WO2018117062A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

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Publication number
WO2018117062A1
WO2018117062A1 PCT/JP2017/045406 JP2017045406W WO2018117062A1 WO 2018117062 A1 WO2018117062 A1 WO 2018117062A1 JP 2017045406 W JP2017045406 W JP 2017045406W WO 2018117062 A1 WO2018117062 A1 WO 2018117062A1
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Prior art keywords
meth
component
acrylate
group
compound
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PCT/JP2017/045406
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English (en)
Japanese (ja)
Inventor
橋本　直樹
佐内　康之
加藤　久雄
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東亞合成株式会社
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Priority to JP2018557982A priority Critical patent/JPWO2018117062A1/ja
Publication of WO2018117062A1 publication Critical patent/WO2018117062A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate

Definitions

  • the present invention relates to a curable composition, and preferably to an active energy ray curable composition. Since the composition of the present invention is excellent in rapid curability, antifogging properties, and flex resistance, particularly when used as an active energy ray curable composition, it can be preferably used in coating agents that require these properties.
  • an acryloyl group and / or a methacryloyl group is represented as a (meth) acryloyl group
  • an allyl group and / or a methallyl group is represented as a (meth) allyl group
  • an acrylate and / or methacrylate is represented by a (meth) acrylate.
  • acrylic acid and / or methacrylic acid is represented as (meth) acrylic acid.
  • (Meth) acrylate is cured by irradiation with active energy rays such as ultraviolet rays and electron beams, or by heating, so as a crosslinking component of a composition such as paint, ink, adhesive, optical lens, filler and molding material, Or it is used in large quantities as a reactive diluent component.
  • a composition containing (meth) acrylate having two or more (meth) acryloyl groups and one or more hydroxyl groups in the molecule is derived from fast curing properties derived from a plurality of (meth) acryloyl groups and hydroxyl groups. It is used in various applications utilizing hydrophilicity and reactivity.
  • the composition containing pentaerythritol tri (meth) acrylate is used in a large amount for various applications because of its industrial availability.
  • a composition containing pentaerythritol tri (meth) acrylate has a feature of exhibiting antifogging properties derived from its hydroxyl group (see Patent Document 1).
  • GLY-DA glycerin di (meth) acrylate
  • GLY-DA glycerin di (meth) acrylate having two or more (meth) acryloyl groups and one or more hydroxyl groups in the molecule.
  • GLY-DA has problems in industrial production, it is more expensive than pentaerythritol tri (meth) acrylate and its market distribution is small.
  • unreacted (meth) acrylic acid and the catalyst are removed by extraction washing using water or an aqueous sodium hydroxide solution.
  • the target GLY-DA is distributed to the aqueous layer side because of its high hydrophilicity, and the yield is very low.
  • Patent Document 2 repeats extraction cleaning and concentration using a plurality of organic solvents, and there is room for improvement in productivity.
  • the yield to GLY-DA is very low. Further, there is no description of a purification method for removing the catalyst after completion of the reaction.
  • the target GLY-DA is obtained in high yield because it does not undergo extraction washing using water or an aqueous sodium hydroxide solution.
  • (meth) acrylic acid chloride is expensive, very reactive and unstable, requires strict handling and storage, is extremely corrosive, Since a corrosion resistant reactor is required, there are significant problems in cost and workability.
  • the present inventors have intensively studied in order to provide a curable composition in which the constituent components are industrially available and the cured product is excellent in hardness and antifogging properties.
  • the present inventors have intensively studied to solve the above problems. As a result, by using a specific basic catalyst or phosphine-based catalyst, and a zinc-based catalyst in combination, glycerol and a compound having one (meth) acryloyl group are transesterified to produce a reaction containing GLY-DA.
  • the present invention has been completed by finding that a product can be obtained in a high yield and that a curable composition containing the reaction product is effective in solving the above-mentioned problems.
  • the present invention will be described in detail.
  • the constituents are industrially available, are fast curable, and the cured product has excellent hardness and antifogging properties. It becomes.
  • the present invention is obtained by subjecting glycerol and a compound having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”) to an ester exchange reaction in the presence of the following catalysts X and Y (
  • the present invention relates to a curable composition comprising a (A) component which is a (meth) acrylate mixture, which contains GLY-DA and has a hydroxyl value of 65 mgKOH / g or more.
  • Catalyst X One or more selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof, and phosphine or a salt or complex thereof Compound.
  • Catalyst Y Compound containing zinc.
  • Component (A) is a (meth) acrylate mixture obtained by subjecting glycerol and a monofunctional (meth) acrylate to an ester exchange reaction in the presence of the catalysts X and Y, and is a GLY-DA A mixture containing [glycerin di (meth) acrylate] and having a hydroxyl value of 65 mgKOH / g or more.
  • Component (A) is a reaction mixture mainly composed of GLY-DA obtained by the transesterification reaction, and is a mixture containing glycerin mono (meth) acrylate and glycerin tri (meth) acrylate in addition to the compound,
  • the value is 65 mgKOH / g or more.
  • the hydroxyl value of the component (A) is preferably 65 to 400 mgKOH / g, more preferably 100 to 350 mgKOH / g, and particularly preferably 150 to 300 mgKOH / g. When the hydroxyl value of the component (A) is less than 65 mgKOH / g, the antifogging property of the cured film of the composition is lowered.
  • the cured film of a composition can be made excellent in hardness by making a hydroxyl value into 400 mgKOH / g or less.
  • the hydroxyl value means the number of mg of potassium hydroxide equivalent to the hydroxyl group in 1 g of a sample.
  • component (A) monofunctional (meth) acrylate
  • catalyst X monofunctional (meth) acrylate
  • catalyst Y catalyst Y
  • a method for producing component (A) a method for producing component (A)
  • preferred forms of component (A) will be described.
  • the glycerin used as a raw material for the glycerin (A) component may contain a small amount of glycerin condensate such as water and diglycerin. Although there is no restriction
  • concentration of the peroxide contained in the glycerol used as a raw material of a component it is preferable that it is 5 wtppm or less, More preferably, it is 2 wtppm or less.
  • concentration of the peroxide is 5 wtppm or less, polymerization of the (meth) acryloyl group is suppressed during production, and the color tone of the reaction solution is good.
  • glycerin and one or more polyhydric alcohols other than glycerin may be used in any combination as long as the effects are not impaired.
  • other polyhydric alcohols may be used in any combination as long as the effects are not impaired.
  • 50 weight part or less is preferable with respect to a total of 100 weight part of glycerol.
  • the monofunctional (meth) acrylate used as a raw material for the monofunctional (meth) acrylate (A) component is a compound having one (meth) acryloyl group in the molecule.
  • it is represented by the following general formula (1).
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents an organic group having 1 to 50 carbon atoms.
  • R 2 in the general formula (1) include carbon such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, and 2-ethylhexyl group.
  • An alkyl group of formula 1 to 8 an alkoxyalkyl group such as 2-methoxyethyl group, 2-ethoxyethyl group and 2-methoxybutyl group, N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group, N And dialkylamino groups such as N, N-dimethylaminopropyl group and N, N-diethylaminopropyl group.
  • R 2 in the general formula (1) include the functional groups described in JP 2017-39916 A, JP 2017-39917 A, and International Publication No. 2017/033732. .
  • these monofunctional (meth) acrylates can be used alone or in combination of two or more.
  • carbon such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate
  • alkyl (meth) acrylates having an alkyl group of 1 to 8
  • alkoxyalkyl (meth) acrylates such as 2-methoxyethyl acrylate
  • N N-dimethylaminoethyl (meth) acrylate, particularly for glycerin.
  • the proportion of glycerin and monofunctional (meth) acrylate used in the method for producing component (A) is not particularly limited, but 0.4 to 10.0 mol of monofunctional (meth) acrylate per mol of hydroxyl group of glycerin.
  • the amount is preferably 0.6 to 5.0 mol.
  • Catalyst X Cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof (hereinafter referred to as “azabicyclo compound”), amidine or a salt or complex thereof (hereinafter referred to as “amidine compound”), a compound having a pyridine ring or One or more compounds selected from the group consisting of salts or complexes thereof (hereinafter referred to as “pyridine compounds”) and phosphines or salts or complexes thereof (hereinafter referred to as “phosphine compounds”).
  • Catalyst Y Compound containing zinc.
  • the catalyst X and the catalyst Y will be described.
