, which allows for the formation of a cured film with excellent corrosion resistance, and component (A) has a low sodium concentration, which allows for the formation of a cured film with excellent water resistance.

[0115] Furthermore, because the resulting cured film of the present invention exhibits excellent surface hardness and scratch resistance, it can be preferably used as a coating agent for various plastics, i.e., as a hard coat agent, and can be preferably used as a solvent-free hard coat agent. Examples of substrates to which hard coating agents can be applied include plastic films used in polarizer protective films and anti-reflective films, and resin molded products used in home appliances and automotive interior and exterior parts.

[0116] The coating agent composition has (A) as an essential component, but various components can be added depending on the purpose. Other components include, specifically, the aforementioned components (B), (C), and (D), surface modifiers, ultraviolet absorbers, antistatic agents, polymerization inhibitors, organic solvents, antioxidants, and silane coupling agents. Other examples include pigments, dyes, and polymers. Specific examples of pigments, dyes, and polymers include compounds similar to those listed in paragraphs

[0088] and

[0094] of the international publication WO2017 / 002964.

[0117] Another use for the coating composition is as a coating agent for metal substrates. As described above, component (A) used in the present invention has a low chlorine concentration, which allows for the formation of a cured film of a corrosion-resistant curable composition on the surface of a metal substrate. A method for manufacturing a metal substrate having a cured film using the composition of the present invention preferably includes the steps of coating a part or all of the metal substrate with the curable composition, and curing the coated composition by irradiating it with active energy rays or by heating. The metal substrate having a cured film obtained from the composition of the present invention is suitable for use as an electrode protective material, a circuit board protective material, and an electrode protective coating agent used in lithium-ion batteries, etc., because the cured film has excellent water resistance and corrosion resistance.

[0118] 3-2. Adhesive Compositions The composition of the present invention has low viscosity and excellent curability, making it suitable for use as an adhesive composition. Furthermore, as mentioned above, since the cured product has excellent corrosion resistance and water resistance, it can be preferably used in applications where these physical properties are required.

[0119] The adhesive composition has (A) as an essential component, but various components can be added depending on the purpose. Other components include, specifically, the components (B), (C), and (D) mentioned above, as well as surface modifiers, ultraviolet absorbers, polymerization inhibitors, organic solvents, antioxidants, silane coupling agents, pigments and dyes, and polymers.

[0120] 3-3. Composition for molding material The composition of the present invention has low viscosity and high hardness of the cured product, making it suitable for use as a molding material composition in applications such as mold transfer and nanoimprinting. In particular, it is suitable for use as a shaping material in microfabrication applications such as nanoimprinting. Furthermore, in this invention, for convenience, the shaping material is also included in the concept of the molding material.

[0121] As a molding material, it can be used in the manufacture of molding films having a fine uneven surface structure, such as lens sheets, nanoimprint films, anti-reflective films with a moth-eye shape, polarizing films, anti-glare films, light extraction films for organic EL / LEDs, light confinement films for solar cells, and heat retroreflective films.

[0122] The molding material composition has (A) as an essential component, but various components can be blended depending on the purpose. Other components include, specifically, the components (B), (C), and (D) mentioned above, as well as surface modifiers, ultraviolet absorbers, polymerization inhibitors, organic solvents, antioxidants, silane coupling agents, pigments and dyes, and polymers.

[0123] 3-4. Ink Compositions Because the composition of the present invention has excellent thin-film curing properties, it can be preferably used for transparent overprint varnish inks that are printed on a printing press after single-color or multi-color printing, as well as for color printing inks such as yellow, red, cyan, and black.

[0124] Various printing methods are possible, including offset printing (conventional lithography using dampening solution and waterless lithography without dampening solution), letterpress printing (flatbed letterpress, semi-rotary letterpress, rotary, intermittent rotary, flexographic), intaglio printing (gravure printing), stencil printing (screen printing), and inkjet printing. Due to its excellent emulsification stability, it is preferably used for offset printing using dampening solution. Furthermore, due to its low viscosity, it is also preferably used for inkjet printing.

[0125] The ink composition has (A) as an essential component, but various components can be added depending on the purpose. Other components include, specifically, the components (B), (C), and (D) mentioned above, as well as binders, pigments, plasticizers, and friction-resistant agents. Specific examples of binders, pigments, plasticizers, and friction inhibitors include compounds similar to those listed in paragraphs

[0101] to

[0107] of the international publication WO2017 / 002964.

[0126] As for the method of manufacturing the ink composition, one can follow the conventional method of manufacturing the ink composition, and examples include a method in which component (A), component (B) (when the active energy ray is ultraviolet light), binder, pigment, polymerization inhibitor, wax, and other additives are blended, then the pigment is added and dispersed using a disperser such as a three-roll mill or a bead mill.

[0127] 3-5. Compositions for pattern formation The composition of the present invention has high exposure sensitivity and excellent developability, and can form precise and accurate patterns, making it suitable for use as a pattern-forming composition.

[0128] The pattern-forming composition has (A) as an essential component, but various components can be added depending on the purpose. Other components include, specifically, (B) and (D) mentioned above, organic solvents, antioxidants, ultraviolet absorbers, silane coupling agents, surface modifiers, and polymerization inhibitors, as well as alkali-soluble resins. Specific examples of alkali-soluble resins include compounds similar to those listed in paragraphs

[0110] to

[0122] of the international publication WO2017 / 002964.

