Curable composition and method of manufacturing the same, coating composition, excipient material composition and adhesive composition

Abstract

[Problem] To provide a curable composition comprising (2-oxo-1,3-dioxolein-4-yl)methyl (meth)acrylate [glycerin carbonate (meth)acrylate], wherein the cured product is free from metal corrosion problems and has excellent water resistance. To further provide a curable coating agent composition, a curable excipient material composition, a curable adhesive sintered product, and a method for manufacturing a curable composition. [Solution] A composition comprising component (A), wherein component (A) comprises a compound represented by the following formula (a), and the chlorine concentration contained in component (A) is less than 100 ppm and the sodium concentration is less than 100 ppb. [In formula (a), Ra represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Rb represents a single bond or an oxyalkylene group.]

Description

Technology Field

[0001] The present invention relates to a curable composition, preferably an active energy beam curable composition, and particularly preferably to a solvent-free active energy beam curable composition, and belongs to the art.

[0002] In addition, in this specification, "acryloyl group and / or methacryloyl group" is denoted as "(meth)acryloyl group," "acrylate and / or methacrylate" as "(meth)acrylate," and "acrylic acid and / or methacrylic acid" as "(meth)acrylic acid."

[0003] In addition, a compound having an ethylenically unsaturated group is indicated as a "curable component" in the composition. Background Technology

[0004] Curable compositions are used for various purposes, such as coatings, adhesives, inks, and electronic materials.

[0005] Among these, active energy beam curing compositions have the advantage of being able to cure in a very short time, and (meth)acrylates with excellent curability are widely used; in the case of UV curing, irradiation devices equipped with UV lamps such as high-pressure mercury lamps, metal halide lamps, and LEDs are used as light sources, while in the case of electron beam curing, electron beam irradiation devices are used.

[0006] Meanwhile, a disadvantage of an active energy beam curing type composition containing (meth)acrylate is that when cured in air, curing is inhibited by the influence of oxygen in the air (hereinafter referred to as "oxygen inhibition").

[0007] Conventionally, to prevent curing inhibition caused by oxygen inhibition, methods are known to involve irradiating ultraviolet rays under a nitrogen atmosphere or coating a substrate with a composition and then laminating a film onto the coated surface to irradiate ultraviolet rays under oxygen blockage; however, the scope of application is limited due to issues such as the large size of the equipment, high costs, and reduced productivity.

[0008] In addition, it is known that oxygen inhibition is reduced by incorporating additives such as amine compounds and phosphorus compounds into the composition, but these relatively effective additives have the problem of the cured product becoming discolored.

[0009] To solve the above problem, (meth)acrylates that are not easily inhibited by oxygen have been under consideration for some time.

[0010] Among them, C. Decker et al. made it clear that (2-oxo-1,3-dioxolein-4-yl)methyl acrylate [glycerin carbonate acrylate. Hereinafter referred to as "Glycarbo-A"], an acrylate having a cyclic carbonate backbone, has high curability even in air (Non-Patent Document 1).

[0011] However, the manufacturing method used in the literature is a high-risk method that involves reacting glycerol with highly toxic phosgene and then reacting the resulting chloride with acrylic acid to obtain the target product, and it has significant problems in terms of high environmental burden and worker safety.

[0012] In addition, G. Wegner et al. obtain (2-oxo-1,3-dioxolein-4-yl)methyl(meth)acrylate [glycerin carbonate(meth)acrylate. Hereinafter referred to as "Glycarbo-(M)A"] by the reaction between glycerol carbonate and (meth)acrylic acid chloride (Non-Patent Document 2).

[0013] However, the manufacturing method described in the literature is based on the acid chloride method, which is problematic when considering the issue of container corrosion and the magnitude of the environmental burden.

[0014] In addition, according to the inventors' review, the compound prepared by the method described in the literature has high sodium and chlorine concentrations, so when used as a component of a curable composition, the cured product had problems such as metal corrosion or low water resistance.

[0015] In addition, Patent Document 1 discloses an abrasion-resistant coating composition comprising a polyacrylate with three or more functions and Glycarbo-(M)A, and the composition is disclosed to have high hardness, fast curing speed, excellent adhesion, and low discoloration of the cured product (Patent Document 1).

[0016] However, the method for manufacturing Glycarbo-(M)A in Patent Document 1 was also by the acid chloride method, and the composition had the problem as described above. Prior art literature

[0017] Patent Document 1: Japanese Patent Publication No. 2001-19875

[0018] Non-patent document 1: Radiation Curing in Polymersience and Technology, 1993, Vol. 3, pages 33-64 Patent document 2: Macromolecules, 2007, Vol. 40, pages 7558-7565 The problem to be solved

[0019] The inventors have conducted extensive research to identify a curable composition comprising Glycarbo-(M)A, wherein the cured product is free from metal corrosion issues and exhibits excellent water resistance. means of solving the problem

[0020] In order to solve the above problem, the inventors discovered that a curable composition comprising Glycarbo-(M)A as component (A) and reducing the chlorine concentration and sodium concentration included in component (A) has excellent metal corrosion resistance and water resistance, and completed the present invention.

[0021] The present invention will be described in detail below. Effects of the invention

[0022] According to the composition of the present invention, the cured product can be made to have excellent metal corrosion resistance and water resistance. Specific details for implementing the invention

[0023] The present invention is a curable composition comprising (A) a component, wherein (A) a compound represented by the later formula (a) has a chlorine concentration of less than 100 ppm and a sodium concentration of less than 100 ppb.

[0024] Hereinafter, (A) the component, the curable composition, the use, and the method of use will be described.

[0025] 1. (A) Ingredient

[0026] The essential component (A) of the present invention comprises a compound represented by the following formula (a).

[0027]

[0028] [In Equation (a), R a represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R b represents a single bond or an oxyalkylene group.

[0029] R in Equation (a) a represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R a A hydrogen atom or a methyl group is preferred.

[0030] R bExamples of oxyalkylene groups in this include ethylene oxide groups, propylene oxide groups, tetramethylene oxide groups, and mixed units of these alkylene oxide groups, and ethylene oxide groups are preferred.

[0031] R b The oxyalkylene group in the above may be an alkylene oxide group having repeating units, preferably 1 to 20, and more preferably 1 to 15.

[0032] (A) A composition containing the component is not easily affected by 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.

[0033] As for the compound of formula (a), R a ga is a hydrogen atom or a methyl group, and R b A compound having a single bond is preferred. That is, Glycarbo-(M)A [(2-oxo-1,3-dioxolein-4-yl)methyl(meth)acrylate] is preferred.

[0034] Furthermore, a compound having a hydrogen atom as R in formula (a), namely Glycarbo-A [(2-oxo-1,3-dioxolein-4-yl)methylacrylate], is more preferable in that it has excellent curability.

[0035] In addition, R is a compound of formula (a). a ga is a hydrogen atom or a methyl group, and R b A compound having an oxyalkylene group is preferred, wherein the repeating unit of the oxyalkylene group is 1 to 15.

[0036] (A) The component may be a mixture of these compounds.

[0037] Furthermore, component (A) has a chlorine concentration of less than 100 ppm and a sodium concentration of less than 100 ppb.

[0038] The cured product of the composition obtained by keeping the chlorine concentration less than 100 ppm and the sodium concentration less than 100 ppb can be made to have excellent water resistance and metal corrosion resistance.

[0039] In addition, the chlorine concentration in the present invention refers to a value obtained by quartz tube combustion-ion chromatography.

[0040] In addition, the sodium concentration in the present invention refers to a value obtained by measuring a sample with an ICP mass spectrometer and quantifying the detected element using the absolute calibration curve method.

[0041] (A) As a method for manufacturing component (A), it is preferable to obtain it by ester (ester) exchange reaction between glycerin carbonate, an alkylene oxide adduct of glycerin carbonate, or a mixture of these compounds [hereinafter collectively referred to as "glycerin carbonate-based compounds"] and a compound having one CH2=C(R)-(C=O)- group [hereinafter referred to as "single-function (meth)acrylate"], in order to easily manufacture component (A) having the chlorine concentration and sodium concentration described above. In addition, R of the CH2=C(R)-(C=O)- group means a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, as in the above.

[0042] In the manufacturing method of dehydrating and esterifying a glycerin carbonate-based compound with (meth)acrylic acid, a large amount of high molecular weight byproducts is generated, and the resulting component (A) becomes highly viscous.

[0043] In addition, the acid chloride method, which reacts a glycerin carbonate-based compound with (meth)acrylic acid chloride, has the problem that it is difficult to reduce the chlorine and sodium concentrations contained in component (A), and the water resistance or metal corrosion resistance of the cured product is reduced.

[0044] In this regard, according to the ester exchange reaction between a glycerin carbonate-based compound and a monofunctional acrylate, it is possible to produce component (A) with good yield and, furthermore, reduce the chlorine concentration and sodium concentration.

[0045] Hereinafter, regarding the method of manufacturing by ester exchange reaction, which is a preferred method of manufacturing component (A), a glycerin carbonate-based compound, a monofunctional (meth)acrylate, a catalyst, and a method of manufacturing component (A) will be described.

[0046] 1-1. Glycerin carbonate compounds

[0047] (A) The glycerin carbonate-based compounds used as raw materials for the component are glycerin carbonate, alkylene oxide adducts of glycerin carbonate, or mixtures of these compounds.

[0048] Commercially available glycerin carbonate (4-hydroxymethyl-1,3-dioxolein-2-one) may be used. Additionally, a carbonate ester compound such as ethylene carbonate, dimethyl carbonate, and diethyl carbonate may be used by performing an ester exchange reaction with glycerin in the presence of a catalyst.

[0049] As an alkylene oxide adduct of glycerin carbonate, a carbonate ester compound such as ethylene oxide adduct of glycerin, ethylene carbonate, dimethyl carbonate, and diethyl carbonate can be synthesized by performing an ester exchange reaction in the presence of a catalyst.

[0050] A mixture of the above-mentioned compounds may also be used as a glycerin carbonate-based compound.

[0051] 1-2. Monofunctional (Meta)Acrylates

[0052] (A) The single-function (meth)acrylate used as a raw material for the component is a compound having one CH2=C(R)-(C=O)- group in the molecule, and for example, a compound represented by the following general formula (1).

[0053]

[0054] In Equation (1), R 1 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and R 2 It represents an organic group with 1 to 50 carbon atoms.

[0055] R in the above general formula (1) 1 A hydrogen atom or a methyl group is preferred.

[0056] R in the above general formula (1) 2 Preferred specific examples include alkyl groups having 1 to 8 carbon atoms, 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.

[0057] R in the above general formula (1) 2 Specific examples of the above include, in addition to the above, functional groups listed in Japanese Patent Publication No. 2017-39916, Japanese Patent Publication No. 2017-39917, and International Publication No. 2017 / 033732.

[0058] In the present invention, these monofunctional (meth)acrylates may be used alone or in an optional combination of two or more types.

[0059] Among these monofunctional (meth)acrylates, alkyl (meth)acrylates having an alkyl group having 1 to 8 carbon atoms, 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, and in particular, acrylates having an alkyl group having 1 to 4 carbon atoms and alkoxyalkyl (meth)acrylates having an alkyl group having 1 to 2 carbon atoms are preferred, which exhibit good reactivity with glycerin carbonate-based compounds and are easily available.

[0060] Furthermore, an alkoxyalkyl (meth)acrylate having a carbon 1-2 alkyl group that promotes the dissolution of glycerin carbonate-based compounds and exhibits very good reactivity is more preferable, and 2-methoxyethyl (meth)acrylate is particularly preferred.

[0061] 1-3. Catalyst

[0062] (A) In the method for manufacturing the component, conventionally known catalysts such as tin-based catalysts, titanium (titanium)-based catalysts, and sulfuric acid may be used as the ester exchange reaction catalyst.

[0063] In the present invention, it is preferable to use catalysts X and Y together as catalysts in order to efficiently produce component (A) in high yield.

[0064] 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-based compounds"), amidine or its salts or complexes (hereinafter referred to as "amidine-based compounds"), compounds having a pyridine ring or their salts or complexes (hereinafter referred to as "pyridine-based compounds"), and phosphine or its salts or complexes (hereinafter referred to as "phosphine-based compounds").

[0065] Catalyst Y: A compound containing zinc.

[0066] Below, catalysts X and Y will be described.

[0067] 1-3-1. Catalyst X

[0068] Catalyst X is one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, pyridine compounds and phosphine compounds.