  • the catalyst X in the method for producing the component (A) is one or more compounds selected from the group consisting of an azabicyclo compound, an amidine compound, a pyridine compound, and a phosphine compound.
  • the catalyst X is preferably one or more compounds selected from the group consisting of an azabicyclo compound, an amidine compound, and a pyridine compound, among the compound groups described above. These compounds are excellent in catalytic activity and can preferably produce the component (A), and also form a complex with catalyst Y described later during and after the reaction, and the complex is a reaction solution after completion of the reaction by a simple method such as adsorption. Can be easily removed from.
  • the complex with the catalyst Y becomes hardly soluble in the reaction solution, the azacyclo compound can be more easily removed by filtration and adsorption.
  • the phosphine compound is excellent in catalytic activity, it is difficult to form a complex with the catalyst Y, or when the complex is formed, it is easily soluble in the reaction solution, and the phosphine compound in the reaction solution after the completion of the reaction. Since most of the compound or complex remains dissolved, it is difficult to remove from the reaction solution by a simple method such as filtration and adsorption. For this reason, the phosphine-based catalyst remains in the final product, thereby causing turbidity and catalyst precipitation during storage of the product, and increasing the viscosity or gelation over time. May cause problems.
  • the azabicyclo compound include various compounds as long as the compound satisfies the cyclic tertiary amine having an azabicyclo structure, a salt of the amine, or a complex of the amine.
  • Preferred compounds include quinuclidine, 3 -Hydroxyquinuclidine, 3-quinuclidinone, 1-azabicyclo [2.2.2] octane-3-carboxylic acid, and triethylenediamine (also known as 1,4-diazabicyclo [2.2.2] octane. DABCO ”).
  • Specific examples of the azabicyclo compounds include the compounds mentioned in JP-A-2017-39916, JP-A-2017-39917, and International Publication No. 2017/033732.
  • amidine compounds include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 1-allylimidazole, 1 , 8-diazabicyclo [5.4.0] undec-7-ene (hereinafter referred to as “DBU”), 1,5-diazabicyclo [4.3.0] non-5-ene (hereinafter referred to as “DBN”) N-methylimidazole hydrochloride, DBU hydrochloride, DBN hydrochloride, N-methylimidazole acetate, DBU acetate, DBN acetate, N-methylimidazole acrylate, DBU acrylate, DBN acrylate, and Examples include phthalimide DBU.
  • 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”) and the like.
  • DMAP N, N-dimethyl- 4-aminopyridine
  • Specific examples of the pyridine-based compound include compounds described in JP-A-2017-39916, JP-A-2017-39917 and International Publication No. 2017/033732.
  • Examples of the phosphine compound include compounds having a structure represented by the following general formula (2).
  • R 3 , R 4 and R 5 are each a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, a carbon number of 6 Means an aryl group having ⁇ 24 or a cycloalkyl group having 5 to 20 carbon atoms.
  • R 3 , R 4 and R 5 may be the same or different.
  • phosphine compound examples include triphenylphosphine, tris (4-methoxyphenyl) phosphine, tri (p-tolyl) phosphine, tri (m-tolyl) phosphine, tris (4-methoxy-3,5-dimethylphenyl). ) Phosphine and tricyclohexylphosphine.
  • phosphine compounds include the compounds mentioned in JP 2017-39916 A, JP 2017-39917 A, and International Publication No. 2017/033732.
  • these catalysts X can be used alone or in any combination of two or more.
  • quinuclidine, 3-quinuclidinone, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, DBN and DMAP are preferable, and particularly have good reactivity with most polyhydric alcohols.
  • the readily available 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU and DMAP are preferred.
  • the proportion of catalyst X used in the method for producing component (A) is not particularly limited, but 0.0001 to 0.5 mol of catalyst X is preferably used with respect to 1 mol of hydroxyl group of glycerin, more preferably 0. .0005 to 0.2 mol.
  • the catalyst X in an amount of 0.0001 mol or more, the yield of the reaction product containing the target GLY-DA can be increased.
  • the coloring process can be suppressed, and the purification process after completion of the reaction can be simplified.
  • the catalyst Y is a compound containing zinc.
  • various compounds can be used as long as they contain zinc, but organic acids zinc and zinc diketone enolate are preferable because of excellent reactivity.
  • organic acid zinc include dibasic acid zinc such as zinc oxalate and a compound represented by the following general formula (3).
  • R 6 and R 7 are each a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, or a 6 to 24 carbon atoms.
  • An aryl group or a cycloalkyl group having 5 to 20 carbon atoms is meant.
  • R 6 and R 7 may be the same or different.
  • the compound of the formula (3) is preferably a compound in which R 6 and R 7 are a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms.
  • the linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms is a functional group having no halogen atom such as fluorine and chlorine, and the catalyst Y having the functional group is: This is preferable because a reaction product containing the desired GLY-DA can be produced in a high yield.
  • Examples of zinc diketone enolate include compounds represented by the following general formula (4).
  • R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are each a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a group having 1 to 20 carbon atoms.
  • a linear or branched alkenyl group, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms is meant.
  • R 8 , R 9 , R 10 , R 11 , R 12 and R 13 may be the same or different.
  • the compound containing zinc represented by the general formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octylate, zinc neodecanoate, zinc laurate, zinc myristate, Examples include zinc stearate, zinc cyclohexanebutyrate, zinc 2-ethylhexanoate, zinc benzoate, zinc t-butylbenzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and zinc methacrylate.
  • this complex with the hydrate, solvate, and catalyst X is also component (A). It can be used as the catalyst Y in the production method.
  • the compound containing zinc represented by the 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.
  • this complex with the hydrate, solvate, and catalyst X is also component (A). It can be used as the catalyst Y in the production method.
  • the organic acid zinc and zinc diketone enolate in the catalyst Y can be used directly, but these compounds can also be generated and used in the reaction system.
  • zinc compounds such as metal zinc, zinc oxide, zinc hydroxide, zinc chloride and zinc nitrate (hereinafter referred to as “raw zinc compounds”) are used as raw materials.
  • raw zinc compounds raw zinc compounds and organic acids are used.
  • zinc diketone enolate a method of reacting a raw material zinc compound and 1,3-diketone can be used.
  • these catalysts Y can be used alone or in any combination of two or more.
  • zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, and zinc acetylacetonate are preferable, and particularly shows good reactivity with most polyhydric alcohols and is easily available.
  • Zinc acetate, zinc acrylate and zinc acetylacetonate are preferred.
  • the ratio of the catalyst Y used in the method for producing the component (A) is not particularly limited, but 0.0001 to 0.5 mol of the catalyst Y is preferably used with respect to 1 mol of the total hydroxyl group of glycerol, more preferably 0.0005 to 0.2 mol.
  • the catalyst Y in an amount of 0.0001 mol or more, the yield of the reaction product containing the target GLY-DA can be increased. The coloring process can be suppressed, and the purification process after completion of the reaction can be simplified.
  • Component (A) is produced by subjecting glycerol and a monofunctional (meth) acrylate to an ester exchange reaction in the presence of the catalysts X and Y.
  • the ratio of the catalyst X and the catalyst Y in the method for producing the component (A) is not particularly limited, but it is preferable to use 0.005 to 10.0 moles of the catalyst X with respect to 1 mole of the catalyst Y.
  • the amount is preferably 0.05 to 5.0 mol.
  • the combination of the catalyst X and the catalyst Y used in the present invention is preferably a combination of the catalyst X being an azabicyclo compound, the catalyst Y being a compound represented by the general formula (3), and the azabicyclo compound being DABCO. And a combination in which the compound represented by the general formula (3) is zinc acetate and / or zinc acrylate is particularly preferable. In addition to being able to obtain a reaction product containing GLY-DA in a good yield, this combination is excellent in color after the reaction is finished (small yellowishness). It can be used suitably. Furthermore, since the catalyst is available at a relatively low cost, it is an economically advantageous production method.
  • the catalyst X and catalyst Y used in the present invention may be added from the beginning of the above reaction or may be added in the middle. Moreover, a desired use amount may be added all at once, or may be added in divided portions.
  • the reaction temperature in the method for producing the component (A) is preferably 40 ° C. to 180 ° C., more preferably 60 ° C. to 160 ° C.