[0129] 4.How to use The composition of the present invention can be used according to conventional methods. For example, one method involves applying the composition to the substrate using a conventional coating method, and then curing it by irradiating it with active energy rays or by heating it. For the irradiation method using active energy rays, a common method known as a conventional curing method should be adopted. Furthermore, a method can be employed in which component (B) (photopolymerization initiator) and component (C) (thermal polymerization initiator) are used in combination in the composition, and then the mixture is irradiated with active energy rays and subsequently heated and cured to improve adhesion to the substrate.

[0130] The composition of the present invention can be applied to a variety of substrates, including plastics, metals, wood, inorganic materials, and paper. Specific examples of plastics include polyolefins such as polyethylene and polypropylene, ABS resin, polyvinyl alcohol, cellulose acetate resins such as triacetylcellulose and diacetylcellulose, acrylic resin, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, norbornene, and other cyclic polyolefin resins, polyvinyl chloride, epoxy resins, and polyurethane resins. Examples of metals include steel plates, aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO). Examples of wood include natural wood and synthetic wood. Examples of inorganic materials include glass, mortar, concrete, and stone.

[0131] The method for coating the composition of the present invention onto a substrate can be appropriately set according to the purpose, and examples include coating with a bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, knife coater, comma coater, reverse roll coater, die coater, lip coater, spray coater, gravure coater, and microgravure coater.

[0132] When the composition of the present invention is used as an active energy ray curable composition, examples of active energy rays for curing include ultraviolet light, visible light, and electron beams, but ultraviolet light or visible light is preferred, and ultraviolet light is particularly preferred. 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 should be set appropriately depending on the type and composition of the active energy rays. For example, when using a high-pressure mercury lamp, the irradiation energy should be 50 to 5,000 mJ / cm². 2 Preferably, 100-1,000 mJ / cm² 2 This is preferable.

[0133] When the composition of the present invention is used as a thermosetting composition, a cured film can be obtained by leaving the cured film standing in a heatable dryer or the like. The heating temperature can be set appropriately depending on the substrate and purpose, but 40 to 180°C is preferable. If the substrate is plastic, it is preferable to keep the temperature below 120°C, as excessively high temperatures may cause the substrate to deform. The heating time can be set appropriately depending on the substrate and heating temperature, and is preferably 0.5 to 60 minutes.

[0134] As described above, the compositions of the present invention can be preferably used in coating agent compositions, adhesive compositions, molding material compositions, ink compositions, and pattern forming compositions, and specific examples thereof will be described.

[0135] 4-1. Method of using the coating agent composition The method of using the coating agent composition should follow conventional methods. For example, one method involves applying the composition to a substrate and then curing it by irradiating it with active energy rays or by heating it. Specifically, examples include applying the composition to the substrate using a conventional coating method, then curing it by irradiating it with active energy rays in the case of an active energy ray-curable composition, or curing it by heating it in the case of a thermosetting composition. Furthermore, a method can be employed in which component (C) (photopolymerization initiator) and component (D) (thermal polymerization initiator) are used in combination in the composition, and then the mixture is irradiated with active energy rays and subsequently heated and cured to improve adhesion to the substrate.

[0136] The composition of the present invention can be applied to a variety of substrates, including plastics, metals, wood, inorganic materials, and paper, with specific examples being those mentioned above.

[0137] The thickness of the cured film of the composition on the substrate can be set appropriately depending on the purpose. The thickness of the cured film can be selected according to the substrate used and the application of the substrate with the manufactured cured film, but it is preferably 1 μm to 5 mm, and more preferably 3 μm to 3 mm.

[0138] The method for coating the composition of the present invention onto a substrate can be appropriately set according to the purpose, and examples include the method described in detail above.

[0139] When used as an active energy ray curing coating agent composition, examples of active energy rays for curing include ultraviolet light, visible light, and electron beams, but ultraviolet light is preferred. Examples of ultraviolet irradiation devices include those described above. The irradiation energy can be set appropriately according to the type and composition of the activated energy rays, and the same irradiation energy as described above can be used.

[0140] 4-2. Method of using the adhesive composition The adhesive composition should be used according to conventional methods. For example, one method involves applying the composition to a substrate, bonding the coated surface to another substrate, and then curing it by irradiating it with active energy rays or by heating. Specifically, examples include applying the composition to the substrate using a conventional coating method, then curing it by irradiating it with active energy rays in the case of an active energy ray-curable composition, or curing it by heating it in the case of a thermosetting composition. Furthermore, in the case of an active energy ray curable adhesive composition, at least one of the above-mentioned substrates shall be one that is light-transmitting. Furthermore, a method can be employed in which component (C) (photopolymerization initiator) and component (D) (thermal polymerization initiator) are used in combination in the composition, and then the mixture is irradiated with active energy rays and subsequently heated and cured to improve adhesion to the substrate.

[0141] The composition of the present invention can be applied to a variety of substrates, including plastics, metals, wood, inorganic materials, and paper, with specific examples being those mentioned above.

[0142] The thickness of the cured film of the composition on the substrate can be set appropriately depending on the purpose. The thickness of the cured film can be selected according to the substrate used and the application of the substrate with the manufactured cured film, but it is preferably 0.1 to 500 μm, and more preferably 1 to 200 μm.

[0143] The method for coating the composition of the present invention onto a substrate can be appropriately set according to the purpose, and examples include the method described in detail above.

[0144] When used as an active energy ray curing adhesive composition, the active energy rays used for curing include ultraviolet light, visible light, and electron beams, but ultraviolet light is preferred. Examples of ultraviolet irradiation devices include those described above. The irradiation energy can be set appropriately according to the type and composition of the activated energy rays, and the same irradiation energy as described above can be used.