[0069] As catalyst X, it is preferable to use one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, and pyridine compounds among the above-mentioned compound groups. In addition to having excellent catalytic activity and being able to preferably produce component (A), these compounds form a complex with catalyst Y, which is described later, after the reaction is finished, so they can be easily removed from the reaction solution after the reaction is finished by simple methods such as filtration and adsorption. In particular, azabicyclo compounds can be removed more easily by filtration and adsorption because the complex with catalyst Y is sparingly soluble in the reaction solution.

[0070] Meanwhile, although phosphine-based compounds have excellent catalytic activity, they are difficult to form complexes with catalyst Y and remain mostly dissolved in the reaction solution after the reaction is finished, making it difficult to remove them from the reaction solution by simple methods such as filtration and adsorption. Consequently, phosphine-based catalysts remain in the final product, which can cause storage stability issues such as turbidity or catalyst precipitation during product storage, or thickening or gelation over time. The same problems can also occur when used as a component of a composition.

[0071] Specific examples of azabicyclo-based compounds include various compounds that satisfy the criteria of a cyclic tertiary amine having an azabicyclo structure, a salt of the amine, or a complex of the amine, and preferred compounds include quinuclidin, 3-hydroxyquinuclidin (3-hydroxyquinuclidin), 3-quinuclidinone (quinuclidinone), 1-azabicyclo[2.2.2]octane-3-carboxylic acid (1-azabicyclo[2.2.2]octane-3-carboxylic acid), and triethylenediamine (triethylenediamine) (alias: 1,4-diazabicyclo[2.2.2]octane. Hereinafter referred to as "DABCO").

[0072] Specific examples of azabicyclo-based compounds include, in addition to the above, compounds 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.

[0073] Specific examples of amidine compounds include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole (1-vinylimidazole), 1-allylimidazole, 1,8-diazabicyclo[5.4.0]undeca-7-en (hereinafter referred to as "DBU"), 1,5-diazabicyclo[4.3.0]nona-5-en (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.

[0074] Major specific 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").

[0075] Specific examples of pyridine-based compounds include, in addition to the above, compounds 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.

[0076] Phosphine or its salt or complex may include compounds having a structure represented by the following general formula (2).

[0077]

[0078] [In Equation (2), R 3 , R 4 and R 5 represents a straight-chain or branched alkyl group having 1 to 20 carbon atoms, a straight-chain 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 5 As such, they may be the same or different from each other.

[0079] 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.

[0080] Specific examples of phosphine-based compounds include, in addition to the above, compounds 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.

[0081] In the present invention, these catalysts X may be used alone or optionally in combination of two or more. Among these catalysts X, quinuclidin, 3-quinuclidinone, 3-hydroxyquinuclidin, DABCO, N-methylimidazole, DBU, DBN, and DMAP are preferred, and in particular, 3-hydroxyquinuclidin, DABCO, N-methylimidazole, DBU, and DMAP are more preferred as they exhibit good reactivity with most glycerin carbonate-based compounds and are readily available.

[0082] (A) There is no particular limit on the ratio of catalyst X used in the method of manufacturing 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-based compound, and more preferably 0.0005 to 0.2 moles. By using 0.0001 moles or more of catalyst X, the amount of component A produced can be increased, and by using 0.5 moles or less, the formation of by-products or discoloration of the reaction solution can be suppressed, and the purification process after the reaction is completed can be simplified.

[0083] 1-3-2. Catalyst Y

[0084] Catalyst Y is a compound containing zinc.

[0085] As catalyst Y, various compounds containing zinc can be used, but zinc organic acid and zinc diketone oleate are preferred due to their excellent reactivity.

[0086] Examples of zinc organic acids include zinc dibasic acids such as zinc oxalate and compounds represented by the following general formula (3).

[0087]

[0088] [In Equation (3), R 6 and R 7represents a straight-chain or branched alkyl group having 1 to 20 carbon atoms, a straight-chain 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 As such, they may be the same or different from each other.

[0089] The compound of the above formula (3) is R 6 and R 7 A compound having a straight-chain or branched alkyl group having 1 to 20 carbon atoms is preferred. R 6 and R 7 In this case, a straight-chain or branched alkyl group having 1 to 20 carbon atoms is a functional group that does not have a halogen (halogen) atom such as fluorine and chlorine, and a catalyst Y having such a functional group is preferred because it can produce component (A) in high yield.

[0090] Examples of zinc diketone enolates include compounds represented by the following general formula (4).

[0091]

[0092] [In Equation (4), R 8 , R 9 , R 10 , R 11 , R 12 and R 13 represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 20 carbon atoms, a straight-chain 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 As such, they may be the same or different from each other.

[0093] Specific examples of compounds containing zinc represented by the above general formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octylate, zinc neodecanoate, zinc laurate, zinc myristate, zinc stearate, zinc cyclohexanebutyrate, 2-ethylhexanate, zinc benzoate, zinc t-butylbenzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and zinc methacrylate.

[0094] In addition, for these zinc-containing compounds, if there is a hydrate, a solvate, or a complex with catalyst X, said hydrate, solvate, and complex with catalyst X can also be used as catalyst Y in the method for preparing component (A).

[0095] 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. Additionally, for these zinc-containing compounds, if there is a hydrate, a solvate, or a complex with catalyst X, the hydrate, the solvate, and the complex with catalyst X can also be used as catalyst Y in the method for preparing component (A).

[0096] As for the zinc organic acid and zinc diketone enolate in catalyst Y, the above-mentioned compounds may be used directly, but these compounds may 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") may 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 may be used, and in the case of zinc diketone enolate, a method of reacting the raw material zinc compound with a 1,3-diketone may be used.

[0097] In the present invention, these catalysts Y can be used alone or optionally in combination of two or more. Among these catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, and zinc acetylacetonate are preferred, and in particular, zinc acetate, zinc acrylate, and zinc acetylacetonate are preferred as they exhibit good reactivity toward glycerin carbonate-based compounds and are readily available.

[0098] (A) There is no particular limit on the ratio of catalyst Y used in the method of manufacturing 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-based compound, and more preferably 0.0005 to 0.2 moles. By using 0.0001 moles or more of catalyst Y, the amount of (A) produced can be increased, and by using 0.5 moles or less, the formation of by-products or discoloration of the reaction solution can be suppressed, and the purification process after the reaction is completed can be simplified.

[0099] 1-4. (A) Method of manufacturing the ingredient

[0100] (A) It is preferable to prepare the component by transesterifying a glycerin carbonate-based compound and a monofunctional (meth)acrylate in the presence of an transesterification catalyst.

[0101] As mentioned above, for the method of manufacturing component (A), a method of using catalysts X and Y together as catalysts is preferred, and the manufacturing method will be described below.

[0102] (A) There are no specific limitations on the ratio of catalyst X and catalyst Y used in the method of manufacturing the component, but it is preferable to use 0.005 to 10.0 moles of catalyst X per 1 mole of catalyst Y, and more preferably 0.05 to 2.0 moles. By using 0.005 moles or more, the amount of the compound of formula (a) of the target can be increased, and by using 10.0 moles or less, the formation of by-products or discoloration of the reaction solution can be suppressed, and the purification process after the reaction is completed can be simplified.

[0103] In the combination of catalyst X and catalyst Y used in combination in the present invention, a combination in which catalyst X is an azabicyclo-based compound and catalyst Y is a compound represented by the general formula (3) is preferred, and furthermore, a combination in which the azabicyclo-based compound is DABCO and the compound represented by the general formula (3) is zinc acetate and / or zinc acrylate is most preferred.

[0104] In addition to this combination allowing for a good yield of component (A), the color tone after the reaction is excellent, making it suitable for various industrial applications where color tone is important. Furthermore, since it is a catalyst that is relatively inexpensive to obtain, it is an economically advantageous manufacturing method.

[0105] The catalysts X and Y used in the present invention may be added from the beginning of the reaction or during the reaction. Additionally, the desired amount may be added all at once or added in divided portions.

[0106] (A) The reaction temperature in the method of manufacturing the component is 40 to 180°C It is preferable that the temperature be 60 to 160°C, and more preferably 60 to 160°C. By making the reaction temperature 40°C or higher, the reaction rate can be accelerated, and by making it 180°C or lower, thermal polymerization of (meth)acryloyl groups in the raw materials or products can be suppressed, discoloration of the reaction solution can be suppressed, and the purification process after the reaction is completed can be simplified.

[0107] (A) In the method for manufacturing the component, the reaction pressure is not particularly limited as long as the predetermined reaction temperature can be maintained, and it may be carried out under reduced pressure or under increased pressure. The reaction pressure is preferably 0.000001 to 10 MPa (absolute pressure).

[0108] (A) In the method for manufacturing the component, a monohydric alcohol derived from monofunctional (meth)acrylate is produced as a byproduct during the ester exchange reaction. The monohydric alcohol may be kept within the reaction system, but the progress of the ester exchange reaction can be further accelerated by discharging the monohydric alcohol from the reaction system.

[0109] (A) In the method for preparing the component, the reaction may be carried out without using an organic solvent, but an organic solvent may be used if necessary.

[0110] Specific examples of organic solvents include hydrocarbons such as n-hexane (n-hexane), cyclohexane, methylcyclohexane, n-heptane (n-heptane), n-octane (n-octane), n-nonane (n-nonane), n-decane (n-decane), benzene, toluene, xylene (xylene), ethylbenzene, diethylbenzene, isopropylbenzene (isopropylbenzene), amylbenzene, diamylbenzene, triamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, isopropyltoluene, decalin, and tetralin; Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diethyl acetal, dihexyl acetal, t-butylmethyl ether, cyclopentylmethyl ether, tetrahydrofuran (tetrahydrofuran), tetrahydropyran, trioxane, dioxane, anisole, diphenyl ether, 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 benzofenone; carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, and 1,2-butylene carbonate; Examples include sulfones such as sulforain; sulfoxides such as dimethyl sulfoxide; urea or its derivatives; phosphine oxides such as tributylphosphine oxide; ionic liquids such as imidazolium salts, piperidinium salts, and pyridinium salts; silicone oil; and water.

[0111] Among these solvents, hydrocarbons, ethers, carbonate compounds, and ionic liquids are preferred.

[0112] These solvents may be used individually, or two or more may be arbitrarily combined to form a mixed solvent.

[0113] (A) In the method for preparing the component, inert gases such as argon, helium, nitrogen, and carbon dioxide may be introduced into the system to maintain a good color tone of the reaction solution, but oxygen-containing gases may also be introduced into the system to prevent the 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 oxygen-containing gases include dissolving them in the reaction solution or blowing them into the reaction solution (so-called bubbling).

[0114] (A) In the method for manufacturing the component, it is preferable to add a polymerization inhibitor to the reaction solution to prevent the polymerization of the (meth)acryloyl group.

[0115] Examples of polymerization inhibitors include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt-based polymerization inhibitors.

[0116] 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, phenothiazine, and N-nitroso-N-phenylhydroxylamineammonium.

[0117] Organic compounds having stable radicals can also be used as organic polymerization inhibitors, such as galvinoxyl and N-oxyl compounds.

[0118] Examples of N-oxyl compounds include 2,2,6,6-tetramethylpiperidin-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl, and 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl.

[0119] Examples of inorganic polymerization inhibitors include copper chloride, copper sulfate, and iron sulfate.

[0120] Examples of organic salt-based polymerization inhibitors include copper dibutyl dithiocarbamate (dibutyl dithiocarbamic acid) and N-nitroso-N-phenylhydroxylamine aluminum salt.

[0121] Polymerization inhibitors may be added as a single type or in a combination of two or more types, and may be added from the very beginning of the invention or during the process. Additionally, the desired amount may be added all at once or added in divided portions. Furthermore, they may be added continuously via a rectification column.

[0122] The addition ratio of the polymerization inhibitor in the reaction solution is preferably 5 to 30,000 wtppm, and more preferably 25 to 10,000 wtppm. By making this ratio 5 wtppm or higher, the polymerization inhibition effect can be sufficiently exerted, and by making it 30,000 wtppm or lower, discoloration of the reaction solution can be suppressed, the purification process after the reaction is completed can be simplified, and the reduction in the curing speed of the obtained component (A) can also be prevented.

[0123] (A) The reaction time in the method of manufacturing the component varies depending on the type and amount of catalyst, reaction temperature, reaction pressure, etc., but is preferably 0.1 to 150 hours, and more preferably 0.5 to 80 hours.