  • the reaction temperature By setting the reaction temperature to 40 ° C. or higher, the reaction rate can be increased, and by setting it to 180 ° C. or lower, thermal polymerization of (meth) acryloyl groups in raw materials and products is suppressed, and coloring of the reaction liquid is performed. And the purification process after completion of the reaction can be simplified.
  • the reaction pressure in the method for producing the component (A) is not particularly limited as long as the predetermined reaction temperature can be maintained, and may be performed in a reduced pressure state or in a pressurized state.
  • the reaction pressure is preferably 0.000001 to 10 MPa (absolute pressure).
  • the monohydric alcohol derived from monofunctional (meth) acrylate byproduces with progress of transesterification.
  • a part of the hydroxyl group of glycerin for example, about 50 mol%) is (meth) acrylated
  • the monohydric alcohol is allowed to coexist in the reaction system to be in an equilibrium state, and the catalyst is removed by adsorption or deactivation.
  • the catalyst is removed by adsorption or deactivation.
  • a product having a controlled acrylate ratio can be stably produced.
  • the hydroxyl group of glycerin is positively (meth) acrylated, it is preferable to discharge the monohydric alcohol out of the reaction system to further promote the progress of the transesterification reaction.
  • the reaction can be carried out without using a solvent, but a solvent may be used as necessary.
  • a solvent include n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, diamyl.
  • Hydrocarbons such as benzene, triamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, isopropyltoluene, decalin and tetralin; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diethyl acetal, dihexyl acetal , T-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, trioxane, dioxane, anisole, diphenyl ether Ethers such as tellurium, dimethylcellosolve, diglyme, triglyme and tetraglyme; crown ethers such as 18-crown-6; esters such as methyl benzoate and ⁇ -butyrolactone; acetone, methyl e
  • solvents at least one solvent selected from the group consisting of hydrocarbons, ethers, carbonate compounds and ionic liquids is preferred. These solvents may be used alone, or two or more kinds may be arbitrarily combined and used as a mixed solvent.
  • an inert gas such as argon, helium, nitrogen and carbon dioxide may be introduced into the system for the purpose of maintaining a good color tone of the reaction solution.
  • an oxygen-containing gas may be introduced into the system.
  • the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like.
  • a method for introducing the oxygen-containing gas there is a method in which the oxygen-containing gas is dissolved in the reaction solution or blown into the reaction solution (so-called bubbling).
  • a polymerization inhibitor in the reaction liquid for the purpose of preventing the polymerization of the (meth) acryloyl group.
  • the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4-tert -Butylcatechol, benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine
  • Organic polymerization inhibitors such as -1-oxyl
  • inorganic polymerization inhibitors such as copper chloride, copper sulfate and iron sulfate
  • organic salt systems such as copper dibutyldithiocarbamate and N-nitro
  • a polymerization inhibitor may be added individually by 1 type, or may be added in combination of 2 or more types, may be added from the beginning of this invention, and may be added from the middle. Moreover, a desired use amount may be added all at once, or may be added in divided portions. Moreover, you may add continuously via a rectification column.
  • the addition ratio of the polymerization inhibitor is preferably 5 to 30,000 wtppm in the reaction solution, more preferably 25 to 10,000 wtppm. By setting this ratio to 5 wtppm or more, the polymerization inhibition effect can be sufficiently exerted, and by setting it to 30,000 wtppm or less, coloring of the reaction solution can be suppressed, and the purification process after completion of the reaction can be simplified. Moreover, the fall of the cure rate of the (A) component obtained can be prevented.
  • reaction time in the production method of component (A) varies depending on the type and amount of catalyst used, reaction temperature, reaction pressure, etc., but is preferably 0.1 to 150 hours, more preferably 0.5 to 80 hours.
  • the manufacturing method of a component can be implemented by any method of a batch type, a semibatch type, and a continuous type.
  • glycerin, monofunctional (meth) acrylate, a catalyst and a polymerization inhibitor are charged into a reactor, and stirred at a predetermined temperature while bubbling oxygen-containing gas into the reaction solution. Then, it can implement by the method of producing
  • the separation / purification operation include an adsorption operation, a crystallization operation, a filtration operation, a distillation operation, and an extraction operation, and these are preferably combined.
  • the adsorption operation includes adsorption of a catalyst by an adsorbent, and examples of the adsorbent include aluminum silicate.
  • Examples of the crystallization operation include cooling crystallization and concentrated crystallization.
  • Examples of the filtration operation include pressure filtration, suction filtration, and centrifugal filtration.
  • Examples of the distillation operation include simple distillation, fractional distillation, molecular distillation, and steam distillation.
  • Examples of the extraction operation include solid-liquid extraction and liquid-liquid extraction.
  • a solvent may be used in the separation and purification operation.
  • Component (A) is a mixture of reaction products containing GLY-DA obtained by transesterification of glycerin and monofunctional (meth) acrylate, and the number of (meth) acryloyl groups is different It is a mixture of (meth) acrylate and side reaction product.
  • the component (A) includes GLY-DA, glycerin mono (meth) acrylate and glycerin tri (meth) acrylate as (meth) acrylates having different numbers of (meth) acryloyl groups,
  • a side reaction product having a Michael addition type structure As a side reaction product having a Michael addition type structure, a side reaction product having a Rauhut-Currier reaction type structure, a side reaction product derived from a polymerization inhibitor, and the like.
  • it contains a small amount of unreacted glycerin used as a raw material.
  • the content of the above-mentioned side reaction product contained in the component (A) includes the side reaction product having the Michael addition type structure, the side reaction product having the Rauhut-Curier reaction type structure, and the side reaction derived from the polymerization inhibitor.
  • the total weight of the product and glycerin used as a raw material is preferably less than 40% by weight, more preferably less than 30% by weight, and still more preferably less than 20% by weight. When the total content of these by-products is less than 40% by weight, the viscosity of the component (A) is moderate and excellent in handleability, the curing rate of the curable composition containing the component (A), and the cured film Excellent hardness.
  • the purity of GLY-DA contained in component (A) is preferably 30% or more, more preferably 40% or more, and still more preferably 50%, as determined using the following formula (1). % Or more.
  • the purity of GLY-DA is preferably 30% or more, more preferably 40% or more, and still more preferably 50%, as determined using the following formula (1). % Or more.
  • GLY-DA (%) [(D ⁇ 1.27) / (M ⁇ 1.74 + D ⁇ 1.27 + T)] ⁇ 100
  • D, M, and T in the calculation formula (1) are obtained by analyzing the component (A) using a high performance liquid chromatograph (hereinafter referred to as “HPLC”) equipped with an ultraviolet (UV) detector. Mean value.
  • D GLY-DA peak area at 210 nm
  • M peak area of glycerol mono (meth) acrylate at 210 nm
  • T peak area of glycerol tri (meth) acrylate at 210 nm
  • the peak area by HPLC is as follows: It means the value measured in.
  • ⁇ Detector UV detector, detection wavelength 210 nm
  • Column type A column packed with silica gel modified with an alkyl group having 18 carbon atoms. Specifically, ACQUITY UPLC BEH C18 (Part No. 186002350, manufactured by Waters Co., Ltd., column inner diameter 2.1 mm, column length 50 mm )
  • (A) A value obtained by gel permeation chromatography (hereinafter referred to as “GPC”) measurement as an index of the weight average molecular weight (hereinafter referred to as “Mw”) of the component, which is a monofunctional (meth) acrylate and
  • Mw weight average molecular weight
  • the Mw of the component (A) excluding the detection peak derived from the solvent is preferably less than 350, more preferably less than 340, and particularly preferably less than 330.
  • the component (A) has an Mw of less than 350, it means that there are few high molecular weight bodies (hereinafter referred to as “side reaction high molecular weight bodies”) due to side reactions (Michael addition, etc.) other than (meth) acrylate formation.
  • the component (A) is preferable because it has a low viscosity and is excellent in operability.
  • the reaction product containing GLY-DA obtained by the dehydration esterification reaction or the like contains more side reaction high molecular weight products than the component (A) obtained by the transesterification reaction of the present invention.
  • These side-reaction high molecular weight substances not only cause high viscosity, but are also distributed to the aqueous layer in the extraction washing process using water or aqueous sodium hydroxide solution after the reaction is completed, so the yield is greatly increased. descend.
  • the (meth) acrylate is preferably an acrylate from the viewpoint of the reactivity during the transesterification reaction and the rapid curability of the component (A).
  • Curable composition TECHNICAL FIELD This invention relates to the curable composition containing the said (A) component.