[0145] 4-3. Method of using the composition for molding materials When using the composition of the present invention as a molding material, conventional methods of use may be followed. Specifically, examples include a method in which a composition is applied to a mold called a stamper having the desired shape, laminated with a film or sheet substrate (hereinafter collectively referred to as "film substrate"), and then cured by irradiation with active energy rays; a method in which a composition is injected into a predetermined mold and then cured by irradiation with active energy rays in the case of an active energy ray curable composition; and a method in which a thermosetting composition is cured by heating.

[0146] Suitable film substrates for use in the present invention include plastic films such as polymethyl methacrylate, polymethyl methacrylate-styrene copolymer film, polyethylene terephthalate, polyethylene naphthalate, polyarylate, polyacrylonitrile, polycarbonate, polysulfone, polyethersulfone, polyetherimide, polyetherketone, polyimide, and polymethylpentene. Glass-based substrates can also be used if necessary.

[0147] The film substrate is preferably transparent or translucent (for example, milky white). The thickness of the film substrate is preferably 20 to 500 μm.

[0148] The thickness of the cured film of the composition on the substrate can be set appropriately depending on the purpose. The thickness of the cured film can be selected according to the substrate used and the application of the substrate with the manufactured cured film, but it is preferably 10 nm to 100 μm, and more preferably 50 nm to 50 μm.

[0149] Examples of active energy rays for curing the composition of the present invention include ultraviolet light, visible light, and electron beams, but ultraviolet light is preferred. Examples of ultraviolet irradiation devices include those described above. The irradiation energy can be set appropriately according to the type and composition of the activated energy rays, and the same irradiation energy as described above can be used.

[0150] An example of manufacturing a lens sheet using the composition of the present invention will be described. When manufacturing a lens sheet with a relatively thin film thickness, the composition of the present invention is applied to a transparent substrate, and then a mold called a stamper, which has the shape of the desired lens, is brought into close contact with it. Next, the composition is cured by irradiating it with active energy rays from the transparent substrate side, and then peeled off from the mold.

[0151] On the other hand, when manufacturing a lens sheet with a relatively thick film thickness, the composition of the present invention is poured between a mold having the shape of the desired lens and a transparent substrate. Next, the composition is cured by irradiating it with active energy rays from the transparent substrate side, and then the mold is demolded.

[0152] The material of the mold is not particularly limited, but examples include metals such as brass and nickel, and resins such as epoxy resin. It is preferable that the mold be made of metal because it has a long lifespan.

[0153] When using the composition of the present invention for nanoimprint applications, conventional methods may be followed. For example, after applying the composition to a substrate, a mold having a micro-machined pattern and being transparent is pressed onto it. Next, a method can be used in which the composition is cured by irradiating it with active energy rays from above a transparent mold, and then the mold is demolded.

[0154] 4-4. Method of using ink compositions The printing substrate used in the printed materials of the present invention is not particularly limited, and examples include paper such as fine paper, coated paper, art paper, imitation paper, thin paper, and cardboard; various synthetic papers; films or sheets such as polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon, polylactic acid, and polycarbonate; cellophane; aluminum foil; and various other substrates that have been conventionally used as printing substrates.

[0155] The thickness of the cured film of the composition on the substrate can be set appropriately depending on the purpose. The thickness of the cured film can be selected according to the substrate used and the application of the substrate with the manufactured cured film, but it is preferably 1 to 20 μm, and more preferably 1 to 10 μm.

[0156] When the composition of the present invention is used for offset ink, it can be suitably used as a coating method for the substrate by using an offset printing press that continuously supplies water onto the printing plate. Furthermore, it can be suitably used with either a sheet-fed offset printing press using sheet-type printing paper or an offset web printing press using reel-type printing paper.

[0157] When the composition of the present invention is used for inkjet ink, it can be suitably used as a coating method for a substrate, such as a known inkjet recording device that ejects by an inkjet method to form an image.

[0158] In the inkjet method, considering ejection performance, it is preferable that the viscosity of the composition is 7 mPa·s to 30 mPa·s at the ejection temperature (for example, 40°C to 80°C, preferably 25°C to 30°C). More preferably, it is 7 mPa·s to 20 mPa·s.

[0159] Examples of active energy rays for curing the composition of the present invention include ultraviolet light, visible light, and electron beams, but ultraviolet light is preferred. Examples of ultraviolet irradiation devices include those described above. The irradiation energy can be set appropriately according to the type and composition of the activated energy rays, and the same irradiation energy as described above can be used.

[0160] 4-5. Method of using the pattern-forming composition Examples of pattern-forming compositions include photosensitive lithographic printing plates, resists such as etching resists and solder resists, columnar spacers in liquid crystal panel manufacturing, coloring compositions for forming pixels and black matrices in color filters, and color filter protective films.

[0161] Among these applications, the composition of the present invention is most preferably used in the manufacturing of liquid crystal panels as a columnar spacer, a colored composition for color filters, and a protective film for color filters. When used for columnar spacers and color filter protective films, nonionic surfactants such as polyoxyethylene lauryl ether or fluorinated surfactants may be added to the composition to improve coating and developing properties. Additionally, adhesive aids, preservative stabilizers, and defoamers may be added as needed. [Examples]

[0162] The present invention will be explained in more detail below with reference to manufacturing examples, examples, and comparative examples. In the following, "parts" refers to parts by weight. High-performance liquid chromatography (HPLC), viscosity, gel permeation chromatography (GPC), gas chromatography (GC), APHA, chlorine content, and sodium content were measured under the following conditions.