[0124] (A) The method of manufacturing component can be carried out by any of the batch, semi-batch, and continuous methods. As an example of the batch method, a glycerin carbonate-based compound, a monofunctional (meth)acrylate, a catalyst, and a polymerization inhibitor are placed in a reactor, and the mixture is stirred at a predetermined temperature while bubbling an oxygen-containing gas into the reaction solution. Afterward, the target component (A) can be produced by methods such as by withdrawing the monohydric alcohol produced as a byproduct from the reactor at a predetermined pressure as the ester exchange reaction proceeds.

[0125] It is desirable to perform separation and purification operations on the reaction product obtained by the method of manufacturing component (A) so that the component (A) of the purpose can be obtained with good purity.

[0126] Separation and purification operations include crystallization, filtration, distillation, and extraction operations, and it is desirable to combine these. Crystallization operations include cooling crystallization and concentrated crystallization; filtration operations include pressurized filtration, suction filtration, and centrifugal filtration; distillation operations include single distillation, fractional distillation, molecular distillation, and steam distillation; and extraction operations include solid-liquid extraction and liquid-liquid extraction.

[0127] A solvent may also be used in the separation and purification operation.

[0128] In addition, a neutralizing agent for neutralizing the catalyst and / or polymerization inhibitor used in the present invention, an adsorbent for adsorption removal, an acid and / or alkali for decomposing or removing by-products, activated carbon for improving color tone, and diatomite for improving filtration efficiency and filtration speed may also be used.

[0129] The component (A) obtained in this way can have 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 cured composition with excellent water resistance and metal corrosion resistance.

[0130] When a compound having an ethylenically unsaturated group other than the component (A) described later [hereinafter referred to as "component (D)"] is incorporated, the content ratio of component (A) is preferably 5 to 100 weight% of the total 100 weight% of the curable components, more preferably 5 to 95 weight%, and particularly preferably 10 to 70 weight%.

[0131] (A) By making the content ratio of the component 5 weight% or more, the composition can be made low viscosity. Meanwhile, by making it 95 weight% or less, the crosslinking density can be increased and heat resistance can be improved.

[0132] In addition, the curable component is as defined above and refers to components (A) and (D).

[0133] 2. Curable composition

[0134] The present invention is a curable composition comprising the above (A).

[0135] A method for preparing a composition is preferred, comprising a process for preparing component (A), which is a mixture of reaction products including (meth)acrylate obtained by transesterifying a glycerin carbonate-based compound and a monofunctional (meth)acrylate in the presence of catalysts X and Y.

[0136] According to the manufacturing method, component (A) can be obtained in high yield, so cost and productivity are excellent. In addition, component (A) obtained by the manufacturing method has few by-product high molecular weight polymers, so it is easy to handle at low viscosity, and furthermore, the chlorine concentration and sodium concentration can be reduced.

[0137] For the process in question, the method of manufacturing component (A) described above should be followed.

[0138] Furthermore, when incorporating the other ingredients described later, the ingredients (A) and the other ingredients can be stirred and mixed.

[0139] The viscosity of the composition can be set appropriately according to the purpose, and is preferably 10 to 3,000 mPa·s, and more preferably 20 to 1,500 mPa·s.

[0140] The composition of the present invention may be used as an active energy beam curable composition or a thermosetting composition, but it may be preferably used as an active energy beam curable composition.

[0141] In addition, the composition of the present invention may be used in any form, such as 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, a commonly used emulsifier or a reactive emulsifier described below may be used as the dispersant.

[0142] The composition of the present invention comprises the above-mentioned component (A) as an essential component, but various components may be combined depending on the purpose.

[0143] Preferred examples of other components include, specifically, a photopolymerization initiator [hereinafter referred to as "Component (B)"], a thermal polymerization initiator [hereinafter referred to as "Component (C)"], and a compound having an ethylenically unsaturated group other than the above-mentioned component (A) [hereinafter referred to as "Component (D)"].

[0144] The following describes these components.

[0145] In addition, regarding the other ingredients described later, only one of the exemplified compounds may be used, or two or more may be used in combination.

[0146] 2-1. (B) Component

[0147] When using the composition of the present invention as an active energy beam curable composition, particularly when ultraviolet and visible light are used as the active energy beam, it is preferable to additionally include component (B) (photopolymerization initiator) from the perspective of ease of curing and cost.

[0148] When using electron beams as the active energy beam, it is not strictly necessary to incorporate it, but a small amount may be added as needed to improve curability.

[0149] (B) Specific examples of components include benzyldimethylketal, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]propanone, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl]-2-methylpropane-1-one, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, Acetophenone compounds such as 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butane-1-one and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-octylcarbazole;

[0150] Benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether;

[0151] Benzophenone compounds such as benzopene (phenzophenone), 2-methylbenzopene, 3-methylbenzopene, 4-methylbenzopene, 2,4,6-trimethylbenzopene, 4-phenylbenzopene, methyl-2-benzopene, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propane-1-one, 4,4'-bis(dimethylamino)benzopene, 4,4'-bis(diethylamino)benzopene, and 4-methoxy-4'-dimethylaminobenzopene;

[0152] 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

[0153] Examples of thioxantone-based compounds include thioxantone (thioxantone), 2-chlorothioxantone, 2,4-diethylthioxantone, isopropylthioxantone, 1-chloro-4-propylthioxantone, 3-[3,4-dimethyl-9-oxo-9H-thioxantone-2-yl-oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride and fluorothioxantone.

[0154] Compounds other than those mentioned above include benzyl, methyl phenylglyoxylate, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, ethylanthraquinone, phenanthrenquinone, and camphorquinone.

[0155] Among these compounds, acetophenone-based compounds are preferred, and furthermore, α-hydroxyphenylketone is preferred because it exhibits good surface curability even when coated as a thin film under atmospheric conditions. As for α-hydroxyphenylketone, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1-phenyl-propane-1-one are more preferred.

[0156] In addition, when it is necessary to increase the film thickness of the cured product, for example, to 50 μm or more, or when using ultraviolet absorbers or pigments in combination for the purpose of improving the curability inside the cured product, it is preferable to use a morpholine compound in combination with an acylphosphine oxide compound and an acetophenone-based compound. Examples of acylphosphine oxide compounds in this case 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 morpholine compounds include 2-methyl-1-[4-(methylthio)]phenyl]-2-morphopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morphopropylphenyl)butane-1-one, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-yl-phenyl)-butane-1-one.

[0157] (B) The content ratio of component (B) is preferably 0.05 to 15 parts by weight per 100 parts by weight of the total amount of curable components, and more preferably 0.1 to 10 parts by weight. By making the ratio of component (B) 0.05 parts by weight or more, the photocurability of the composition can be improved and the adhesion excellent, and by making it 15 parts by weight or less, the internal curability of the cured product It can be made good, and the adhesion to the substrate can be made good.

[0158] 2-2. (C) Component

[0159] (C) is a thermal polymerization initiator, and when the composition is used as a thermosetting composition, (C) may be incorporated.

[0160] The composition of the present invention may be formulated with a thermal polymerization initiator and heat-cured.

[0161] Various compounds can be used as thermal polymerization initiators, and organic peroxides and azo-based initiators are preferred.

[0162] 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-hexylperoxyisopropylmonocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, and t-butylperoxylaurate. 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-di-methyl-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, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, Examples include t-butylcumyl peroxide, di-t-butyl peroxide, p-methanene 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, t-butyl hydroperoxide, etc.

[0163] Specific examples of azo compounds include 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, azodi-t-butane, etc.

[0164] These can be used individually or in combination of two or more types. In addition, organic peroxides can be combined with a reducing agent to produce a redox reaction.

[0165] (C) The content ratio of the component is preferably 10 parts by weight or less per 100 parts by weight of the total amount of the curable component.

[0166] (C) When component (C) is used alone, it can be carried out according to the standard method of radical thermal polymerization, and in some cases, it can be used in combination with component (B) (photopolymerization initiator) and, after photocuring, further thermal curing can be performed to increase the reaction heat.

[0167] 2-3. (D) Component

[0168] (D) The component is a compound having an ethylenically unsaturated group, and is a compound other than the above (A) component.

[0169] (D) As for the ethylene unsaturated group of the component, a (meth)acryloyl group is preferred in terms of the excellent curability of the composition, and an acryloyl group is more preferred.

[0170] (D) The component may be a compound having one or more ethylenically unsaturated groups, and may be a compound other than (A) above. Specifically, examples include a compound having one ethylenically unsaturated group (hereinafter referred to as a "monofunctional unsaturated compound"), a compound having two ethylenically unsaturated groups (hereinafter referred to as a "bifunctional unsaturated compound"), and a compound having three or more ethylenically unsaturated groups (hereinafter referred to as a "triple-functional unsaturated compound").

[0171] Specific examples of monofunctional unsaturated compounds include compounds having a (meth)acryloyl group, monofunctional (meth)acrylamide ((meth)acrylamide) and compounds having a vinyl group.

[0172] Examples of compounds having a (meth)acryloyl group include compounds having a carboxyl group and an ethylenically unsaturated group, such as (meth)acrylic acid, a dimer of the Michael addition form of (meth)acrylic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, and phthalate monohydroxyethyl (meth)acrylate;

[0173] (Meta)acrylates having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate;

[0174] Carbitol (meth)acrylates such as ethyl carbitol (meth)acrylate, butyl carbitol (meth)acrylate, and 2-ethylhexyl carbitol (meth)acrylate;

[0175] Monofunctional (meth)acrylates having aromatic groups, such as benzyl (meth)acrylate, (meth)acrylate of an alkylene oxide adduct of phenol, (meth)acrylate of an alkylene oxide adduct of alkylphenol, (meth)acrylate of an alkylene oxide adduct of paracumylphenol, orthophenylphenol (meth)acrylate, (meth)acrylate of an alkylene oxide adduct of orthophenylphenol (orthophenylphenol), and 2-hydroxy-3-phenoxypropyl (meth)acrylate;

[0176] Monofunctional (meth)acrylates having a ring-shaped group, such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate; and

[0177] Examples include monofunctional (meth)acrylates having a complex ring, such as tetrahydrofurfuryl (meth)acrylate, (meth)acryloylmorpholine, N-(2-(meth)acryloxyethyl)hexahydrophthalimide and N-(2-(meth)acryloxyethyl)tetrahydrophthalimide.

[0178] Single-acting (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;

[0179] N-hydroxyalkyl(meth)acrylamides such as N-hydroxyethyl(meth)acrylamide; and

[0180] Examples include N,N-dialkyl(meth)acrylamides such as 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.

[0181] Examples of compounds having a vinyl group include N-vinylpyrrolidone and N-vinylcaprolactam.

[0182] As a binary unsaturated compound, binary (meth)acrylate is preferred.

[0183] As for bifunctional (meth)acrylates, specifically, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol 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, and di(meth)acrylates of alkylene oxide adducts of bisphenol A, and Examples include di(meth)acrylates of alkylene oxide adducts of bisphenol F.

[0184] In addition to the compounds mentioned above, oligomers such as urethan (meth)acrylate (urethane (meth)acrylate), epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate can be used as 2-function (meth)acrylates.

[0185] As for the 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, tri or tetra(meth)acrylate of pentaerythritol, tri or tetra(meth)acrylate of ditrimethylolpropane, tri or tetra(meth)acrylate of diglycerin, tri or tetra(meth)acrylate of dipentaerythritol, and tri, tetra, penta, or hexa(meth)acrylate of dipentaerythritol; and

[0186] Examples include poly(meth)acrylates of polyolalkylene oxide adducts such as tri(meth)acrylates of glycerin alkylene oxide adducts, tri or tetra(meth)acrylates of pentaerythritol alkylene oxide adducts, tri or tetra(meth)acrylates of ditrimethylolpropane alkylene oxide adducts, tri or tetra(meth)acrylates of diglycerin alkylene oxide adducts, and tri, tetra, penta, or hexa(meth)acrylates of dipentaerythritol alkylene oxide adducts; and tri(meth)acrylates of isocyanuric acid (isocyanuric acid) alkylene oxide adducts.

[0187] Examples of the above-mentioned alkylene oxide adducts include ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts.

[0188] In addition to the compounds mentioned above, uretain (meth)acrylates can also be used as 3 or more (meth)acrylates.

[0189] Among these compounds, tri- or tetra(meth)acrylates of pentaerythritol, tri, tetra, penta, or hexa(meth)acrylates of dipentaerythritol, and urethan (meth)acrylates with three or more functions are preferred because the cured product of the resulting composition has high hardness and excellent adhesion to the substrate. Below, urethan (meth)acrylates with three or more functions will be described in detail.