  • a method for producing the composition a mixture of reaction products containing GLY-DA obtained by subjecting glycerol and a monofunctional (meth) acrylate to a transesterification reaction in the presence of the catalysts X and Y, A production method including a step of producing a mixture (A) having a hydroxyl value of 65 mgKOH / g or more is preferred. According to the said manufacturing method, since (A) component can be obtained with a high yield, it is excellent in cost and productivity.
  • the component (A) obtained by the production method is preferable because it has a low amount of side reaction high molecular weight and is easy to handle because of low viscosity, and is excellent in fast curability, hardness of the cured product and antifogging property. What is necessary is just to follow the manufacturing method of above-described (A) component as the said process. Furthermore, when blending other components described later, the component (A) and other components may be stirred and mixed.
  • the component (A) When used for a preferred application such as a coating agent, ink, and pattern formation, it may be appropriately set according to the purpose, preferably 1 to 100,000 mPa ⁇ s, more preferably 5 to 50, 000 mPa ⁇ s. By setting it as the said viscosity range, it is excellent in the leveling property at the time of the coating of a composition, and shall be excellent in the external appearance of hardened
  • the viscosity in the present invention means a value measured at 25 ° C. using an E type viscometer (cone plate type viscometer).
  • the content of the component (A) in the composition is preferably 20 to 100% by weight with respect to 100% by weight of the total amount of the curable components in terms of fast curability, hardness and antifogging, More preferably, it is ⁇ 100% by weight.
  • the “curable component” is “a component that is cured by heat or active energy rays”, means the component (A), and when blending the component (D) described later, ) And (D) components.
  • compounds having polymerizable functional groups other than the components (A) and (D) such as cationic curable compounds (for example, epoxy compounds and oxetane compounds) and reactive surfactants (hereinafter “other polymerizable components”).
  • the “curable component” means “(A) component and other polymerizable component” and “(A) component, (D) component and other polymerizable component”.
  • composition of this invention can be used for both an active energy ray hardening-type composition and a thermosetting type composition, an active energy ray hardening-type composition is preferable.
  • the composition of the present invention can be used in any form of a solvent-free composition containing no organic solvent, a solvent-type composition containing an organic solvent, and an aqueous composition in which the component (A) is dissolved or dispersed in water. can do.
  • a commonly used emulsifier or a reactive emulsifier described later can be used as the dispersant.
  • composition of the present invention contains (A) as an essential component, but various components can be blended depending on the purpose.
  • Other preferred components include a photopolymerization initiator (hereinafter referred to as “component (B)”), a thermal polymerization initiator (hereinafter referred to as “component (C)”), and an ethylenic polymer other than the component (A).
  • component (D) Compound having saturated group [hereinafter referred to as “component (D)”], pigment or dye [hereinafter referred to as “component (E)”], organic solvent or water (hereinafter referred to as “component (F)”), colloidal Inorganic fine particles (hereinafter referred to as “component (G)”), polymers (hereinafter referred to as “component (H)”), reactive surfactants (hereinafter referred to as “component (I)”), and the like.
  • component (D) pigment or dye [hereinafter referred to as “component (E)”]]
  • component (F) organic solvent or water
  • component (G) colloidal Inorganic fine particles
  • component (H) polymers
  • component (I) reactive surfactants
  • composition of the present invention when used as an active energy ray curable composition and further used as an electron beam curable composition, it does not contain the component (B) (photopolymerization initiator) and is an electron. It can also be cured by a wire.
  • component (B) photopolymerization initiator
  • the composition of the present invention is used as an active energy ray-curable composition, particularly when ultraviolet rays or visible rays are used as active energy rays, it is necessary to further contain the component (B).
  • an electron beam is used as the active energy ray, it is not always necessary to add it, but a small amount can be added as necessary in order to improve curability.
  • component (B) examples include benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl.
  • Examples of other compounds include benzyl, ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate, methyl phenylglyoxylate, ethyl anthraquinone, phenanthrenequinone, camphorquinone, and the like.
  • the content ratio of the component (B) is preferably 10 parts by weight or less, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the curable components.
  • the component (B) may be carried out in accordance with conventional means of normal radical thermal polymerization.
  • the reaction rate is further increased after photocuring in combination with the component (C) (thermal polymerization initiator).
  • thermosetting can also be performed.
  • thermosetting type composition (C) component
  • thermosetting type composition (C) component (thermal polymerization initiator) can be mix
  • component (C) various compounds can be used, and organic peroxides and azo initiators are preferable.
  • organic peroxide examples include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 2-bis (4,4-dibutylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t- Butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, 2,5-dimethyl-2 5-di (m-tol
  • azo compound examples include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. Azodi-t-octane, azodi-t-butane, and the like. These may be used alone or in combination of two or more. Moreover, an organic peroxide can also be made into a redox reaction by combining with a reducing agent.
  • component (C) As a content rate of a component, 10 weight part or less is preferable with respect to 100 weight part of sclerosing
  • the component (C) When the component (C) is used alone, it may be carried out in accordance with conventional means for radical thermal polymerization. In some cases, the reaction rate is further used after being combined with the component (B) (photopolymerization initiator) and photocured. For the purpose of improving the temperature, thermosetting can also be performed.
  • Component (D) is a compound having an ethylenically unsaturated group other than component (A), and is blended for the purpose of imparting various physical properties to the cured product of the composition.
  • the ethylenically unsaturated group in component (D) include a (meth) acryloyl group, a (meth) acrylamide group, a maleimide group, a vinyl group, and a (meth) allyl group, with a (meth) acryloyl group being preferred.
  • “monofunctional” means a compound having one ethylenically unsaturated group
  • “X function” means a compound having X ethylenically unsaturated groups
  • “polyfunctional”. Means a compound having two or more ethylenically unsaturated groups.
  • Specific examples of the component (D) include (meth) acrylate compounds, (meth) acrylamides, vinyl ether compounds, maleimide compounds, and the like, and (meth) acrylate compounds are preferred. Among these compounds, acrylate compounds, acrylamide compounds, or vinyl ether compounds are preferable from the viewpoint of curability, and acrylate compounds are more preferable.
  • the polyfunctional ethylenically unsaturated compound is a compound having two ethylenically unsaturated groups (D-1) [hereinafter referred to as “component (D-1)”], 3 or more Examples thereof include compounds having an ethylenically unsaturated group (D-2) [hereinafter referred to as “component (D-2)”] and monofunctional ethylenically unsaturated compounds (hereinafter referred to as “component (D-3)”). .
  • component (D-1) ethylenically unsaturated groups
  • component (D-2) ethylenically unsaturated group
  • component (D-3) monofunctional ethylenically unsaturated compounds
  • Component (D-1) is a compound having two ethylenically unsaturated groups other than the component (A), and may be a low molecular weight compound or an oligomer. .
  • a low molecular weight monomer is blended as the component (D-1)
  • a low-viscosity composition can be obtained without a solvent.
  • a high molecular weight urethane (meth) acrylate oligomer is blended, it is possible to impart elongation to the cured film and improve adhesion to the adherend.
  • component (D-1) include, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di
  • Di (meth) acrylates of aliphatic diols such as (meth) acrylate and nonanediol di (meth) acrylate
  • Di (meth) acrylates of alicyclic diols such as cyclohexanedimethanol di (meth) acrylate, norbornane dimethylol di (meth) acrylate and tricyclodecane dimethylol di (meth) acrylate
  • Polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol
  • component (D-1) examples include 2-vinyloxyethyl (meth) acrylate, 2-vinyloxyethoxyethyl (meth) acrylate, 1,4-butanediol divinyl ether, neopentyl glycol divinyl ether, cyclohexane di Bifunctional monomers including functional groups other than (meth) acryloyl groups such as methanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and dipropylene glycol divinyl ether are also included.
  • the preferable content varies depending on the use of the composition of the present invention.
  • the content of the component (D-1) is preferably 0 to 80 parts by weight and preferably 0 to 70 parts by weight with respect to 100 parts by weight of the curable component. More preferred.
  • the content of the component (D-1) is preferably 0 to 40 parts by weight, more preferably 0 to 20 parts by weight with respect to 100 parts by weight of the curable component.
  • Component (D-2) is a compound having three or more ethylenically unsaturated groups other than the component (A), and may be a low molecular weight compound or an oligomer. good.