[0163] ◆HPLC measurement conditions • Equipment: ACQUITY UPLC manufactured by Waters Co., Ltd. • Detector: UV detector • Detection wavelength: 210nm • Column: Waters Corporation ACQUITY UPLC BEH C18 (Part No. 186002350, column inner diameter 2.1 mm, column length 50 mm) Column temperature: 40°C • Eluent composition: Mixture of 0.03 wt% trifluoroacetic acid aqueous solution and methanol. • Eluent flow rate: 0.3 mL / min

[0164] ◆Viscosity measurement conditions A cone-plate viscometer (Type E viscometer) was used to measure the viscosity at 25°C.

[0165] ◆GPC measurement conditions • Equipment: Waters Corporation GPC System Name 1515 2414 717P RI • Detector: RI detector • Columns: Guard column Shodex KFG (8μm 4.6×10mm) manufactured by Showa Denko K.K., and two types of main columns Waters Co., Ltd.: styragel HR 4E THF (7.8×300mm) + styragel HR 1THF (7.8×300mm) manufactured by Waters Co., Ltd. Column temperature: 40°C • Eluent composition: THF (containing 0.03% sulfur as an internal standard), flow rate 0.75 mL / min • Calibration curve: A calibration curve was created using standard polystyrene. • How to calculate purity (%) Of the peaks detected by GPC measurement, the area of ​​all peaks originating from the purified product was taken as 100%, and the area of ​​the peaks containing glycerin carbonate acrylate and / or glycerin carbonate ethylene oxide adduct acrylate was calculated based on the following formula (1). If the peaks were not completely separated, vertical splitting was performed to obtain the area of ​​each peak. Purity of the purified product (%) = (I / S) × 100 ... (1) The symbols and terms in equation (1) are as described above. • S: Total area of ​​detection peaks derived from the purified product • I: Area of ​​the detection peak containing acrylates from glycerin carbonate acrylate and / or glycerin carbonate ethylene oxide adduct.

[0166] ◆GC measurement conditions • Equipment: Shimadzu Corporation GC-14B • Detector: FID detector • Column: ZB-1 (Length 60m, Inner diameter 0.32mm, Film thickness 3μm) Injection temperature: 230°C or 270°C Detector temperature: 330℃ • Column temperature: Hold at 125°C for 5 minutes, then increase temperature at a rate of 10°C / minute. Hold at 325°C for 20 minutes after reaching 325°C. • Carrier gas: Nitrogen • Injection volume: 0.4 μL after diluting with methanol or acetone to 10% by weight. • How to calculate purity (%) Of the peaks detected by GC measurement, peaks originating from the undiluted sample were not considered. The sum of the areas of all peaks originating from the undiluted sample was taken as 100%, and the area of ​​the target substance was calculated from the peak area based on the following formula (2). If the peaks were not completely separated, vertical splitting was performed to obtain the area of ​​each peak. Purity of the target substance (%) = (I / S) × 100 ... (2) The symbols and terms in equation (2) are as described above. • S: Total area of ​​detection peaks derived from the sample before solvent dilution. • I: Peak area of ​​the target object

[0167] ◆APHA APHA was measured using a colorimeter [OME-2000 Petroleum Product Color Tester manufactured by Nippon Denshoku Industries Co., Ltd.].

[0168] ◆Chlorine content Collect 30 mg of the sample in a quartz boat of a trace chlorine and sulfur analyzer, combust it under an argon / oxygen stream, and finally combust it under a pure oxygen stream. Pass the resulting combustion gas through 10 ml of an absorption solution (0.3% hydrogen peroxide solution) to collect the chlorine content as Cl ions. Repeat the same operation three times to collect the chlorine content in the same absorption solution to obtain a test solution. Measure the test solution with an ion chromatograph and quantify the Cl ions by the calibration curve method. · Trace chlorine and sulfur analyzer: TOX-100 manufactured by Mitsubishi Chemical Analytech Co., Ltd. · Ion chromatograph: DIONEX ICS-3000 manufactured by Thermo Fisher Scientific K.K. (Column: IonPac AG20 / AS20)

[0169] ◆Sodium content Collect 1 g of the sample in a 20 ml PFA bottle (fluororesin bottle), dilute it to a total of 10 g with NMP (N-methylpyrrolidone) to obtain a test solution. Measure the test solution with an ICP mass spectrometer. Quantify the detected elements by the absolute calibration curve method. · Pretreatment environment: Clean room G (class 1000) and clean draft (class 100) · NMP: For electronic industry use [manufactured by Fujifilm Wako Pure Chemical Corporation] · Mixed standard solution: XSTC-622B (manufactured by SPEX) · ICP mass spectrometer: Agilent 7700s manufactured by Agilent Technologies K.K. (organic solvent measurement mode: He / H2)

[0170] 1. Manufacturing example In addition, the abbreviations in the production examples have the following meanings. · MCA: 2-methoxyethyl acrylate · MEL: 2-methoxyethanol · DABCO: Triethylenediamine [[ID=�1]] · MEHQ: Hydroquinone monomethyl ether · TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl · DEHA: N,N-diethylhydroxylamine