[0190] Examples of urethan (meth)acrylates with three or more functions include reactants of polyhydric alcohols, polyhydric isocyanates, and hydroxyl-containing (meth)acrylates, and reactants between organic polyhydric isocyanates and hydroxyl-containing (meth)acrylate compounds.

[0191] Examples of polyhydric alcohols include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by the reaction between the polyhydric alcohol and the polybasic acid, caprolactone polyols obtained by the reaction between the polyhydric alcohol and the polybasic acid and ε-caprolactone, and polycarbonate polyols (e.g., polycarbonate polyols obtained by the reaction between 1,6-hexanediol and diphenyl carbonate).

[0192] Examples of organic polyvalent isocyanates include diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and dicyclopentanyl diisocyanate; and

[0193] Examples include organic polyisocyanates having three or more isocyanate groups, such as hexamethylene diisocyanate trimers and isophorone diisocyanate trimers.

[0194] 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; and

[0195] Examples include hydroxyl group-containing multifunctional (meth)acrylates such as 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, and glycerin di(meth)acrylate.

[0196] Examples of desirable uretaine (meth)acrylates with three or more functions include a reaction product of an organic polyisocyanate having two isocyanate groups and a hydroxyl group-containing polyfunctional (meth)acrylate. Among these, isophorone diisocyanate or hexamethylene diisocyanate are preferred as organic polyisocyanates having two isocyanate groups due to their low viscosity, high hardness of the cured product, and low coloration, and hydroxyl group-containing polyfunctional (meth)acrylates include pentaerythritol di or tri(meth)acrylate, di, tri, tetra, or penta(meth)acrylate of dipentaerythritol, and glycerin di(meth)acrylate.

[0197] Urethane (meth)acrylate manufactured by the standard method may be used.

[0198] For example, methods include preparing an isocyanate group-containing compound by heating and stirring an organic polyvalent isocyanate and a polyvalent ol in the presence of an addition catalyst such as dibutyltin dilaurate, and further adding a hydroxyl group-containing (meth)acrylate to the compound and heating and stirring to carry out an addition reaction.

[0199] In the case of reactants of an organic polyvalent isocyanate and a hydroxyl group-containing (meth)acrylate, methods such as heating and stirring the organic polyvalent isocyanate and the hydroxyl group-containing (meth)acrylate in the presence of an addition catalyst and carrying out an addition reaction can be used.

[0200] Examples of uretaine poly(meth)acrylates other than these include compounds such as those described on pages 70 to 74 of the literature “UV·EB Curing Materials” [CMC Inc., 1992].

[0201] (D) The content ratio of the component is preferably 0 to 80 weight% of the total amount of the curable component (100 weight%), and more preferably 10 to 50 weight%.

[0202] (D) By keeping the content of the component at 80% by weight or less, the composition is prevented from becoming too viscous, and when used as a coating agent, it can be made to have excellent adhesion to the substrate.

[0203] (D) By making the content ratio of the component 10 weight% or more, it can be made to have excellent adhesion to plastic when used as a coating agent.

[0204] 2-4. Other components other than those mentioned above

[0205] Desirable other components include surface modifiers, antistatic agents, polymerization inhibitors, organic solvents, antioxidants, ultraviolet absorbers, and silane (silane) coupling agents.

[0206] The following describes these components.

[0207] 2-4-1. Surface Modifiers

[0208] The composition of the present invention may also include a surface modifier for purposes such as increasing leveling properties during application or increasing the slipperiness of the cured product to increase scratch resistance.

[0209] Examples of surface modifiers include surface modifiers, surfactants, leveling agents, defoaming agents, slip-improving agents, and antifouling agents, and these known surface modifiers may be used.

[0210] Among them, silicone-based surface modifiers and fluorine-based surface modifiers are suitable examples. Specific examples include organopolysiloxanes having a polyoxyalkylene backbone in their molecular structure, organopolysiloxanes having a polyester backbone, fluorine-based polymers and oligomers having perfluoroalkyl groups and polyalkylene oxide chains, and fluorine-based polymers and oligomers having perfluoroalkyl ether chains and polyalkylene oxide chains.

[0211] In addition, a surface modifier having an ethylenically unsaturated group, preferably a (meth)acryloyl group, in the molecule may be used for purposes such as increasing the maintenance of slipperiness.

[0212] Among these, it is preferable to use an organopolysiloxane having a polyoxyalkylene backbone [hereinafter referred to as "Component (E)"] because it has excellent surface smoothness and can also significantly improve the antistatic function described later.

[0213] Examples of oxyalkylenes that constitute the polyoxyalkylene backbone include oxyethylene, oxypropylene, oxybutylene, and combinations of these oxyalkylenes.

[0214] The form of the polyoxyalkylene backbone bond may be at one end, both ends, or side chains of the polysiloxane chain.

[0215] (E) Specific examples of the component include polyoxyethylene-methylpolysiloxane copolymer and poly(oxyethylene-oxypropylene)methylpolysiloxane copolymer.

[0216] (E) The ingredients are commercially available, for example, 71ADDITIVE, 74ADDITIVE, 57ADDITIVE, 8029ADDITIVE, 8054ADDITIVE, 8211ADDITIVE, 8019ADDITIVE, 8526ADDITIVE, FZ-2123, FZ-2191 [manufactured by Toray Dow Corning Toray Co., Ltd.];

[0217] TSF4440, TSF4441, TSF4445, TSF4446, TSF4450, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Inc.);

[0218] SILFACE SAG002, SILFACE SAG003, SILFACE SAG005, SILFACE SAG503A, SILFACE SAG008, SILFACE SJM003 [Manufactured by Nissin Chemical Industry Co., Ltd.];

[0219] TEGO Wet KL245, TEGO Wet 250, TEGO Wet 260, TEGO Wet 265, TEGO Wet 270, TEGO Wet 280 (manufactured by Evonik Co., Ltd.); and

[0220] Examples include BYK-345, BYK-347, BYK-348, BYK-375, and BYK-377 (manufactured by BYK JAPAN KK).

[0221] It is preferable that the content ratio of the surface modifier be 0.01 to 5.0 parts by weight per 100 parts by weight of the total amount of the curable component.

[0222] 2-4-2. Antistatic Agent

[0223] The composition of the present invention may also include an antistatic agent for the purpose of imparting an antistatic function.

[0224] Examples of antistatic agents include various cationic antistatic agents having cationic groups such as quaternary ammonium salts, pyridinium salts, and 1st to 3rd 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; non-ionic antistatic agents such as amino alcohol-based, glycerin-based, and polyethylene glycol-based agents; and polymeric antistatic agents obtained by increasing the molecular weight of the antistatic agents described above.

[0225] In addition, ionic liquids and metal salts may be used as antistatic agents. Ionic liquids and metal salts are not particularly limited, and various commonly used ionic liquids and metal salts may be used. The metal salts are useful because they exhibit high ionic dissociation even in trace amounts, thereby demonstrating excellent antistatic properties. Meanwhile, the ionic liquids are useful because they themselves exhibit excellent conductivity, allowing them to provide sufficient antistatic properties even in trace amounts.

[0226] Among these, an anionic metal salt having a fluoro group and a sulfonyl group (sulfonyl group) [hereinafter referred to as "(F) component"] is preferred because it has excellent antistatic ability and optical properties.

[0227] (F) In the component, a trifluoromethanesulfonyl group is preferred as the anion having a fluoro group and a sulfonyl group. In addition, alkali metals, group 2A elements, transition metals, and amphoteric metals are preferred as the metals forming the metal salt, and alkali metals are more preferred.

[0228] (F) Specific compounds of the component include metal salts of bis(trifluoromethanesulfonyl)imide, alkali metal salts of tris(trifluoromethanesulfonyl)mide, and alkali metal salts of trifluoromethanesulfonate ions.

[0229] That is, any one of the compounds represented by the following general formulas (D1) to (D3) is preferred.

[0230] M(CF3SO2)2N … … (D1)

[0231] M(CF3SO2)3C … … (D2)

[0232] M(CF3SO3) … … (D3)

[0233] In general formulas (D1) to (D3), M represents an alkali metal.

[0234] As alkali metal salts, lithium, sodium, and potassium are preferred, and lithium is more preferred.

[0235] Specific examples of the above components include bis(fluoroalkylsulfonyl)imide ions, tris(fluoroalkylsulfonyl)methide ions, and fluoroalkylsulfonate ions, specifically bis(trifluoromethanesulfonyl)imide lithium [Li(CF3SO2)2N], bis(trifluoromethanesulfonyl)imide potassium [K(CF3SO2)2N], bis(trifluoromethanesulfonyl)imide sodium [Na(CF3SO2)2N], tris(trifluoromethanesulfonyl)methide lithium [Li(CF3SO2)3C], tris(trifluoromethanesulfonyl)methide potassium [K(CF3SO2)3C], tris(trifluoromethanesulfonyl)methide sodium [Na(CF3SO2)3C], and lithium trifluoromethanesulfonate [Li(CF3SO3)]. Examples include potassium trifluoromethanesulfonate [K(CF3SO3)], sodium trifluoromethanesulfonate [Na(CF3SO3)], etc.

[0236] Among these compounds, bis(trifluoromethanesulfonyl)imide lithium, tris(trifluoromethanesulfonyl)mide lithium, and lithium trifluoromethanesulfonate are preferred, and bis(trifluoromethanesulfonyl)imide lithium and lithium trifluoromethanesulfonate are particularly preferred.

[0237] The content ratio of the antistatic agent is preferably 0.1 to 20 parts by weight per 100 parts by weight of solids in the composition, and more preferably 0.5 to 10 parts by weight.

[0238] By making the content ratio of the antistatic agent 0.1 parts by weight or more, the effect of reducing surface resistivity is achieved, while by making it 20 parts by weight or less, the water resistance of the cured product can be made excellent.

[0239] In the present invention, it is preferable to use component (E) and component (F) together to more effectively reduce surface resistivity.

[0240] 2-4-3. Polymerization Inhibitors

[0241] A polymerization inhibitor may be incorporated into the composition of the present invention for the purpose of improving storage stability, such as preventing gelation of the composition.

[0242] Examples of polymerization inhibitors include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt-based polymerization inhibitors exemplified in the method for manufacturing component (A) described above, and compounds identical to those above are exemplified.

[0243] Among these compounds, organic compounds possessing stable radicals are preferred as polymerization inhibitors because they improve storage stability without reducing the hardness of the cured product. Examples of organic compounds possessing stable radicals include galvinoxyl and N-oxyl compounds, and N-oxyl compounds are more preferred for the following reasons. Specifically, when applying a coating using the composition, work is often performed under fluorescent lamps excluding ultraviolet light (UV-blocking fluorescent lamps) due to their superior work efficiency; even when storing the composition under such fluorescent lamps, the composition containing N-oxyl compounds exhibits excellent storage stability.

[0244] Specific examples of N-oxyl compounds include 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl, 2,2,6,6-tetramethylpiperidin-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxyl, and 4-methoxy-2,2,6,6-tetramethylpiperidin-1-oxyl.

[0245] The polymerization inhibitor may be added to the composition, or if it is included in component (A), it may be used as is. Additionally, even if the polymerization inhibitor is included in component (A), the polymerization inhibitor may be added additionally.

[0246] The content ratio of the polymerization inhibitor in the composition is preferably 0.0005 to 1 weight%, and more preferably 0.005 to 0.1 weight%. By making the content ratio of the polymerization inhibitor 0.0005 weight% or more, the polymerization inhibition effect can be sufficiently exerted, and by making it 1 weight% or less, a decrease in the hardness of the cured product can be avoided.

[0247] 2-4-4. Organic Solvents

[0248] The composition of the present invention substantially does not require an organic solvent, but may include an organic solvent as needed for purposes such as viscosity adjustment.

[0249] Examples of organic solvents include compounds identical to the organic solvent used in the method for preparing component (A) described above.

[0250] The content ratio of the organic solvent is preferably 0.1 to 1000 parts by weight per 100 parts by weight of the total amount of the curable component, and more preferably 5 to 500 parts by weight. Within the above range, the composition can be made to a viscosity suitable for coating, and the composition can be easily applied using a known coating method described later.

[0251] 2-4-5. Antioxidants

[0252] Antioxidants are added to improve the durability of the cured product, such as heat resistance and weather resistance.