  • component (D-2) include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri- or tetra (meth) acrylate, ditrimethylolpropane tri- or tetra (meth) acrylate, diglycerin tri- Or tetra (meth) acrylate, dipentaerythritol tri, tetra, penta or hexa (meth) acrylate, tripentaerythritol tri, tetra, penta, hexa, hepta, and octa (meth) acrylate, polypentaerythritol poly (meta ) Polyol, poly (meth) acrylate, such as acrylate, polyglycerin poly (meth) acrylate; Tri (meth) acrylate of glycerin alkylene oxide adduct, tri (meth) acrylate of trimethylo
  • alkylene oxide adduct examples include ethylene oxide adduct, propylene oxide adduct, ethylene oxide and propylene oxide adduct, and the like.
  • organic polyisocyanate examples include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated xylylene. Examples thereof include range isocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate trimer, and the like.
  • the composition of the present invention when used as a hard coat, it preferably contains dipentaerythritol poly (meth) acrylate as the component (D-2), and can improve the curability and hardness of the cured composition. it can.
  • the component (D-2) preferably contains a urethane (meth) acrylate having 3 or more (meth) acryloyl groups, and the curability and flexibility of the cured composition can be improved.
  • dipentaerythritol poly (meth) acrylate, component (D-2-1) and urethane (meth) acrylate having three or more (meth) acryloyl groups may be used in combination. The scratch resistance of the cured product can be improved.
  • the preferred content varies depending on the use of the composition of the present invention.
  • the amount is preferably 0 to 80 parts by weight, more preferably 0 to 70 parts by weight with respect to 100 parts by weight of the curable component.
  • the amount is preferably 0 to 40 parts by weight, more preferably 0 to 20 parts by weight with respect to 100 parts by weight of the curable component.
  • Component (D-3) is a compound having one ethylenically unsaturated group per molecule, and may be a low molecular weight compound or an oligomer. By blending the component (D-3), it is possible to impart elongation to the cured film or improve the adhesion to the adherend.
  • component (D-3) include the same compounds as the monofunctional (meth) acrylate described above.
  • compounds other than the above-mentioned monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 1,4-cyclohexane.
  • a compound having both an ethylenically unsaturated group and an alkoxysilyl group is also called a silane coupling agent.
  • a silane coupling agent or a compound having both an ethylenically unsaturated group and a phosphoric acid group is preferable for improving the adhesion to an inorganic substrate.
  • Components (D-3) other than monofunctional (meth) acrylates include N-vinylpyrrolidone, N-vinylcaprolactam, (meth) acrylamide, (meth) acryloylmorpholine, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, maleic anhydride, N-phenylmaleimide, N-hydroxyethylmaleimide, N-hydroxyethylcitracimide, cyclohexyl Vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, dipropylene glycol monovinyl ether Acetoxyethyl vinyl ether, acetoxy butyl ether
  • the preferred content varies depending on the use of the composition of the present invention, the type of adherend, the light source, the curing atmosphere, and the like.
  • the content ratio of the component (D-3) is 100% by weight of the curable component from the viewpoint of rapid curing.
  • the content is preferably 0 to 30% by weight, and more preferably 0 to 15% by weight.
  • the component (D-3) is 80% by weight in 100% by weight of the curable component. You may include with the following content.
  • the component (E) is a coloring component selected from pigments or dyes, and is necessary when the composition of the present invention is used as an ink composition.
  • the pigment include organic pigments and inorganic pigments. Specific examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, benzidine yellow and pyrazolone red; soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet and Permanent Red 2B; Alizarin, Indantron And derivatives from vat dyes such as thioindigo maroon; phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone organic pigments such as quinacridone red and quinacridone magenta; perylene organic pigments such as perylene red and perylene scarlet; Isoindolinone organic pigments such as indolinone yellow and isoindolinone orange; pyranthrone
  • the inorganic pigment include carbon black, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, Examples include bitumen, chromium oxide green, cobalt green, amber, titanium black, and synthetic iron black.
  • the dye include azo dyes and extracts from plants.
  • the content ratio of the component (E) may be appropriately adjusted according to the application and film thickness, but in the case of the ink composition, it is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the total curable components. More preferred is 10 to 100 parts by weight.
  • composition of the present invention may contain an organic solvent or water as the component (F) for the purpose of reducing the viscosity.
  • organic solvent include, for example, low molecular weight alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; Aromatic compounds such as benzene, toluene and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methyl Examples include pyrrolidone and the like. Among these, an alkylene glycol monoether compound and a low molecular weight alcohol compounds such as methanol, ethanol
  • the component (A) which is an essential component of the composition of the present invention, dissolves water to some extent when the proportion of hydroxyl groups in one molecule is large. For this reason, water can be mix
  • a preferable content ratio of the component (F) varies depending on the use of the composition of the present invention, but is preferably 0 to 1,000 parts by weight with respect to 100 parts by weight of the total amount of the curable components. More preferably, it is ⁇ 500 parts by weight, and further preferably 0 to 300 parts by weight.
  • the composition of the present invention may contain colloidal inorganic particles as the (G) component.
  • inorganic particles include metal oxides such as silica, alumina, titania, zinc oxide, tin oxide and indium oxide, metals such as gold, silver, platinum and palladium, metal chalcogenide compounds such as zinc sulfide and zinc selenide. It is done. Of these, colorless metal oxides are preferred for applications where scratch resistance and colorless transparency are required, such as hard coats.
  • silica, titania, zinc oxide, tin oxide, and indium oxide are preferred. Particularly preferred is silica.
  • the average particle diameter is a particle diameter determined from a specific surface area measurement by the BET method, preferably 1 to 200 nm, more preferably 5 to 150 nm, and still more preferably 10 to 100 nm.
  • component (G) there are colloidal inorganic particles (hereinafter referred to as “component (G-1)”) having radically polymerizable unsaturated groups and photoreactive groups bonded to the surface, radically polymerizable unsaturated groups and light. And colloidal inorganic particles having no reactive group (hereinafter referred to as “component (G-2)”).
  • component (G) is preferably used when importance is attached to the scratch resistance, and when the curling suppression when coating on a thin substrate such as a film is important ( It is preferable to use the component G-2).
  • Specific examples of the component (G-1) include a reaction product of (meth) acryloyloxypropyltrimethoxysilane and colloidal silica.
  • the content of the component (G-1) is preferably 0 to 60 parts by weight and preferably 0 to 30 parts by weight with respect to 100 parts by weight of the curable component. Is more preferable.
  • the blending amount of the component (G-2) is preferably 0 to 100 parts by weight with respect to 100 parts by weight of the curable component, and 0 to 50 parts by weight. More preferably.
  • the component (G-1) is included in the curable component, and the component (G-2) is not included in the curable component.
  • a polymer may be blended as the (H) component.
  • Suitable polymers include (meth) acrylic polymers, and suitable constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, N- ( 2- (meth) acryloxyethyl) tetrahydrophthalimide and the like.
  • glycidyl (meth) acrylate may be added to introduce a (meth) acryloyl group into the polymer chain.
  • various polymers such as polyester, polyurethane, polycarbonate, polyvinyl pyrrolidone, polyvinyl acetate, vinyl pyrrolidone and vinyl acetate copolymer, polyvinyl alcohol, cellulose alkylate, diallyl phthalate resin are blended. can do.
  • component (H) a polymer having a radically polymerizable unsaturated group or photoreactive group bonded thereto (hereinafter referred to as “(H-1) component”) and a radically polymerizable unsaturated group or photoreactive group are included.
  • Polymer [hereinafter referred to as “component (H-2)”].
  • component (H) when the composition of the present invention is used as a hard coat, the component (H-1) is preferable.
  • the content ratio of the component (H-1) is preferably 0 to 60 parts by weight, and 0 to 30 parts by weight with respect to 100 parts by weight of the curable component. Is more preferable.
  • the blending amount of the component (H-2) is preferably 0 to 50 parts by weight, and 0 to 25 parts by weight with respect to 100 parts by weight of the curable component. More preferably.
  • the component (H-1) is included in the curable component, and the component (H-2) is not included in the curable component.
  • component (I) In the composition of this invention, you may mix
  • reactive surfactants reactive surfactants having propenyl groups (I-1) (hereinafter referred to as “component (I-1)”), reactive surfactants having (meth) allyl groups (I- 2) [hereinafter referred to as “component (I-2)”] and the like.
  • component (I-1) examples include compounds represented by the following formula (5).