[0171] 1) Manufacturing Example 1 In a 3-liter flask equipped with a stirrer, thermometer, gas inlet tube, rectification column, and condenser, 660.00 parts (5.59 moles) of glycerin carbonate, 1891.10 parts (14.53 moles) of MCA, 1.22 parts (0.011 moles) of DABCO (triethylenediamine) as catalyst X, 4.52 parts (0.022 moles) of zinc acrylate as catalyst Y, 1.02 parts of MEHQ (474 ​​ppm relative to the total weight of the charged raw materials), and 0.74 parts of TEMPOL (288 ppm relative to the total weight of the charged raw materials) were charged, and an oxygenated gas (5% oxygen by volume, 95% nitrogen by volume) was bubbled into the liquid. While heating and stirring the reaction mixture at a temperature of 110-120°C, the pressure in the reaction system was adjusted to a range of 140-180 mmHg. The mixed solution of MEL and MCA produced as a by-product during the transesterification reaction was withdrawn from the reaction system via a rectification column and condenser. In addition, an equal weight of MCA was added to the reaction system as needed. Furthermore, MCA containing MEHQ and TEMPOL was added to the reaction system as needed via the rectification column. Heating was terminated 17 hours after the start of heating and stirring, and the pressure in the reaction system was returned to atmospheric pressure to terminate the extraction. A portion of the reaction solution was taken and its composition was analyzed using HPLC, confirming that it contained the target product, Glycarbo-A [(2-oxo-1,3-dioxolan-4-yl)methyl acrylate].

[0172] 54 parts of aluminum silicate [Kyoword 700 (product name), manufactured by Kyowa Chemical Industry Co., Ltd.; hereinafter the product name will be omitted] were added to the filtrate as an adsorbent, and the mixture was heated and stirred for 1 hour at atmospheric pressure in the range of 80-105°C to perform contact treatment. Then, 3.0 parts of calcium hydroxide were added at an internal temperature of 20-40°C and stirred for 1 hour at atmospheric pressure. After separating insoluble matter by pressure filtration, vacuum distillation was performed for 16 hours at a temperature of 70-90°C and a pressure of 0.001-100 mmHg while bubbling dry air through the filtrate, to separate the distillate containing unreacted MCA.

[0173] 0.87 parts DEHA (900 ppm relative to the second-step processed product) was added to the obtained kettle liquid, and the mixture was stirred at atmospheric pressure in the range of 70-90°C for 3 hours. Then, 4.50 parts diatomaceous earth [Radiolite (trade name), manufactured by Showa Chemical Industry Co., Ltd.; hereinafter, the trade name will be omitted] was added to the kettle liquid, and pressure filtration was performed. The obtained filtrate was used as the purified product. The weight of the filtrate was 945.75 parts, and compositional analysis using HPLC confirmed that it contained the target product, Glycarbo-A. Hereinafter, this will be referred to as compound a1. Table 1 shows the results of various analyses of the obtained compound a1 (purified product).

[0174] 2) Manufacturing Example 2 (1) Production of glycerin carbonate ethylene oxide adduct First, the ethylene oxide adduct of glycerin, which is the raw material for glycerin carbonate ethylene oxide adduct, was purified. In a 3-liter flask equipped with a stirrer, thermometer, and condenser, 1722 parts of ethylene oxide adduct of glycerin [Emulgen GE-1 (product name), manufactured by Kao Corporation, hydroxyl value 1190 mg KOH / g] were charged. Vacuum distillation was performed for 43 hours at a boiler temperature of 125-140°C and a system pressure of 70-7 Pa. First, 475 parts were withdrawn (hereinafter referred to as the "initial distillate"), and then 508 parts were withdrawn (hereinafter referred to as the "main distillate"). GC analysis of this distillate revealed that it contained 6% glycerin, 72% a compound in which one ethylene oxide molecule was attached only to the hydroxyl group at position 1 of the glycerin, and 10% a compound in which two ethylene oxide molecules were attached only to the hydroxyl group at position 1 of the glycerin.

[0175] In a 3-liter flask equipped with a stirrer, thermometer, and condenser, 504 parts of the main distillate obtained above, 411 parts of ethylene carbonate, and 0.9 parts of activated alumina as a catalyst were charged. The reaction mixture was heated and stirred at a reaction temperature of 130-150°C, while the pressure in the reaction system was adjusted to a range of 4700-30 Pa. As the transesterification reaction progressed, the by-product mixture of ethylene glycol and ethylene carbonate was withdrawn from the reaction system via the condenser. Heating was stopped 15 hours after the start of heating and stirring, and the pressure in the reaction system was returned to atmospheric pressure to end the withdrawal. Subsequently, the liquid in the flask was pressure filtered to remove the activated alumina added as a catalyst, and the filtrate was obtained. The filtrate weighed 560 parts, and GC analysis revealed that it contained 5% glycerol carbonate, 68% a compound in which one ethylene oxide molecule was added only to the hydroxyl group at position 1 of glycerol, and the hydroxyl groups at positions 2 and 3 were carbonated to form an intramolecular cyclic carbonate structure, and 4% a compound in which two ethylene oxide molecules were added only to the hydroxyl group at position 1 of glycerol, and the hydroxyl groups at positions 2 and 3 were carbonated to form an intramolecular cyclic carbonate structure.