[0253] Examples of antioxidants include phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

[0254] Examples of phenolic antioxidants include hindered phenols such as di-butylhydroxytoluene. Commercially available examples include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by ADEKA CORPORATION.

[0255] Phosphate-based antioxidants include phosphines such as trialkylphosphine and triarylphosphine, as well as trialkyl phosphite and triaryl phosphite. Examples of commercially available derivatives of these include ADEKA STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, and 3010 manufactured by ADEKA STAB.

[0256] Examples of sulfur-based antioxidants include thioether compounds, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Co., Ltd.

[0257] One type or two or more types may be used. Preferable combinations of these antioxidants include the combined use of phenolic antioxidants and phosphorus-based antioxidants, and the combined use of phenolic antioxidants and sulfur-based antioxidants.

[0258] The content ratio of the antioxidant can be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight per 100 parts by weight of the total amount of curable components, and more preferably 0.1 to 1 part by weight.

[0259] The durability of the composition can be improved by making the content ratio of the antioxidant 0.1 parts by weight or more, while the curability and adhesion can be improved by making it 5 parts by weight or less.

[0260] 2-4-6. UV Absorber

[0261] UV absorbers are incorporated to improve the light resistance of the cured material.

[0262] 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.

[0263] The content ratio of the UV absorber can be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight per 100 parts by weight of the total amount of curable components, and more preferably 0.1 to 1 part by weight. By making the content ratio of the UV absorber 0.01% by weight or more, the light resistance of the cured product can be made good, while by making it 5% by weight or less, the curability of the composition can be made excellent.

[0264] 2-4-7. Silane Coupling Agents

[0265] Silane (silane) coupling agents are incorporated to improve the interfacial adhesion strength between the cured material and the substrate.

[0266] As for the silane coupling agent, it is not particularly limited to any that can contribute to improving adhesion with the substrate.

[0267] Specifically, silane coupling agents include 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane (3-glycidoxypropyltrimethoxysilane), 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane. Examples include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

[0268] The content ratio of the silane coupling agent can be appropriately set according to the purpose, and is preferably 0.1 to 10 parts by weight and more preferably 1 to 5 parts by weight per 100 parts by weight of the total amount of curable components.

[0269] By making the content ratio of the silane coupling agent 0.1 parts by weight or more, the adhesive strength of the composition can be improved, while by making it 10 parts by weight or less, changes in adhesive strength over time can be prevented.

[0270] 3. Uses

[0271] In the present invention, component (A) has excellent curability, and in particular, Glycarbo-A [(2-oxo-1,3-dioxolein-4-yl)methylacrylate] has excellent curability and can further reduce the viscosity of the composition and can be preferably used in a composition containing component (A) as a reactive diluent.

[0272] The present invention relates to a curable composition, preferably an active energy beam curable composition, more preferably a solvent-free active energy beam curable composition, and is capable of being used for various applications.

[0273] Examples include molding agents for forming coating agents such as paints, adhesives, pressure-sensitive adhesives, inks, and molding materials, as well as pattern-forming agents such as resists.

[0274] The composition of the present invention can be preferably used in coating compositions, adhesive compositions, and excipient material compositions among these uses, and more preferably in active energy beam curable coating compositions, adhesive compositions, and excipient material compositions.

[0275] The following describes the preferred uses.

[0276] In addition, among the other components listed below, only one of the exemplified compounds may be used, or two or more may be used in combination.

[0277] 3-1. Coating composition

[0278] The composition of the present invention can be preferably used as a coating composition because it has excellent thin film curability and high hardness of the cured product, and component (A) can be more preferably used as a solvent-free coating composition because it has low viscosity.

[0279] Furthermore, as mentioned above, component (A) has a low chlorine concentration, and thus can form a hardened film with excellent corrosion resistance, and has a low sodium concentration, and thus can form a hardened film with excellent water resistance.

[0280] Furthermore, since the resulting cured film of the composition of the present invention has excellent surface hardness and scratch resistance, it can be preferably used as a coating agent for various plastics, i.e., a hard coat agent, and can be preferably used as a solvent-free hard coat agent.

[0281] Materials to which hard coating agents are applied include plastic films used in polarizer protection films or anti-reflective films, and resin molded products used in home appliances or automotive interior and exterior parts.

[0282] The coating composition may have (A) as an essential component, but may incorporate various components depending on the purpose.

[0283] Other components may specifically include the above-mentioned components (B), (C), and (D), surface modifiers, ultraviolet absorbers, antistatic agents, polymerization inhibitors, organic solvents, antioxidants, and silane coupling agents.

[0284] In addition to these, pigments, dyes, and polymers can be cited.

[0285] Specific examples of pigments, dyes, and polymers include compounds identical to those listed in paragraphs

[0088] and

[0094] of International Publication WO2017 / 002964.

[0286] Another use of the coating composition is that it can be preferably used as a coating agent for metal substrates.

[0287] As described above, component (A) used in the present invention has a low chlorine concentration, and accordingly, a cured film of a curable composition with excellent corrosion resistance can be formed on the surface of a metal substrate.

[0288] A method for manufacturing a metal substrate having a cured film using the composition of the present invention preferably includes a process of coating a part or all of the metal substrate with a curable composition and a process of curing the coated composition by irradiating it with active energy rays or by heating.

[0289] A metal substrate having a hardened film obtained from the composition of the present invention can be suitably used as an electrode protective coating agent for electrode protective materials, substrate circuit protective materials, and lithium-ion batteries, etc., because the hardened film has excellent water resistance and corrosion resistance.

[0290] 3-2. Adhesive Composition

[0291] The composition of the present invention can be preferably used as an adhesive composition because it has low viscosity and excellent curability.

[0292] Furthermore, as mentioned above, since the cured material has excellent corrosion resistance and water resistance, it can be preferably used in applications where these properties are required.

[0293] The adhesive composition may have (A) as an essential component, but may incorporate various components depending on the purpose.

[0294] Specifically, other components include, in addition to the above-mentioned components (B), (C), and (D), surface modifiers, ultraviolet absorbers, polymerization inhibitors, organic solvents, antioxidants, silane coupling agents, pigments, dyes, and polymers.

[0295] 3-3. Composition for molding materials

[0296] Since the composition of the present invention has low viscosity and high hardness of the cured product, it can be preferably used as a composition for molding materials used in mold transfer or nanoimprint, and in particular, it can be preferably used as a molding material used for micro-processing such as nanoimprint.

[0297] In addition, for convenience, the molding material is also included in the concept of the molding material in this invention.

[0298] The molding material can be used to manufacture molding films having a micro-roughness structure on the surface, such as lens sheets, nanoimprint films, anti-reflective films having a moth-eye shape, polarizing films, anti-glare films, light extraction films for organic EL / LEDs, light trapping films for solar cells, and heat-retroreflective films.

[0299] The composition for the molding material has (A) as an essential component, but various components may be combined depending on the purpose.

[0300] Specifically, other components include, in addition to the above-mentioned components (B), (C), and (D), surface modifiers, ultraviolet absorbers, polymerization inhibitors, organic solvents, antioxidants, silane coupling agents, pigments, dyes, and polymers.

[0301] 3-4. Ink composition

[0302] Because the composition of the present invention has excellent thin film curing properties, it can be preferably used for transparent overprint varnish ink that is additionally printed on a printing press after single-color or multi-color printing, or for color printing inks such as yellow, magenta, cyan, and black.

[0303] Various printing methods can be cited, such as offset printing (conventional flatbed printing using dampening water and waterless flatbed printing not using dampening water), relief printing (flatbed relief, relief semi-rotary, rotary, intermittent rotary, flexo), intaglio printing (gravure printing), stencil printing (screen printing), and inkjet printing. Since it has excellent emulsification stability, it can be preferably used for offset printing using dampening water. In addition, because it has low viscosity, it can also be preferably used for inkjet printing.

[0304] The ink composition may include the above (A) as an essential component, but may incorporate various components depending on the purpose.

[0305] Specifically, other components include binders, pigments, plasticizers, and anti-friction agents in addition to the above-mentioned components (B), (C), and (D).

[0306] Specific examples of binders, pigments, plasticizers, and anti-friction agents include compounds identical to those presented in paragraphs

[0101] to

[0107] of International Publication WO2017 / 002964.

[0307] The method for manufacturing an ink composition may follow the conventional method for manufacturing an ink composition, and may include a method of mixing (A) component, (B) component (when the active energy line is ultraviolet light), binder, pigment, polymerization inhibitor, wax, and other additives, and then adding pigment and dispersing it using a disperser such as a triple roll mill or a bead mill.

[0308] 3-5. Composition for pattern formation

[0309] The composition of the present invention has high exposure sensitivity and excellent developability, and can form precise and accurate patterns, so it can be preferably used as a composition for forming patterns.

[0310] The pattern-forming composition has (A) as an essential component, but various components may be combined depending on the purpose.

[0311] Other components include, specifically, the above-mentioned (B), (D), organic solvent, antioxidant, ultraviolet absorber, silane coupling agent, surface modifier and polymerization inhibitor, as well as alkali-soluble resin.

[0312] Specific examples of alkali-soluble resins include compounds identical to those presented in paragraphs

[0110] to

[0122] of International Publication WO2017 / 002964.

[0313] 4. How to use

[0314] The method of using the composition of the present invention may follow commercial law.

[0315] For example, a method may be used in which the composition is applied to the substrate by a conventional coating method, and then cured by irradiating with active energy rays or heating.

[0316] The method for irradiating active energy rays can be the general method known as the conventional curing method.

[0317] In addition, a method may be employed to improve adhesion to the substrate by using component (B) (photopolymerization initiator) and component (C) (thermal polymerization initiator) in combination in the composition, irradiating it with an active energy beam, and then heat-curing it.

[0318] The composition of the present invention can be applied to various materials, such as plastic, metal, wood, inorganic materials, and paper.

[0319] 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, polyacrylate, cyclic polyolefin resins having cyclic olefins as monomers such as polyethersulfone and norbornene, polyvinyl chloride, epoxy resin, and polyurethane resin.

[0320] Examples of metals include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).

[0321] Examples of wood include natural wood and synthetic wood.

[0322] Examples of weapon materials include glass, mortar, concrete, and stone.

[0323] The coating method for the substrate of the composition of the present invention may be appropriately set according to the purpose, and may include methods of coating using a bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, knife coater, comma coater, reverse roll coater, die coater, rip coater, spray coater, gravure coater, and microgravure coater.

[0324] When the composition of the present invention is used as an active energy beam curing composition, the active energy beam for curing may include ultraviolet rays, visible light, and electron beams, but ultraviolet rays or visible light are preferred, and ultraviolet rays are particularly preferred.

[0325] Examples of ultraviolet irradiation devices include high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, and light-emitting diodes (LEDs).

[0326] The irradiation energy can be appropriately set depending on the type of active energy line or the composition of the mixture; for example, when using a high-pressure mercury lamp, the irradiation energy can be 50 to 5,000 mJ / cm². 2 It is desirable to have 100 to 1,000 mJ / cm² 2 It is more desirable.

[0327] When the composition of the present invention is used as a thermosetting composition, a cured film can be obtained by placing the cured film in a heatable dryer or the like.

[0328] The heating temperature can be set appropriately depending on the material or purpose used, and 40 to 180°C is preferred. In the case where the material is plastic, it is preferable to have a temperature of 120°C or lower, as there is a risk that the material may deform if the temperature is excessively high.

[0329] The heating time can be appropriately set according to the substrate and heating temperature to be applied, and preferably 0.5 to 60 minutes.

[0330] As described above, the composition of the present invention can be preferably used in coating compositions, adhesive compositions, compositions for molding materials, compositions for inks, and compositions for pattern forming, and specific examples thereof will be described.

[0331] 4-1. Method of using the coating composition

[0332] The method of use for the coating composition should follow the Commercial Law.

[0333] For example, methods such as curing by applying a composition to a substrate and then irradiating it with active energy rays or heating it may be used.

[0334] Specifically, examples include a method in which the composition is applied to the substrate by a conventional coating method, and then, in the case of an active energy beam curing type composition, cured by irradiating with an active energy beam, and in the case of a heat-curing type composition, cured by heating.

[0335] In addition, a method may be employed to improve adhesion to the substrate by using component (C) (photopolymerization initiator) and component (D) (thermal polymerization initiator) in combination in the composition, and then irradiating it with an active energy beam and heat-curing it.