  • R 14 , R 15 , R 16 , A 1 , a, and X 1 are as shown below.
  • R 14 is a group selected from the group consisting of an alkyl group, an alkenyl group, an alkylaryl group and an aralkylaryl group having 6 to 30 carbon atoms.
  • R 15 is an alkyl group having a hydrogen atom and 6 to 30 carbon atoms.
  • R 14 as the alkyl group, for example, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, Nonadecyl group, eicosyl group, etc. are mentioned.
  • alkenyl group examples include hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group and octadecenyl group.
  • Alkylaryl groups include monobutylphenyl, dibutylphenyl, sec-butylphenyl, disec-butylphenyl, tert-butylphenyl, octylphenyl, nonylphenyl, dinonylphenyl, dodecylphenyl And a didecylphenyl group.
  • aralkylaryl group include a styrenated phenyl group, a benzylphenyl group, and a cumylphenyl group, and may be a di- or tri-form of an aralkyl group, and further may be substituted with an alkyl group.
  • alkyl group, alkenyl group, and alkylaryl group aralkylaryl group having 6 to 30 carbon atoms in R 15 include the same groups as those described for R 14 .
  • the preferable range of a is 1 to 50, more preferably 1 to 20.
  • the alkylene group having 2 to 4 carbon atoms of A 1 is specifically an ethylene group, a propylene group, a butylene group, an isobutylene group, or the like, in which different alkylene groups are bonded in blocks or randomly in one molecule. But you can.
  • a 1 is preferably an ethylene group.
  • X 1 is preferably a hydrogen atom because the cured film has excellent anti-fogging durability.
  • the propenyl group includes trans and cis stereoisomers, and in the present invention, any of the isomers can be used alone or as a mixture.
  • a preferable example of the compound represented by the formula (5) is a compound represented by the following formula (6).
  • the compound represented by the formula (6) is a compound in which R 14 is a nonyl group, R 15 , R 16 and X 1 are hydrogen atoms and A 1 is an ethylene group in the formula (5).
  • Examples include Aqualon RN-20, Aqualon RN-2025, Aqualon RN-30, Aqualon RN-50, Aqualon HS-5, Aqualon HS-10 and the like manufactured by Daiichi Kogyo Seiyaku.
  • component (I-2) examples include compounds represented by the following formula (7).
  • R 17 , R 18 , b, c, A 2 , A 3 and X 2 are as shown below.
  • R 17 is a group having 6 to 30 carbon atoms, selected from the group consisting of an alkyl group, an alkenyl group, an alkylaryl group, an aralkylaryl group and an alkylphenyl group.
  • R 18 is a hydrogen atom or a methyl group.
  • B 0 C is an integer of 0 to 100 c is an integer of 0 to 100
  • a 2 is an alkylene group having 2 to 4 carbon atoms
  • a 3 is an alkylene group having 2 to 4 carbon atoms
  • X 2 is a hydrogen atom or sulfate [—SO 3 L , L includes alkali metal, NH 4 and alkanolamine residues, etc.]
  • alkyl group, alkenyl group, alkylaryl group and aralkylphenyl group having 6 to 30 carbon atoms in R 17 include the same groups as those described above for R 14 in formula (5).
  • examples of the alkylphenyl group include a phenyl group having the same alkyl group as that described for R 14 in the formula (5) as the alkyl group.
  • B and c are preferably in the range of 1 to 50, more preferably 1 to 20, respectively.
  • a 2 and A 3 are the same as those described for A 1 in Formula (5).
  • a 2 and A 3 an ethylene group is preferable.
  • X 2 is preferably a hydrogen atom because the cured film is excellent in anti-fogging durability.
  • the compound represented by the formula (8) is a compound in which R 17 is a nonylphenyl group, R 18 is a hydrogen atom and b is 0 in the formula (7).
  • the content of the component (I) is preferably 0.1 to 40 parts by weight and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the curable component. preferable.
  • the component (I) is 0.1 part by weight or more, the cured film has excellent antifogging durability, and when it is 30 parts by weight or less, the cured coating film has excellent hardness.
  • additives In addition to the above-described components, various additives may be blended in the composition of the present invention depending on the purpose.
  • Various additives include surface modifiers, antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, particles, polymerization inhibitors, conductivity imparting agents, pigment dispersants, antifoaming agents, antibacterial agents, Examples include photoacid generators, photobase generators, thermal radical polymerization initiators and the like.
  • Surface modifier A surface modifier may be added to the composition of the present invention for the purpose of increasing the leveling property at the time of coating, the purpose of increasing the slipping property of the cured film and improving the scratch resistance, and the like.
  • the surface modifier include a surface modifier, a surfactant, a leveling agent, an antifoaming agent, a slipperiness imparting agent, and an antifouling imparting agent, and these known surface modifiers can be used. . Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred.
  • silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain silicone polymers and oligomers having a silicone chain and a polyester chain, and fluorine polymers having a perfluoroalkyl group and a polyalkylene oxide chain.
  • fluorine-based polymer and an oligomer having a perfluoroalkyl ether chain and a polyalkylene oxide chain a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group, in the molecule may be used.
  • the content of the surface modifier is preferably 0.01 to 1.0 part by weight with respect to 100 parts by weight of the total amount of curable components. It is excellent in the surface smoothness of a cured film as it is the said range.
  • Antioxidant Antioxidant is mix
  • the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
  • phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene.
  • commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by Adeka Corporation.
  • Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphites and triaryl phosphites.
  • Examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. Etc.
  • Examples of the sulfur-based antioxidant include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation. These may be used alone or in combination of two or more. Preferred combinations of these antioxidants include the combined use of phenolic antioxidants and phosphorus antioxidants, and the combined use of phenolic antioxidants and sulfurous antioxidants.
  • the content ratio of the antioxidant may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the total amount of the curable components. It is. When the content ratio is 0.1 parts by weight or more, the durability of the composition can be improved. On the other hand, when the content ratio is 5 parts by weight or less, curability and adhesion can be improved.
  • UV absorbers UV absorbers can be blended for the purpose of improving the light resistance of the cured film.
  • the ultraviolet absorber include triazine ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole ultraviolet absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
  • the content ratio of the ultraviolet absorber may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the total amount of the curable components. It is. When the content ratio is 0.01% by weight or more, the light resistance of the cured film can be improved, and when it is 5% by weight or less, the curability of the composition is excellent. be able to.
  • Light stabilizer A light stabilizer can be mix
  • a hindered amine light stabilizer (so-called HALS) is preferable.
  • HALS include TINUVIN123, TINUVIN144, TINUVIN111FDL, TINUVIN152, TINUVIN292, and TINUVIN5100 manufactured by BASF.
  • Silane coupling agent not belonging to component (D-3) The silane coupling agent can be blended for the purpose of improving the interfacial adhesive strength between the cured film and the substrate.
  • the silane coupling agent is not particularly limited as long as it can contribute to improvement in adhesion to the substrate.
  • the silane coupling agent mentioned here is a compound having no radically polymerizable unsaturated group, and is a compound different from the component (D-3). Adhesion may be improved without having a radically polymerizable unsaturated group.
  • silane coupling agent different from the component (D-3) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidide.
  • the mixing ratio of the silane coupling agent may be appropriately set according to the purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable components. .
  • the blending ratio is 0.1 parts by weight or more, the adhesive strength of the composition can be improved.
  • the blending ratio is 10 parts by weight or less, it is possible to prevent the adhesive force from changing over time.
  • Particles not belonging to component (G) For the purpose of providing the composition of the present invention with antiglare properties to the cured film or providing slipperiness when the substrates with the cured film are overlaid. Particles other than the component (G) may be blended.
  • the particle diameter of the fine particles varies depending on the application, but generally 0.2 to 100 ⁇ m can be preferably used.
  • the fine particles may be inorganic or organic. Examples of the inorganic fine particles include metal oxides such as silica, alumina, and titania that are not colloidal. Examples of the organic material include particles in which a polymer of a monomer such as alkyl (meth) acrylate or styrene is crosslinked.
  • polymerization inhibitor In addition to the polymerization inhibitor contained in the component (A), a polymerization inhibitor can be further added to the composition of the present invention.
  • the polymerization inhibitor the same compounds as those added in the synthesis of the component (A) are suitable.
  • Conductivity-imparting agent such as an antistatic agent can be added to the composition of the present invention.