[0176] (2) Production of acrylates of glycerin carbonate ethylene oxide adducts In a 3-liter flask equipped with a stirrer, thermometer, gas inlet tube, rectification column, and condenser, 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 of MEHQ (464 ppm relative to the total weight of the charged raw materials), and 0.56 parts of TEMPOL (279 ppm relative to the total weight of the charged raw materials) were charged, and an oxygenated gas (5% oxygen by volume, 95% nitrogen by volume) was bubbled into the liquid. While heating and stirring the reaction mixture at a temperature of 110-120°C, the pressure in the reaction system was adjusted to a range of 120-160 mmHg. The mixed solution of MEL and MCA produced as a by-product during the transesterification reaction was withdrawn from the reaction system via a rectification column and condenser. In addition, an equal weight of MCA to the extracted liquid was added to the reaction system as needed. Furthermore, MCA containing MEHQ and TEMPOL was added to the reaction system as needed via the rectification column. Heating was terminated 40 hours after the start of heating and stirring, and the pressure in the reaction system was returned to atmospheric pressure to terminate the extraction. After the reaction was complete, 18 parts aluminum silicate was added as an adsorbent to the reaction vessel liquid, and the mixture was heated and stirred for 1 hour at atmospheric pressure in the range of 80-105°C to perform contact treatment. Then, 0.9 parts calcium hydroxide was added at an internal temperature of 20-40°C and stirred for 1 hour at atmospheric pressure. After separating insoluble matter by pressure filtration, vacuum distillation was performed for 16 hours at a temperature of 70-90°C and a pressure of 0.001-100 mmHg while bubbling dry air through the filtrate, to separate the distillate containing unreacted MCA.

[0177] 0.75 parts DEHA were added to the obtained kettle liquid, and the mixture was stirred for 3 hours under atmospheric pressure at an internal temperature of 70-90°C. Subsequently, 4.5 parts diatomaceous earth were added to the kettle liquid, and pressure filtration was performed. The resulting filtrate was used as the purified product. This product is hereafter referred to as compound a2. The weight of compound a2 (filtrate) was 630 parts. GC analysis revealed that it contained 7% glycerin carbonate acrylate, 59% acrylate of a 1-mol ethylene oxide adduct of glycerin carbonate, and 4% acrylate of a 2-mol ethylene oxide adduct of glycerin carbonate. Table 1 shows the results of various analyses of the obtained compound a2.

[0178] 3) Manufacturing Example 3 200 parts of the purified product obtained in Production Example 2 and 1525 parts of n-hexane were placed in a 3-liter separatory funnel, and the separatory funnel was vigorously shaken to perform the extraction. After standing, the liquid separated into two layers. Components with a carbonate structure, such as glycerin carbonate acrylate, were mainly distributed to the lower layer, while the upper layer, mainly composed of n-hexane, contained many acrylate compounds that do not have a carbonate structure, such as glycerin triacrylate and compounds in which one ethylene oxide molecule was added only to the hydroxyl group at the 2nd position of glycerin before triacrylate formation. The upper layer was taken out from the separating funnel and concentrated under reduced pressure using an evaporator to recover most of the normal hexane as the distillate. The recovered normal hexane and fresh normal hexane were added to the remaining separating funnel in the lower layer, and the extraction operation was performed again. After repeating this extraction operation and the normal hexane recovery operation a total of 8 times, the lower layer of the separating funnel was taken out, 0.105 parts of MEHQ and 0.001 parts of TEMPOL were added, and while bubbling dry air, vacuum distillation was carried out at a temperature of 60 °C and a pressure range of 3 - 100 mmHg for 5 hours to distill off the small amount of normal hexane contained in the lower layer, and the resulting kettle liquid was used as the purified product. Hereinafter, it is referred to as compound a3. The weight of compound a3 (kettle liquid) was 155 parts. As a result of GC analysis, it contained 9% glycerin carbonate acrylate, 77% acrylate of ethylene oxide 1 - mol adduct of glycerin carbonate, and 5% acrylate of ethylene oxide 2 - mol adduct of glycerin carbonate. The various analysis results of the obtained compound a3 are shown in Table 1.

[0179] 4) Comparative manufacturing example 1 [Manufacturing by transesterification reaction using a titanium catalyst] 2.502 parts (0.212 mol) of glycerin carbonate, 4.958 parts (0.0381 mol) of MCA, 0.003 parts of MEHQ, and 0.001 part of phenothiazine were charged into a 20 - milliliter test tube equipped with a rotor, thermometer, gas introduction tube, and condenser tube. While bubbling oxygen - containing gas (5 vol% oxygen and 95 vol% nitrogen) into the liquid, heating was carried out at a reaction liquid temperature in the range of 105 - 120 °C for 0.5 hours. Thereafter, 0.245 parts (0.0007 mol) of titanium tetranormal butoxide was added as a catalyst, and heating was carried out at a reaction liquid temperature in the range of 105 - 120 °C for 6 hours. A part of the reaction liquid was sampled and composition analysis was performed using HPLC, but the formation of the target product Glycarbo - A was not confirmed.

[0180] 5) Comparative manufacturing example 2 [Manufacturing by dehydration esterification reaction] In a flask equipped with a stirrer, thermometer, gas inlet tube, condenser, and water divider, 213.46 parts (1.81 mol) of glycerin 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 charged. The reaction was heated and stirred for 7 hours at a reaction pressure of 370 Torr and a reaction temperature in the range of 86-90°C while bubbling oxygen-containing gas (5% oxygen by volume, 95% nitrogen by volume) into the liquid, and the water produced by the dehydration reaction was removed through the water divider. A portion of the reaction solution was taken and its composition was analyzed using HPLC, confirming that it contained the target product, Glycarbo-A. After cooling the reaction mixture to room temperature, 274.34 parts of toluene and 87.50 parts of water were added and the mixture was stirred. After stopping the stirring and allowing it to stand, it separated into three layers. The upper layer contained almost no target substance and was mainly composed of toluene. The middle layer was an aqueous layer. The lower layer contained the target substance. After draining the upper and middle layers, 250.00 parts of tetrahydrofuran and 55.48 parts of a 20% sodium hydroxide aqueous solution were added to the lower layer and stirred. After stopping the stirring and allowing it to stand, it separated into two layers. The lower layer was an aqueous layer, and the upper layer contained the target substance. After draining the lower layer, 87.50 parts of water were added to the upper layer and stirred. When the stirring was stopped and the mixture was allowed to stand, it separated into two layers. The lower layer was an aqueous layer, and the upper layer contained the target substance. After draining the lower layer, the upper layer was transferred to a flask, 0.14 parts of MEHQ were added, and vacuum distillation was performed for 6 hours at a temperature of 40-80°C and a pressure of 0.01-600 mmHg while bubbling dry air, to remove low-boiling-point components such as tetrahydrofuran, toluene, and water. 1.40 parts of diatomaceous earth (Radiolite, product name, manufactured by Showa Chemical Industry Co., Ltd.) were added to the kettle liquid and subjected to pressure filtration. The resulting filtrate was used as the purified product. The weight of the filtrate was 147.19 parts, and compositional analysis using HPLC confirmed that it contained the target compound, Glycarbo-A. Hereinafter referred to as compound a'2. Table 1 shows the results of various analyses of the obtained compound a'2 (purified product).