[0336] The composition of the present invention can be applied to various materials, such as plastics, metals, wood, inorganic materials, and paper, and specific examples thereof are as described above.

[0337] The thickness of the cured film of the composition on the substrate can be appropriately set according to the purpose. The thickness of the cured film can be selected according to the use of the substrate or the substrate having the manufactured cured film, but it is preferable to be 1 μm to 5 mm, and more preferable to be 3 μm to 3 mm.

[0338] The coating method for the substrate of the composition of the present invention can be appropriately set according to the purpose, and methods such as those described in detail above may be cited.

[0339] When used as an active energy beam curing type coating composition, the active energy beam for curing may include ultraviolet rays, visible light, and electron beams, but ultraviolet rays are preferred.

[0340] The same device as above can be cited as an ultraviolet irradiation device.

[0341] The irradiation energy can be set appropriately depending on the type of active energy line or the composition of the mixture, and the same irradiation energy as above can be used.

[0342] 4-2. Method of using the adhesive composition

[0343] The method of using the adhesive composition should follow the Commercial Law.

[0344] For example, methods include applying a composition to a substrate, bonding the coated surface to another substrate, and then curing it by irradiating with active energy rays or heating.

[0345] Specifically, examples include a method in which the composition is applied to the substrate by a conventional coating method, and then, in the case of an active energy beam curing type composition, cured by irradiating with an active energy beam, and in the case of a heat-curing type composition, cured by heating.

[0346] In addition, in the case of an active energy beam curing adhesive composition, at least one side of the above-mentioned material is used to have light transmittance.

[0347] In addition, a method may be employed to improve adhesion to a substrate by using component (C) (photopolymerization initiator) and component (D) (thermal polymerization initiator) in combination in the composition, irradiating it with an active energy beam, and then heat-curing it.

[0348] The composition of the present invention can be applied to various materials, such as plastics, metals, wood, inorganic materials, and paper, and specific examples thereof are as described above.

[0349] The thickness of the cured film of the composition on the substrate can be appropriately set according to the purpose. The thickness of the cured film can be selected according to the use of the substrate or the substrate having the manufactured cured film, but it is preferable to be 0.1 to 500 μm, and more preferable to be 1 to 200 μm.

[0350] The coating method for the substrate of the composition of the present invention can be appropriately set according to the purpose, and methods such as those described in detail above may be cited.

[0351] When used as an active energy beam curing adhesive composition, the active energy beam for curing may include ultraviolet rays, visible light, and electron beams, but ultraviolet rays are preferred.

[0352] The same device as above can be cited as an ultraviolet irradiation device.

[0353] The irradiation energy can be set appropriately depending on the type of active energy line or the composition of the mixture, and the same irradiation energy as above can be used.

[0354] 4-3. Method of using the composition for molding materials

[0355] When using the composition of the present invention as a molding material, the method of use may follow the Commercial Code.

[0356] Specifically, examples include a method of applying a composition to a mold called a stamper having a desired shape, laminating it onto a film or sheet substrate (hereinafter collectively referred to as "film substrate"), and then irradiating it with active energy rays to cure it; a method of injecting a composition into a predetermined mold and, in the case of an active energy ray curing type composition, curing it by irradiating it with active energy rays; and, in the case of a heat-curing type composition, curing it by heating it.

[0357] As film substrates that can be used in the present invention, plastic films such as polymethyl methacrylate, polymethyl methacrylate-styrene copolymer film, polyethylene terephthalate, polyethylene naphthalate, polyarylate, polyacrylnitrile, polycarbonate, polysulfone, polyethersulfone, polyetherimide, polyetherketone, polyimide, and polymethylpentane are preferred, and if necessary, glass-based substrates may be used.

[0358] It is preferable that the film substrate be transparent or translucent (e.g., milky white). It is preferable that the thickness of the film substrate be 20 to 500 μm.

[0359] The thickness of the cured film of the composition on the substrate can be appropriately set according to the purpose. The thickness of the cured film can be selected according to the use of the substrate or the substrate having the manufactured cured film, but it is preferable to be 10 nm to 100 μm, and more preferable to be 50 nm to 50 μm.

[0360] Examples of active energy rays for curing the composition of the present invention include ultraviolet rays, visible light, and electron beams, but ultraviolet rays are preferred.

[0361] The same device as above can be cited as an ultraviolet irradiation device.

[0362] The irradiation energy can be set appropriately depending on the type of active energy line or the composition of the mixture, and the same irradiation energy as above can be used.

[0363] An example of manufacturing a lens sheet using the composition of the present invention will be described.

[0364] 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 having the shape of a target lens is pressed against it.

[0365] Next, the composition is cured by irradiating an active energy line from the transparent substrate side, and then peeled off from the mold.

[0366] Meanwhile, when manufacturing a lens sheet with a relatively thick film, the composition of the present invention is poured between a mold having the shape of the target lens and a transparent substrate.

[0367] Next, active energy rays are irradiated from the transparent substrate side to cure the composition, and then the mold is demolded.

[0368] The material of the above 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 to ensure a long lifespan.

[0369] When using the composition of the present invention for nanoimprinting purposes, commercial laws may be followed.

[0370] For example, after applying the composition to a substrate, a mold having a micro-processed pattern and transparency is pressed.

[0371] Next, methods such as curing the composition by irradiating an active energy beam onto a transparent mold and then demolding the mold can be used.

[0372] 4-4. Method of using ink composition

[0373] There are no particular limitations on the printing substrate used in the printed material of the present invention, and examples include paper such as high-quality paper, coated paper, art paper, imitation paper, thin paper, and thick paper, various synthetic papers, polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon, polylactic acid, polycarbonate, films or sheets, cellophane, aluminum foil, and various other substrates conventionally used as printing substrates.

[0374] The thickness of the cured film of the composition on the substrate can be appropriately set according to the purpose. The thickness of the cured film can be selected according to the use of the substrate or the substrate having the manufactured cured film, but it is preferable to be 1 to 20 μm, and more preferable to be 1 to 10 μm.

[0375] When the composition of the present invention is used for offset ink, the coating method on the substrate can be suitably used by using an offset printing press that continuously supplies water onto the plate surface. In addition, it can be suitably used in any paper feeding method, such as a sheet-fed offset printing press using sheet-type printing paper or an offset rotary printing press using reel-type printing paper.

[0376] When the composition of the present invention is used for inkjet ink, a known inkjet recording device that forms an image by ejecting by an inkjet method can be suitably used as a coating method on a substrate.

[0377] In the inkjet method, ejection performance is considered, and it is preferable that the viscosity of the composition be 7 mPa·s to 30 mPa·s at the temperature during ejection (e.g., 40°C to 80°C, preferably 25°C to 30°C). More preferably, it is 7 mPa·s to 20 mPa·s.

[0378] Examples of active energy rays for curing the composition of the present invention include ultraviolet rays, visible light, and electron beams, but ultraviolet rays are preferred.

[0379] The same device as above can be cited as an ultraviolet irradiation device.

[0380] The irradiation energy can be set appropriately depending on the type of active energy line or the composition of the mixture, and the same irradiation energy as above can be used.

[0381] 4-5. Method of using the pattern-forming composition

[0382] Examples of compositions for forming patterns include photosensitive flat printing plates, resists such as etching resist and solder resist, columnar spacers in the manufacture of liquid crystal panels, coloring compositions for forming pixels or black matrices in color filters, and color filter protective films.

[0383] The composition of the present invention can be used more preferably among these applications for pillar-type spacers in the manufacture of liquid crystal panels, coloring compositions for color filters, and protective films for color filters.

[0384] When used for columnar spacers and color filter protective films, nonionic surfactants such as polyoxyethylene lauryl ether or fluorine-based surfactants may be added to the composition to improve coating properties and developability. Additionally, adhesion aids, preservative stabilizers, and defoaming agents may be added appropriately as needed.

[0385] Example of implementation

[0386] The present invention will be explained in more detail below by showing manufacturing examples, embodiments, and comparative examples.

[0387] In addition, "part" below refers to a part by weight.

[0388] High-speed liquid chromatography (hereinafter referred to as "HPLC"), viscosity, gel permeation chromatography (hereinafter referred to as "GPC"), gas chromatography (hereinafter referred to as "GC"), APHA, chlorine content, and sodium content were measured under the following conditions.

[0389] ◆ Measurement Conditions

[0390] · Equipment: ACQUITY UPLC manufactured by Waters, Inc.

[0391] · Detector: UV detector

[0392] · Detection wavelength: 210 nm

[0393] · Column: Waters, Inc. ACQUITY UPLC BEH C18 (Part No. 186002350, column bore 2.1 mm, column length 50 mm)

[0394] · Column temperature: 40℃

[0395] · Composition of eluent: A mixed solution of 0.03 wt% aqueous trifluoroacetic acid and methanol

[0396] · Eluent flow rate: 0.3 mL / min

[0397] ◆ Viscosity measurement conditions

[0398] The viscosity at 25°C was measured using an E-type viscometer (Cone and Plate Viscometer).

[0399] ◆ Measurement Conditions

[0400] · Device: GPC manufactured by Waters, Inc. System Name 1515 2414 717P RI

[0401] · Detector: RI detector

[0402] · Columns: Guard column Shodex KFG (8 μm 4.6 x 10 mm) manufactured by Showa Denko KK; Main column (2 types) Styragel HR 4E THF (7.8 x 300 mm) + Styragel HR 1THF (7.8 x 300 mm) manufactured by Waters Corp.

[0403] · Column temperature: 40℃

[0404] · Eluent composition: THF (containing 0.03% sulfur as an internal standard), flow rate 0.75 mL / min

[0405] · Calibration curve: A calibration curve was prepared using standard polystyrene.

[0406] · Calculation method of purity (%)

[0407] Among the peaks detected by GPC measurement, the sum of all peaks originating from the purified product was defined as 100%, and the area was calculated based on the following formula (1) from the area of ​​the peak containing acrylate of glycerin carbonate and / or acrylate of glycerin carbonate ethylene oxide adduct. In addition, if each peak was not completely separated, vertical splitting was performed to determine the area of ​​each peak.

[0408] Purity (%) of purified product = (I / S) × 100 … (1)

[0409] The symbols and terms in Equation (1) are as follows.

[0410] S: Total area of ​​the detection peak originating from the purified product

[0411] I: Area of ​​detection peak containing glycerin carbonate acrylate and / or acrylate of glycerin carbonate ethylene oxide adduct

[0412] ◆ GC Measurement Conditions

[0413] · Device: GC-14B manufactured by Shimadzu Corporation

[0414] · Detector: FID detector

[0415] · Column: ZB-1 (Length 60 m, Inner diameter 0.32 mm, Film thickness 3 μm)

[0416] · Injection temperature: 230℃ or 270℃

[0417] · Detector temperature: 330℃

[0418] · Column temperature: Hold at 125℃ for 5 minutes, then increase at a rate of 10℃ / min. Hold for 20 minutes after reaching 325℃.

[0419] · Carrier gas: Nitrogen

[0420] · Injection volume: Inject 0.4 μL after diluting to 10 wt% with methanol or acetone.

[0421] · Calculation method of purity (%)

[0422] Among the peaks detected by GPC measurement, the peaks originating from the dilution solvent were not considered, and the total area of ​​all peaks originating from the sample before dilution was set to 100%, and the result was calculated based on the following equation (2) from the peak area of ​​the target object. In addition, if each peak was not completely separated, vertical splitting was performed to obtain the area of ​​each peak.

[0423] Purity of the object (%) = (I / S) × 100 … (2)

[0424] The symbols and terms in Equation (2) are as follows.

[0425] S: Total area of ​​the detection peak originating from the sample before solvent dilution

[0426] I: Peak area of ​​the object

[0427] ◆ APHA

[0428] APHA was measured using a colorimeter [PELP product color tester OME-2000 manufactured by DENSHOKU INDUSTRIES Co., Ltd.].

[0429] ◆ Chlorine content

[0430] 30 mg of sample is collected in a quartz boat of a trace chlorine sulfur analyzer, combusted under an argon / oxygen stream, and finally combusted under a pure oxygen stream. The generated combustion gas is passed through 10 ml of an absorption solution (0.3% hydrogen peroxide solution), and the chlorine is collected as Cl ions. This operation is repeated three times to collect chlorine in the same absorption solution and used as a test solution. The test solution is measured using an ion chromatograph, and the Cl ions are quantified by the calibration curve method.

[0431] · Trace Chlorine Sulfur Analysis Device: TOX-100 manufactured by Mitsubishi Chemical Analytech Co., Ltd.