  • the antistatic agent include nonionic surfactants such as glycerin fatty acid ester, polyoxyalkylene alkyl ether and alkyldiethanolamine; Anionic surfactants such as alkyl sulfonates, alkyl benzene sulfonates, and alkyl phosphates; Cationic surfactants such as tetraalkylammonium salts and trialkylbenzylammonium salts; Amphoteric surfactants such as alkylbetaines and alkylimidazolium betaines; Polymer type antistatic agents such as polyether esters, polyether ester amides, polystyrene sulfonates, (meth) acrylate polymers containing four-ball ammonium salts, polyether polyethers; Monomers having acidic groups such as phosphoric acid
  • Urethane (meth) acrylate The present invention relates to a curable composition containing the component (A). After the component (A) is reacted with an organic polyvalent isocyanate to form a urethane (meth) acrylate, The effects of the present invention can also be expressed as a curable composition by blending with the components B) to (I) and the various additives described above. In particular, a cured product having excellent bending resistance can be obtained.
  • the organic polyvalent isocyanate compound to be reacted with the organic polyvalent isocyanate (A) component is preferably a divalent isocyanate compound, and is preferably an aliphatic polyvalent isocyanate compound.
  • preferable organic polyvalent isocyanate compounds include aliphatic divalent isocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and norbornane diisocyanate, and 2,4-tolylene diisocyanate and naphthalene.
  • aromatic divalent isocyanates such as diisocyanate, xylene diisocyanate and diphenylmethane diisocyanate, and nurate type trimers of these compounds. These may be used individually by 1 type, or may use 2 or more types together, but it is preferable to use individually by 1 type.
  • Urethane (meth) acrylate is produced by reacting the hydroxyl group in component (A) with the isocyanate group in the organic polyvalent isocyanate compound to form a urethane bond.
  • a manufacturing method of urethane (meth) acrylate A well-known method can be used.
  • the component (A) and the organic polyvalent isocyanate compound may be heated and stirred.
  • the hardness of the obtained cured film is more excellent as it is the said aspect.
  • the reaction between the hydroxyl group and the isocyanate group in the production of urethane (meth) acrylate can be performed without a catalyst, but a catalyst may be added in order to advance the reaction efficiently.
  • catalysts include organotin compounds such as dibutyltin dilaurate; acetylacetonate metal complexes such as iron acetylacetonate, zinc acetylacetonate and ruthenium acetylacetonate; weak metal organic acid salts such as lead naphthenate and potassium acetate; and , Triethylamine, triethanolamine, dimethylbenzylamine, trioctylamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] tertiary amine compounds such as nonene-5; and trialkylphosphine compounds such as triethy
  • the ratio of the catalyst may be appropriately set according to the organic polyvalent isocyanate compound used, the catalyst, etc., but is preferably 0.01 to 1,000 wtppm, more preferably 0.1 to 1 with respect to the reaction solution. , 000 wtppm.
  • the reaction temperature may be appropriately set according to the type and ratio of the organic polyisocyanate compound to be used and the catalyst, and is preferably 60 ° C to 130 ° C, more preferably 70 ° C to 90 ° C.
  • a chain extender can also be mix
  • the chain extender those usually used in a urethanization reaction can be used.
  • Specific examples of the chain extender include low molecular weight polyols, polyether polyols, polycarbonate polyols and polyester polyols.
  • Examples of the low molecular weight polyol include ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol, trimethylolpropane glycerin, diglycerin and the like. And polyols such as these alkylene oxide adducts.
  • Examples of the polyether polyol include polyalkylene glycol having 3 or more oxyalkylene units, and specific examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • Examples of the polycarbonate polyol include a reaction product of carbonate and diol.
  • the carbonate include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.
  • the diol include the low molecular weight polyol described above.
  • the polyester polyol include a reaction product of an acid component with at least one selected from the group consisting of the low molecular weight polyol, the polyether polyol, and the polycarbonate polyol.
  • the acid component include dibasic acids such as adipic acid, sebacic acid, succinic acid, maleic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or anhydrides thereof.
  • the ring-opening reaction product of polycarbonate diol and caprolactone is also mentioned.
  • the proportion of the chain extender used is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, with respect to 100 parts by weight of the urethane (meth) acrylate finally obtained.
  • the component (A) does not have an isocyanate group or a small amount of the isocyanate group is preferable from the viewpoint of hardness and stability.
  • a compound having two or more (meth) acryloyl groups hereinafter also referred to as “hydroxyl group-containing polyfunctional (meth) acrylate”) may be added.
  • hydroxyl group-containing polyfunctional (meth) acrylate various compounds can be used, which are (meth) acrylates derived from a trihydric or higher polyhydric alcohol, having two or more (meth) acryloyl groups, It is preferable that it is (meth) acrylate which has 1 or more.
  • Specific examples of the hydroxyl group-containing polyfunctional (meth) acrylate include trimethylolpropane di (meth) acrylate, di (meth) acrylate of trimethylolpropane alkylene oxide adduct, and di (meth) acrylate of alkylene oxide adduct of glycerin.
  • examples of the alkylene oxide include ethylene oxide and propylene oxide.
  • examples of the alkylene oxide include ethylene oxide and propylene oxide.
  • trimethylolpropane di (meth) acrylate, di or tri (meth) acrylate of pentaerythritol, di or tri (meth) acrylate of ditrimethylolpropane and di, tri, tetra or penta (meth) acrylate of dipentaerythritol Preferably mentioned.
  • a method of using the composition of the present invention a conventional method may be followed. For example, after apply
  • the composition is injected into a predetermined mold and then cured in the case of an active energy ray curable composition by irradiation with active energy rays, or a thermosetting composition.
  • the method of heating and hardening etc. is mentioned.
  • a general method known as a conventional curing method may be adopted as the active energy ray irradiation method and heating method.
  • the component (B) (photopolymerization initiator) and the component (C) (thermal polymerization initiator) are used in combination with the composition, irradiated with active energy rays, and then heat-cured, thereby adhering to the substrate.
  • a method for improving the property can also be adopted.
  • the substrate examples include paper, plastic film, plastic plate, wood, metal, inorganic materials other than metal, nails, bones, leather, and the like.
  • the composition of the present invention is excellent in the bending resistance of the cured product, it can be preferably applied to a thin substrate such as paper or plastic film.
  • plastics include cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, cyclic polyolefin resins having cyclic olefins such as polyvinyl alcohol, acrylic resins, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, norbornene as monomers. , Polyvinyl chloride, epoxy resin, polyurethane resin and the like.
  • the wood include natural wood and synthetic wood.
  • the inorganic material include metals such as steel plates, stainless steel, aluminum, gold, silver, copper, and chromium, and metal oxides such as zinc oxide (ZnO), tin oxide, aluminum oxide, and indium tin oxide (ITO). It is done. Examples of other inorganic materials include glass, mortar, concrete and stone. As a nail
  • the film thickness of the cured film of the composition is preferably 0.5 to 100 ⁇ m, more preferably 1 to 20 ⁇ m.
  • the substrate of the composition of the present invention may be appropriately set according to the purpose, and brush, brush, bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, Examples of the method include coating or printing using a knife coater, comma coater, reverse roll coater, die coater, lip coater, gravure coater, micro gravure coater, and inkjet.
  • the composition of the present invention contains an organic solvent or water as the component (F), it is preferably dried after coating.
  • a hot air dryer In the case of a production line, it is preferable to provide a hot air dryer. It is preferable to install a local exhaust device in the hot air dryer.
  • the drying step is not necessarily required.
  • the water content is low, a cured film that is transparent and has no problem in performance may be formed even if it is cured while containing water.
  • the film thickness is as thin as about 2 ⁇ m, most of the water volatilizes even at room temperature, and a cured film that is transparent and has no performance problems can be formed. There is a case.
  • Examples of the active energy ray for curing the composition of the present invention include ultraviolet rays, visible rays, and electron beams, and ultraviolet rays are preferred.
  • Examples of the light source in the ultraviolet irradiation include a high pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, a UV-LED (ultraviolet light emitting diode), and sunlight.
  • the amount of irradiation energy may be set as appropriate depending on the light source, application, and the type and amount of component (B). 000 mJ / cm 2 is preferable, and 200 to 1,000 mJ / cm 2 is more preferable.