[0181] 6) Comparative manufacturing example 3 [Manufacturing by acid chloride method] The method described in the non-patent literature [Gerhard Wegner et al., Macromolecules, 2007, Vol. 40, pp. 7558-7565] was used as a reference. A 2-liter flask equipped with a stirrer, thermometer, dropping funnel, and gas inlet tube was charged with 130.00 parts (1.10 moles) of glycerin carbonate, 111.40 parts (1.10 moles) of triethylamine, and 700 mL of tetrahydrofuran. The flask was then cooled to an internal temperature of 0-5°C while nitrogen was flowed through the gas phase. 99.64 parts (1.10 moles) of acryloyl chloride and 260 mL of tetrahydrofuran were placed in a dropping funnel, and the mixture was slowly added dropwise over approximately 3 hours while stirring, ensuring that the internal temperature remained within the range of 0-5°C. After the dropwise addition was complete, the mixture was stirred for 1 hour, the supernatant was transferred to a separatory funnel, 50 mL of tetrahydrofuran washed with the precipitate remaining in the flask was added to the separatory funnel, and the organic solvent layer was washed 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 vacuum distillation was performed for 10 hours at a temperature of 50-70°C and a pressure of 20-100 mmHg while bubbling dry air, to separate the distillate containing tetrahydrofuran. The solids were separated by pressure filtration, and the resulting filtrate was used as the purified product. The weight of the filtrate was 59.72 parts, and compositional analysis using HPLC confirmed that it contained the target compound, Glycarbo-A. Hereinafter, this compound will be referred to as compound a'3. Table 1 shows the results of various analyses of the obtained compound a'3 (purified product).

[0182] [Table 1]

[0183] 2. Examples 1) Production of activated energy ray curable compositions 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 produce activated energy ray-curable compositions. In addition, the numbers in Tables 2 to 4 represent the number of copies, and the abbreviations have the following meanings. • M1200: Urethane acrylate [Manufactured by Toagosei Co., Ltd., product name: Aronics M-1200] • M402: Dipentaerythritol penta / hexaacrylate mixture [Manufactured by Toagosei Co., Ltd., product name: Aronics M-402] • Om907: 2-Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [Manufactured by IGM Resins, trade name: Omnirad907] • DETX: 2,4-Diethylthioxanthone [Manufactured by Nippon Kayaku Co., Ltd., Product name: Kayacure DETX-S] • TPO: Phosphorus-based photopolymerization initiator (2,4,6-trimethylbenzoyl-diphenylphosphine oxide) [Manufactured by IGM Resins, trade name: Omnirad TPO]

[0184] 2) Evaluation Method The obtained compositions were used for the following evaluations. The results are shown in Tables 2 to 4.

[0185] (1) Viscosity The viscosity of the obtained composition was measured using an E-type viscometer (cone plate viscometer) at 25°C.

[0186] (2) Moist heat test A 100 μm thick easy-adhesion polyethylene terephthalate (PET) film [Cosmoshine A4300, manufactured by Toyobo Co., Ltd.] was coated with the compositions obtained in Table 2 to a thickness of 10 μm using a bar coater, and then the compositions were cured by ultraviolet irradiation. The ultraviolet irradiation device uses a metal halide lamp manufactured by I-Graphics Co., Ltd., and irradiates in the ultraviolet region (UV-A) centered at 365 nm with an irradiation intensity of 200 mW / cm². 2 , integrated light intensity 2,000 mJ / cm 2 The ultraviolet irradiation was performed under these conditions. After UV irradiation, the obtained samples were held at 85°C and 85% RH for 100 hours for a moist heat test. The changes in the appearance of the cured film after the moist heat test were observed visually and evaluated on the following three levels. ○: No change, △: Some defects such as foaming or peeling occurred, ×: Peeling occurred across the entire hardened film.

[0187] (3) Insulation reliability A comb-shaped pattern with a line / space = 100 / 100 was formed on a polyimide / copper laminated film substrate (hereinafter referred to as the "comb-shaped substrate") using photolithography. The compositions obtained in Table 2 were then coated to a thickness of 10 μm using a bar coater, and the compositions were cured by ultraviolet irradiation under the same conditions as the moist heat test. Using the evaluation samples obtained by the above method, the insulation reliability test was evaluated by measuring the time it took for the resistance to drop below 100 MΩ while continuously applying a voltage of 20 V under conditions of 85°C and 85% RH.