[0432] · Ion Chromatograph: DIONEX ICS-3000 manufactured by Thermo Fisher Scientific Inc. (Column: IonPac AG20 / AS20)

[0433] ◆ Sodium content

[0434] 1 g of sample is placed in a 20 ml PFA bottle (fluoropolymer bottle), diluted with 10 g of NMP (N-methylpyrrolidone) to form the test solution. The test solution is measured using an ICP mass spectrometer. The detected elements are quantified using the absolute calibration curve method.

[0435] · Pre-processing environment: Clean room G (Class 1000) and clean draft (Class 100)

[0436] · NMP: For the electronics industry [Manufactured by FUJIFILM Wako Pure Chemical Corporation]

[0437] · Mixed Standard Solution: XSTC-622B (Manufactured by SPEX)

[0438] ·ICP Mass Spectrometer: Agilent 7700s manufactured by Agilent Technologies, Inc. (Organic solvent measurement mode: He / H2)

[0439] 1. Manufacturing Example

[0440] In addition, the abbreviations in the manufacturing examples mean the following.

[0441] ·MCA: 2-Methoxyethylacrylate

[0442] ·MEL: 2-Methoxyethanol

[0443] ·DABCO: Triethylenediamine

[0444] ·MEHQ: Hydroquinone monomethyl ether

[0445] ·TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl

[0446] ·DEHA: N,N-Diethylhydroxylamine

[0447] 1) Manufacturing Example 1

[0448] In a 3-liter flask equipped with a stirrer, thermometer, gas inlet tube, rectification column, and cooling tube, 660.00 parts (5.59 mol) of glycerin carbonate, 1891.10 parts (14.53 mol) of MCA, 1.22 parts (0.011 mol) of DABCO (triethylenediamine) as catalyst X, 4.52 parts (0.022 mol) of zinc acrylate as catalyst Y, 1.02 parts of MEHQ (474 ​​ppm relative to the total weight of the added raw materials), and 0.74 parts of TEMPOL (288 ppm relative to the total weight of the added raw materials) were added, and an oxygen-containing gas (5 volume% oxygen, 95 volume% nitrogen) was bubbled into the liquid.

[0449] While heating and stirring the reaction solution in the range of 110 to 120°C, the pressure in the reaction system was adjusted in the range of 140 to 180 mmHg, and the mixture of MEL and MCA produced as a byproduct during the ester exchange reaction was drawn out of the reaction system through a rectification column and a cooling tube.

[0450] In addition, an equal weight part of MCA as the extracted liquid was added to the reaction system from time to time. In addition, MCA containing MEHQ and TEMPOL was added to the reaction system from time to time through a rectification column. Heating was stopped 17 hours after the start of heating and stirring, and extraction was terminated by returning the pressure in the reaction system to atmospheric pressure. A portion of the reaction liquid was collected and compositional analysis was performed using HPLC, and it was confirmed that it contained the target product, Glycarbo-A [(2-oxo-1,3-dioxolein-4-yl)methylacrylate].

[0451] 54 parts of aluminum silicate [KYOWAAD 700 manufactured by Kyowa Chemical Industry Co., Ltd. (product name. Hereinafter the product name is abbreviated.)] were added as an adsorbent to the filtered liquid, and contact treatment was performed by heating and stirring for 1 hour under atmospheric pressure in a temperature range of 80 to 105°C, after which 3.0 parts of calcium hydroxide were added in a temperature range of 20 to 40°C and stirred for 1 hour under atmospheric pressure.

[0452] After separating the 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 into the filtrate to separate the effluent containing unreacted MCA.

[0453] 0.87 parts of DEHA (900 ppm relative to the second process treatment) were added to the obtained kiln liquid, and the mixture was stirred for 3 hours under atmospheric pressure at a temperature range of 70 to 90°C. Afterwards, 4.50 parts of diatomite [Radiolite manufactured by Showa Chemical Industry Co., Ltd. (product name). Hereinafter the product name is abbreviated] were added to the kiln liquid and pressure filtration was performed, and the obtained filtrate was used as the purified treatment. The weight of the filtrate was 945.75 parts, and compositional analysis was performed using HPLC, confirming that it contained the target product, Glycarbo-A. Hereinafter referred to as compound a1.

[0454] Various analysis results of the obtained compound a1 (purified product) are shown in Table 1.

[0455] 2) Manufacturing Example 2

[0456] (1) Preparation of glycerin carbonate ethylene oxide adduct

[0457] First, the ethylene oxide adduct of glycerin, which is the raw material for the glycerin carbonate ethylene oxide adduct, was purified.

[0458] 1,722 parts of ethylene oxide adduct of glycerin [EMULGEN GE-1 (trade name) manufactured by Kao Corporation, hydroxyl value 1,190 mgKOH / g] were added to a 3-liter flask equipped with a stirrer, thermometer, and condenser, and vacuum distillation was performed for 43 hours at a temperature of 125 to 140°C and an internal pressure of 70 to 7 Pa, to first extract 475 parts (hereinafter referred to as the "initial extract"), and then 508 parts (hereinafter referred to as the "main extract").

[0459] According to GC analysis results, this main liquid contained 6% glycerin, 72% of a compound in which one ethylene oxide is added only to the hydroxyl group at the 1st position of glycerin, and 10% of a compound in which two ethylene oxides are added only to the hydroxyl group at the 1st position of glycerin.

[0460] In a 3-liter flask equipped with a stirrer, a thermometer, and a cooling tube, 504 parts of the main liquid obtained above, 411 parts of ethylene carbonate, and 0.9 parts of activated alumina as a catalyst were added. The reaction liquid was heated and stirred in the range of 130–150°C, while the pressure within the reaction system was adjusted in the range of 4700–30 Pa. As the ester exchange reaction proceeded, the byproduct mixture of ethylene glycol and ethylene carbonate was withdrawn from the reaction system through the cooling tube. Heating was stopped 15 hours after the start of stirring, and the pressure within the reaction system was returned to atmospheric pressure to terminate the withdrawal process. Subsequently, the liquid was pressurized to remove the activated alumina added as a catalyst, and the filtrate was obtained.

[0461] The weight of the filtrate was 560 parts, and GC analysis revealed that it contained 5% glycerin carbonate, 68% a compound in which one ethylene oxide is added only to the hydroxyl group at the 1st position of glycerin and the hydroxyl groups at the 2nd and 3rd positions are carbonated to form a cyclic carbonate structure within the molecule, and 4% a compound in which two ethylene oxides are added only to the hydroxyl group at the 1st position of glycerin and the hydroxyl groups at the 2nd and 3rd positions are carbonated to form a cyclic carbonate structure within the molecule.

[0462] (2) Preparation of acrylates of glycerin carbonate ethylene oxide adducts

[0463] In a 3-liter flask equipped with a stirrer, thermometer, gas inlet tube, rectification column, and cooling tube, 450 parts of the filtrate obtained above, 1553 parts (11.93 mol) of MCA, 0.31 parts (0.028 mol) of DABCO as catalyst X, 1.15 parts (0.056 mol) of zinc acrylate as catalyst Y, 2.09 parts of pure water, 0.78 parts of MEHQ (464 ppm relative to the total weight of the added raw materials), and 0.56 parts of TEMPOL (279 ppm relative to the total weight of the added raw materials) were added, and an oxygen-containing gas (5 vol% oxygen, 95 vol% nitrogen) was bubbled into the liquid.

[0464] While heating and stirring the reaction solution in the range of 110 to 120°C, the pressure in the reaction system was adjusted in the range of 120 to 160 mmHg, and the mixture of MEL and MCA produced as a byproduct during the ester exchange reaction was drawn out of the reaction system through a rectification column and a cooling tube.

[0465] In addition, an equal weight part of MCA as the extracted liquid was added to the reaction system from time to time. In addition, MCA containing MEHQ and TEMPOL was added to the reaction system from time to time through a rectification column. After 40 hours from the start of heating and stirring, heating was stopped, and the pressure in the reaction system was returned to atmospheric pressure to stop extraction.

[0466] 18 parts of aluminum silicate were added as an adsorbent to the reaction end kiln liquid, and contact treatment was performed by heating and stirring for 1 hour under atmospheric pressure at a temperature range of 80 to 105°C, then 0.9 parts of calcium hydroxide were added at a temperature range of 20 to 40°C and stirred for 1 hour under atmospheric pressure.

[0467] After separating the 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 into the filtrate to separate the effluent containing unreacted MCA.

[0468] 0.75 parts of DEHA were added to the obtained kiln liquid and stirred for 3 hours under atmospheric pressure at a temperature in the range of 70 to 90°C. Afterwards, 4.5 parts of diatomite were added to the kiln liquid and pressure filtration was performed, and the obtained filtrate was used as the purified product. Hereinafter referred to as compound a2.

[0469] The weight of compound a2 (filtrate) was 630 parts, and GC analysis revealed that it contained 7% glycerin carbonate acrylate, 59% acrylate of 1 mole ethylene oxide adduct of glycerin carbonate, and 4% acrylate of 2 mole ethylene oxide adduct of glycerin carbonate.

[0470] Various analysis results of the obtained compound a2 are shown in Table 1.

[0471] 3) Manufacturing Example 3

[0472] 200 parts of the purified product obtained in Preparation Example 2 and 1,525 parts of normal hexane were placed in a 3-liter separatory funnel, and the extraction operation was performed by vigorously shaking the separatory funnel. After settling, the liquid separated into two layers, and components having a carbonate structure such as glycerin carbonate acrylate were mainly distributed in the lower layer, while the upper layer, which mainly consisted of normal hexane, contained a large amount of acrylate compounds that did not have a carbonate structure, such as glycerin triacrylate or compounds that were triacrylated after having only one ethylene oxide group added to the hydroxyl group at the 2nd position of glycerin.

[0473] The upper layer was removed from the separatory funnel and concentrated under reduced pressure using an evaporator to recover most of the normal hexane as distillate. The recovered normal hexane and fresh normal hexane were added to the lower layer of the separatory funnel, 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 separatory funnel was removed, 0.105 parts of MEHQ and 0.001 parts of TEMPOL were added, and vacuum distillation was performed for 5 hours at a temperature of 60°C and a pressure of 3 to 100 mmHg while bubbling dry air, and the normal hexane contained in a small amount in the lower layer was distilled off, and the resulting liquid was used as the purified product. Hereinafter referred to as compound a3.

[0474] The weight of compound a3 (kiln liquid) was 155 parts, and GC analysis results showed that it contained 9% glycerin carbonate acrylate, 77% acrylate of 1 mole ethylene oxide adduct of glycerin carbonate, and 5% acrylate of 2 mole ethylene oxide adduct of glycerin carbonate.

[0475] Various analysis results of the obtained compound a3 are shown in Table 1.

[0476] 4) Comparative Manufacturing Example 1 [Preparation by Ester Exchange Reaction Using Titanium Catalyst]

[0477] 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 parts of phenothiazine were added to a 20 ml test tube equipped with a rotor, thermometer, gas inlet tube, and cooling tube. The reaction solution was heated for 0.5 hours at a temperature range of 105–120°C while bubbling oxygen-containing gas (5 volume% oxygen, 95 volume% nitrogen) into the liquid. Afterward, 0.245 parts (0.0007 mol) of titanium tetranormal butoxide was added as a catalyst, and the reaction solution was heated for 6 hours at a temperature range of 105–120°C.

[0478] A portion of the reaction solution was collected and compositional analysis was performed using HPLC, but the formation of the target product, Glycarbo-A, was not confirmed.

[0479] 5) Comparative Manufacturing Example 2 [Manufacturing by Dehydration Esterification Reaction]

[0480] 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 added to a flask equipped with a stirrer, thermometer, gas inlet tube, condenser, and water produced by the dehydration reaction was drawn out through the water pipe while heating and stirring for 7 hours at a reaction pressure of 370 Torr and a reaction liquid temperature of 86–90°C while bubbling oxygen-containing gas (5 vol% oxygen, 95 vol% nitrogen) into the liquid. A portion of the reaction liquid was collected and compositional analysis was performed using HPLC, confirming that it contained the target product, Glycarbo-A.

[0481] After cooling the reaction mixture to room temperature, 274.34 parts of toluene and 87.50 parts of water were added and stirred. When stirring was stopped and the mixture was allowed to stand, it separated into three layers. The top layer contained almost no target substance and was mainly composed of toluene. The middle layer was an aqueous layer. The bottom layer was a layer containing the target substance.