  • the curable composition of the present invention is preferably used as an active energy ray curable composition, and exhibits the effects of the above-described fast curability, hardness of the cured product, and antifogging properties, and uses the effect. It can be used for various purposes. Examples of preferred applications include coating agents such as clear coating agents and paints, inks such as offset inks and inkjet inks, adhesives, shaping resins, resin films, resists, pattern forming compositions, and molding materials. .
  • parts means parts by weight.
  • Production example 1-1) Production Example 1 [Production of component (A), hydroxyl value: 238 mgKOH / g] Into a 3 liter flask equipped with a stirrer, thermometer, gas introduction tube, rectifying column and cooling tube, glycerin [refined glycerin (trade name) manufactured by Sakamoto Pharmaceutical Co., Ltd., peroxide concentration 0.95 wtppm] 302.75 g (3.29 mol), 2312.84 g (17.77 mol) of 2-methoxyethyl acrylate, 6.51 g (0.06 mol) of DABCO as catalyst X, and 24.
  • glycerin refined glycerin (trade name) manufactured by Sakamoto Pharmaceutical Co., Ltd., peroxide concentration 0.95 wtppm] 302.75 g (3.29 mol), 2312.84 g (17.77 mol) of 2-methoxyethyl acrylate, 6.51 g (0.06 mol) of DABCO as catalyst
  • component (A) 5.0 g of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.] was added to the kettle and subjected to pressure filtration, and the resulting filtrate was used as component (A).
  • the yield of component (A) was 651 g.
  • 302.75 g of the charged glycerin is all converted to glycerin diacrylate (hereinafter referred to as “GLY-DAA”)
  • the yield is 658 g.
  • the yield of the component (A) calculated based on this is 99. %Met.
  • the purity of GLY-DAA contained in the component (A) was calculated from the above formula (1) and found to be 62%.
  • the obtained component (A) had a viscosity: 43 mPa ⁇ s (25 ° C.) and a hydroxyl value: 238 mgKOH / g. Mw by GPC measurement: 314.
  • the content of by-product contained in component (A) was determined by gas chromatography (hereinafter referred to as “GC”), and the hydroxyl group of 2-methoxyethanol was added to the acryloyl group of 2-methoxyethyl acrylate by Michael.
  • GC gas chromatography
  • HPLC, peroxide concentration, viscosity, hydroxyl value, GPC and GC were measured under the following conditions.
  • HPLC measurement conditions and equipment ACQUITY UPLC manufactured by Waters Co., Ltd.
  • ⁇ Detector UV detector ⁇ Detection wavelength: 210 nm
  • Viscosity measurement conditions Using an E-type viscometer, the viscosity at 25 ° C was measured.
  • ⁇ Hydroxyl value measurement conditions Add an acetylating reagent to the sample and heat-treat in a warm bath at 92 ° C for 1 hour. After standing to cool, a small amount of water is added and heat-treated in a warm bath at 92 ° C. for 10 minutes. After allowing to cool, the hydroxyl value was determined by titrating the acid with a potassium hydroxide ethanol solution using a phenolphthalein solution as an indicator.
  • RI-Detector Differential refractive index (RI) detector-Column: Guard column Shodex KFG (8 ⁇ m 4.6 ⁇ 10 mm) manufactured by Showa Denko K.K., two types of this column Watergel HR 4E THF (7. 8 x 300 mm) + styragel HR 1THF (7.8 x 300 mm) Column temperature: 40 ° C Eluent composition: Tetrahydrofuran (THF, containing 0.03% sulfur as internal standard), flow rate 0.75 mL / min Calibration curve: Standard polystyrene was used to create a calibration curve.
  • detection peaks derived from component (A) detection peaks derived from monofunctional (meth) acrylates, solvents, and detection peaks with a retention time later than those derived from water are not considered in the calculation of Mw.
  • Mw was calculated by regarding a plurality of other detection peaks as one peak.
  • GC-17A manufactured by Shimadzu Corporation Detector: FID detector Carrier gas: Helium Column: Inert Cap (film thickness 0.5 ⁇ m, 0.32 mm ID ⁇ 60 m) ⁇ Injection temperature: 200 °C ⁇ FID temperature: 250 °C Column temperature: held at 120 ° C. for 5 minutes, then heated to 240 ° C. at a rate of 10 ° C./min and then held for 25 minutes. ⁇ Injection volume: 0.2 ⁇ L -The content of by-products was determined in wt% by the internal standard method.
  • component M-240 polyethylene glycol diacrylate [Aronix M-240 (n ⁇ 4) (trade name) (D-1) component manufactured by Toagosei Co., Ltd.]]
  • MT-3533 Pentaerythritol tri and tetraacrylate mixture [Aronix MT-3533 (trade name) (D-2) component manufactured by Toagosei Co., Ltd.]
  • RN-20 Polyoxyethylene nonylpropenyl phenyl ether [Aqualon RN-20 (trade name) (I-1) component manufactured by Daiichi Kogyo Seiyaku Co., Ltd.]
  • the curable composition of the present invention can be used for various applications such as a coating agent, an ink, an adhesive, a shaping resin, a resin film, and a pattern forming composition, preferably as an active energy ray hardening composition.
  • the cured film thus obtained is excellent in hardness and antifogging properties, and can be preferably used as a coating agent composition.

Abstract

La présente invention concerne : une composition durcissable qui forme un produit durci possédant d'excellentes propriétés de dureté et antibuée ; et un procédé de production de cette composition durcissable. L'invention concerne une composition durcissable qui contient un composant (A), qui est un mélange de (méth)acrylate qu'on obtient en soumettant du glycérol et un composé comportant un groupe (méth)acryloyle à une réaction de transestérification en présence de catalyseurs X et Y, ledit mélange contenant du di(méth)acrylate de glycérol et présentant un nombre hydroxyle supérieur ou égal à 65 mg de KOH/g. Catalyseur X : un ou plusieurs composé(s) sélectionné(s) dans le groupe constitué par les amines tertiaires cycliques présentant une structure azabicyclo et leurs sels et complexes, des amidines et leurs sels et complexes, les composés comportant un noyau pyridine et leurs sels et complexes, et la phosphine et ses sels et complexes. Catalyseur Y : un composé contenant du zinc.
PCT/JP2017/045406 2016-12-20 2017-12-19 Composition durcissable WO2018117062A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020033404A (ja) * 2018-08-28 2020-03-05 東亞合成株式会社 硬化型組成物
US20210147634A1 (en) * 2019-11-20 2021-05-20 Sakamoto Yakuhin Kogyo Co., Ltd. (poly) glycerol-based alkoxysilane
WO2022225041A1 (fr) * 2021-04-23 2022-10-27 東亞合成株式会社 Composition durcissable, composition durcissable par rayonnement d'énergie active, et composition de revêtement durcissable par rayonnement d'énergie active

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10130569A (ja) * 1996-10-31 1998-05-19 Toray Ind Inc 塗料用樹脂組成物
JP2015042715A (ja) * 2013-08-26 2015-03-05 東亞合成株式会社 （メタ）アクリレート混合物及びこれを含む硬化型組成物
WO2016163208A1 (fr) * 2015-04-10 2016-10-13 東亞合成株式会社 Procédé de fabrication de (méth)acrylate
WO2017002964A1 (fr) * 2015-07-02 2017-01-05 東亞合成株式会社 Composition durcissable

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10130569A (ja) * 1996-10-31 1998-05-19 Toray Ind Inc 塗料用樹脂組成物
JP2015042715A (ja) * 2013-08-26 2015-03-05 東亞合成株式会社 （メタ）アクリレート混合物及びこれを含む硬化型組成物
WO2016163208A1 (fr) * 2015-04-10 2016-10-13 東亞合成株式会社 Procédé de fabrication de (méth)acrylate
WO2017002964A1 (fr) * 2015-07-02 2017-01-05 東亞合成株式会社 Composition durcissable

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020033404A (ja) * 2018-08-28 2020-03-05 東亞合成株式会社 硬化型組成物
JP7119773B2 (ja) 2018-08-28 2022-08-17 東亞合成株式会社 硬化型組成物
US20210147634A1 (en) * 2019-11-20 2021-05-20 Sakamoto Yakuhin Kogyo Co., Ltd. (poly) glycerol-based alkoxysilane
WO2022225041A1 (fr) * 2021-04-23 2022-10-27 東亞合成株式会社 Composition durcissable, composition durcissable par rayonnement d'énergie active, et composition de revêtement durcissable par rayonnement d'énergie active

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