[0188] (4) Adhesive strength (initial) A 100 μm thick easy-adhesion polyethylene terephthalate (hereinafter referred to as "easy-adhesion PET") film [Cosmoshine A4300, manufactured by Toyobo Co., Ltd.] was coated with the compositions obtained in Table 3 to a thickness of 10 μm using a bar coater. The other easy-adhesion PET film was then laminated over it, and the composition was cured by ultraviolet irradiation under the same conditions as the moist heat test. The above laminate was subjected to a T-shaped peel test in accordance with JIS K-6854 under conditions of a peel width of 25 mm and 25°C, and its peel strength was determined.

[0189] (5) Adhesion strength (after wet heat test) The laminate obtained in (4) was held in an atmosphere of 85°C and 85%RH for 100 hours, and a T-shaped peel test was performed in accordance with JIS K-6854 under conditions of a peel width of 25 mm and 25°C, and the peel strength after the moist heat test was determined.

[0190] (6) Shape reproducibility A transfer mold (hereinafter referred to as the "nickel mold"), on which microfabrication (a semicircular pattern with a diameter of 3 μm and a film thickness of 5 μm) was formed on a nickel-plated stainless steel plate, was coated with the compositions obtained in Table 4 to a thickness of 10 μm using a bar coater. After lamination with easily adhering PET, the compositions were cured by ultraviolet irradiation under the same conditions as the moist heat test. Subsequently, the hardened film was peeled from the nickel mold, its pattern shape was observed under a microscope, its dimensions were measured and compared with those of the nickel mold, and its shape reproducibility was evaluated at the following two levels. ○: Dimensional change of nickel mold and cured resin pattern shape is less than 5%; ×: Dimensional change is 5% or more, or chipping is observed in the pattern.

[0191] (7) Mold Corrosion A transfer mold (hereinafter referred to as the "nickel mold") had microfabrication (a 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 then applied to a thickness of 10 μm using a bar coater, laminated with easily adhering PET, and cured by ultraviolet irradiation under the same conditions as the moist heat test. Subsequently, the molds were kept in an atmosphere of 40°C and 80% RH for 24 hours, and a metal corrosion test was conducted. The changes in the appearance of the nickel molds after the metal corrosion test were visually observed and evaluated on the following three levels. ○: No change, △: Part of the nickel mold discolored, ×: The entire nickel mold discolored

[0192] [Table 2]

[0193] [Table 3]

[0194] [Table 4]

[0195] Based on the analysis in Table 2, the compositions of Examples 1 to 3, which contained component (A) (compounds a1 to a3) obtained in Production Examples 1 to 3, had low viscosity, good moist heat test and insulation reliability, and exhibited excellent performance as active energy ray curable coating agent compositions. In contrast, the compositions of Comparative Examples 1 and 2, which contained component (A)' (compounds a'2 and a'3) obtained in Comparative Production Examples 2 and 3, respectively, showed significant changes in appearance in the moist heat test and low insulation reliability. Furthermore, based on the analysis in Table 3, the compositions of Examples 4 to 6, which contain component (A) (compounds a1 to a3) obtained in Production Examples 1 to 3, exhibited excellent adhesive strength and performance in the moist heat test, demonstrating superior performance as active energy ray curable adhesive compositions. In contrast, the compositions of Comparative Examples 3 and 4, which contain component (A)' (compounds a'2 and a'3) obtained in Comparative Production Examples 2 and 3, respectively, showed a significant decrease in adhesive strength in the moist heat test. Furthermore, based on the analysis in Table 4, the compositions of Examples 7 to 9, which contain component (A) (compounds a1 to a3) obtained in Production Examples 1 to 3, were suitable as active energy ray curable excipient compositions because they exhibited excellent shape reproducibility and good mold corrosion resistance when used as such compositions. In contrast, the compositions of Comparative Examples 5 and 6, which contain component (A)' (compounds a'2 and a'3) obtained in Comparative Production Examples 2 and 3, respectively, were unsuitable for this application. Comparative Example 5 had high viscosity, resulting in problems with shape reproducibility, and Comparative Examples 5 and 6 had problems with mold corrosion resistance. [Industrial applicability]

[0196] The curable composition of the present invention can be preferably used as an active energy ray curable composition, and can be preferably used as a solvent-free active energy ray curable composition. The curable composition of the present invention can be used in a variety of applications, including coating agents such as paints, adhesives, sealants, inks, molding agents for forming excipients, and pattern-forming agents such as resists. It can be preferably used as a coating agent, adhesive, and excipient.

Claims

1. A curable 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. 【Chemistry 1】 [In formula (a), Ra represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Rb represents an oxyalkylene group.]

2. A method for producing a curable composition, comprising the step of producing a mixture of compounds obtained by transesterifying an alkylene oxide adduct of glycerin carbonate 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 chlorine concentration in the mixture is less than 100 ppm and the sodium concentration is less than 100 ppb (component A). Catalyst X: One or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or its salt or complex, amidine or its salt or complex, a compound having a pyridine ring or its salt or complex, and phosphine or its salt or complex. Catalyst Y: A compound containing zinc.

3. A method for producing a curable composition according to claim 2, wherein the compound having one CH2=C(R)-(C=O)- group in the molecule is an alkoxyalkyl (meth)acrylate.

4. A method for producing a curable composition according to claim 2 or 3, wherein the catalyst X is one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, amidine or a salt or complex thereof, and a compound having a pyridine ring or a salt or complex thereof.

5. A method for producing a curable composition according to any one of claims 2 to 4, wherein the catalyst Y is at least one of an organic acid zinc and a zinc diketone enolate.

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