[0482] After discharging the upper and middle layers, 250.00 parts of tetrahydrofuran and 55.48 parts of a 20% aqueous sodium hydroxide solution were added to the lower layer and stirred. When 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 was a layer containing the target substance.

[0483] After discharging the lower layer, 87.50 parts of water were added to the upper layer and stirred. When stirring was stopped and the layer was left to stand, it separated into two layers. The lower layer was a water layer, and the upper layer was a layer containing the target material.

[0484] After discharging the lower layer, the upper layer was transferred to a flask, and 0.14 parts of MEHQ were added. 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, and low-boiling point components such as tetrahydrofuran, toluene, and water were removed.

[0485] 1.40 parts of diatomaceous earth [Radiolite manufactured by Showa Chemical Industry Co., Ltd. (product name)] were added to the kiln liquid and pressure filtration was performed, and the obtained filtrate was used as the purified product. The weight of the filtrate was 147.19 parts, and compositional analysis was performed using HPLC, confirming that it contained the target product, Glycarbo-A. Hereinafter referred to as compound a'2.

[0486] Various analysis results of the obtained compound a'2 (purified product) are shown in Table 1.

[0487] 6) Comparative Manufacturing Example 3 [Manufacturing by Acid Chloride Method]

[0488] The method was carried out with reference to the method described in non-patent literature [G. Wegner et al., Macromolecules, 2007, Vol. 40, pp. 7558-7565].

[0489] 130.00 parts (1.10 mol) of glycerin carbonate, 111.40 parts (1.10 mol) of triethylamine, and 700 mL of tetrahydrofuran were added to a 2-liter flask equipped with a stirrer, thermometer, dropping funnel, and gas inlet tube, and the mixture was cooled to a temperature range of 0 to 5°C while flowing nitrogen through the gas phase.

[0490] 99.64 parts (1.10 mol) of acryloyl chloride and 260 mL of tetrahydrofuran were added to a dropping funnel, and while stirring, the mixture was slowly added dropwise over about 3 hours until the temperature was within the range of 0 to 5°C.

[0491] After the dropping was finished, the mixture was stirred for 1 hour, the supernatant was transferred to a separatory funnel, and 50 mL of tetrahydrofuran, which had been washed to remove 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.

[0492] 0.047 parts of MEHQ and 0.0047 parts of TEMPOL were added to an organic solvent layer, and vacuum distillation containing tetrahydrofuran was performed for 10 hours at a temperature of 50–70°C and a pressure of 20–100 mmHg while bubbling dry air.

[0493] Solids were separated by pressure filtration, and the obtained filtrate was used as the purified product. The weight of the filtrate was 59.72 parts, and compositional analysis was performed using HPLC, confirming that it contained the target product, Glycarbo-A. Hereinafter, it will be referred to as compound a'3.

[0494] Various analysis results of the obtained compound a'3 (purified product) are shown in Table 1.

[0495]

[0496] 2. Example

[0497] 1) Preparation of an active energy beam curable composition

[0498] The compounds shown in Tables 2 to 4 below were stirred, mixed, and dissolved in a stainless steel container in the ratios shown in Table 2 to prepare an active energy beam curable composition.

[0499] In addition, the numbers in Tables 2 to 4 represent the radicals, and the abbreviations represent the following.

[0500] · M1200: Uretaine Acrylate [Manufactured by TOAGOSEI CO., LTD., Product Name: ARONIX M-1200]

[0501] · M402: Dipentaerythritol penta / hexaacrylate mixture [Manufactured by Doa Synthetic Co., Ltd., Product name: Aronics M-402]

[0502] ·Om907: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one [Manufactured by IGM Resins BV, Trade name: Omnirad 907]

[0503] ·DETX: 2,4-Diethylthioxanthine [Manufactured by Nippon Kayaku Co., Ltd., Trade Name: KAYACURE DETX-S]

[0504] ·TPO: Phosphorus-based photopolymerization initiator (2,4,6-trimethylbenzoyl-diphenylphosphine oxide) [Manufactured by IGM Resins, Trade name: Omnirad TPO]

[0505] 2) Evaluation Method

[0506] The following evaluations were performed using the obtained compositions. The results are shown in Tables 2 to 4.

[0507] (1) Viscosity

[0508] The viscosity of the obtained composition was measured using an E-type viscometer (cone plate type viscometer) (25°C).

[0509] (2) Damp-heat test

[0510] The composition obtained in Table 2 was applied to a thickness of 10 μm using a bar coater onto a 100 μm thick easy-to-adhesive polyethylene terephthalate (hereinafter referred to as "PET") film [Cosmo Shine A4300 manufactured by TOYOBO CO., LTD.], and then the composition was cured by irradiating with ultraviolet light.

[0511] The UV irradiation device used a metal halide lamp manufactured by EYE GRAPHICS CO., LTD., with an irradiation intensity of 200 mW / cm² in the ultraviolet region (UV-A) centered at 365 nm. 2 , accumulated luminous energy 2,000 mJ / cm² 2 UV irradiation was performed under the conditions of.

[0512] After UV irradiation, the obtained samples were maintained at 85°C and 85% RH for 100 hours, and a moist heat test was performed. Changes in the appearance of the cured film after the moist heat test were observed visually and evaluated at the following three levels.

[0513] ○: No change, △: Problems such as foaming or peeling occurred in some areas, Х: Peeling occurred across the entire surface of the hardened film

[0514] (3) Insulation reliability

[0515] A composition obtained in Table 2 was applied to a substrate (hereinafter referred to as the "comb-shaped substrate") on which a comb-shaped pattern of line / space = 100 / 100 was formed by photolithography on a polyimide / copper laminated film, to a thickness of 10 μm using a bar coater, and then the composition was cured by ultraviolet irradiation under the same conditions as the moist heat test.

[0516] Using the evaluation sample obtained by the above method, the time until the resistance value became 100 MΩ or less was measured while continuously applying a voltage of 20 V under an atmosphere of 85°C and 85% RH, and the insulation reliability test was evaluated.

[0517] (4) Adhesion (Initial)

[0518] After applying the composition obtained in Table 3 to a thickness of 10 μm using a bar coater to a 100 μm thick film of adhesive-friendly polyethylene terephthalate (hereinafter referred to as "adhesive-friendly PET") [Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.], the remaining adhesive-friendly PET was laminated and irradiated with ultraviolet light under the same conditions as the moist heat test, and the composition was cured.

[0519] 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 the peel strength was determined.

[0520] (5) Adhesion (after moist heat test)

[0521] The laminate obtained in (4) was maintained for 100 hours in an atmosphere of 85°C and 85% RH, 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 used.

[0522] (6) Shape reproducibility

[0523] The composition obtained in Table 4 was applied to a thickness of 10 μm using a bar coater on a transfer mold (hereinafter referred to as the "nickel mold") having a micro-process (a semicircular pattern with a diameter of 3 μm and a film thickness of 5 μm) formed on a nickel-plated stainless steel plate, then laminated with an adhesive PET, irradiated with ultraviolet light under the same conditions as the moist heat test, and cured.

[0524] Afterward, the film was peeled off from the nickel mold, the pattern shape of the obtained hardened film was observed under a microscope, the dimensions of the shape were measured and compared with those of the nickel mold, and the shape reproducibility was evaluated at the following two levels.

[0525] ○: Dimensional change in the pattern shape of the nickel mold and cured resin is less than 5%, Х: Dimensional change is 5% or more or chipping is visible in the pattern

[0526] (7) Mold corrosion

[0527] The composition obtained in Table 4 was applied to a thickness of 10 μm using a bar coater on a transfer mold (hereinafter referred to as the "nickel mold") having a fine pattern (bowl-shaped pattern with a diameter of 10 μm and a film thickness of 5 μm) formed on a nickel-plated stainless steel plate, then laminated with an adhesive PET, irradiated with ultraviolet light under the same conditions as the moist heat test, and cured.

[0528] Afterwards, the mold was maintained at 40°C and 80% RH for 24 hours, and a metal corrosion test was performed. Changes in the appearance of the nickel mold after the metal corrosion test were observed visually and evaluated at the following three levels.

[0529] ○: No change, △: Part of the nickel mold discolored, Х: Entire surface of the nickel mold discolored

[0530]

[0531]

[0532]

[0533] Based on Table 2, the compositions of Examples 1 to 3 containing component (A) (compounds a1 to a3) obtained in Manufacturing Examples 1 to 3 had low viscosity, good insulation reliability in the moist heat test, and excellent performance as active energy beam curing type coating compositions. In contrast, the compositions of Comparative Examples 1 and 2 containing component (A)' (compounds a'2 and a'3) obtained in Comparative Examples 2 and 3, respectively, showed a large change in appearance in the moist heat test and also had low insulation reliability.

[0534] In addition, based on Table 3, the compositions of Examples 4 to 6 containing component (A) (compounds a1 to a3) obtained in Manufacturing Examples 1 to 3 showed excellent adhesion and wet heat test results, and demonstrated excellent performance as active energy beam curing adhesive compositions. In contrast, the compositions of Comparative Examples 3 and 4 containing component (A)' (compounds a'2 and a'3) obtained in Comparative Examples 2 and 3, respectively, showed significantly reduced adhesion in the wet heat test.

[0535] In addition, upon reviewing based on Table 4, the compositions of Examples 7 to 9 containing component (A) (compounds a1 to a3) obtained in Manufacturing Examples 1 to 3 were desirable compositions for active energy beam curable extrusion material compositions because they exhibited excellent shape reproducibility and good mold corrosion resistance when used as active energy beam curable extrusion material compositions. In contrast, the compositions of Comparative Examples 5 and 6 containing component (A)' (compounds a'2 and a'3) obtained in Comparative Examples 2 and 3, respectively, were unsuitable for this application because Comparative Example 5 had a problem with shape reproducibility due to its high viscosity, and Comparative Examples 5 and 6 also had a problem with mold corrosion resistance. Industrial applicability

[0536] The curable composition of the present invention can preferably be used as an active energy beam curable composition, and furthermore, can preferably be used as a solvent-free active energy beam curable composition.

[0537] The curable composition of the present invention can be used for various purposes, and may include coating agents such as paints, adhesives, pressure-sensitive adhesives, inks, molding agents for forming excipient materials, and pattern-forming agents such as resists, and can be preferably used in coating agents, adhesives, and excipient materials.

Claims

Claim 1 (A) A composition comprising a component, wherein the component (A) comprises a compound represented by the following formula (a), and the chlorine concentration contained in the component (A) is less than 100 ppm and the sodium concentration is less than 100 ppb [Chemical Formula 1] [In Equation (a), R a represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R b means an alkylene oxide group having 1 to 20 repeating units. Claim 2 A curable composition according to claim 1, wherein component (A) is 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. 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. Claim 3 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. Claim 4 A curable composition according to claim 2, wherein the catalyst X is 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, and a compound having a pyridine ring or its salt or complex. Claim 5 A curable composition according to claim 2, wherein the catalyst Y is at least one of zinc organic acid and zinc diketone enolate. Claim 6 A curable composition according to claim 1, wherein in addition to component (A), component (B): a photopolymerization initiator. Claim 7 A curable composition according to claim 1, wherein in addition to component (A), component (C): a thermal polymerization initiator. Claim 8 A curable composition according to claim 1, wherein in addition to component (A), component (D): a compound having an ethylenically unsaturated group other than component (A). Claim 9 A curable coating composition comprising the curable composition described in claim 1. Claim 10 A curable excipient material composition comprising the curable composition described in claim 1. Claim 11 A curable adhesive composition comprising the curable composition described in claim 1. Claim 12 A method for preparing a curable composition comprising a process for preparing a component (A) in which the chlorine concentration contained in the mixture is less than 100 ppm and the sodium concentration is less than 100 ppb, wherein the component (A) comprises a compound represented by the following formula (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. [In Equation (a), R a represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R b means an alkylene oxide group having 1 to 20 repeating units. Claim 13 A method for preparing a curable composition according to claim 12, wherein the compound having one CH2=C(R)-(C=O)- group in the molecule is an alkoxyalkyl (meth)acrylate. Claim 14 A method for preparing a curable composition according to claim 12 or claim 13, wherein the catalyst X is 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, and a compound having a pyridine ring or its salt or complex. Claim 15 A method for preparing a curable composition according to claim 12 or claim 13, wherein the catalyst Y is at least one of zinc organic acid and zinc diketone enolate. Claim 16 delete Claim 17 delete

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