WO2018021352A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

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Publication number
WO2018021352A1
WO2018021352A1 PCT/JP2017/026931 JP2017026931W WO2018021352A1 WO 2018021352 A1 WO2018021352 A1 WO 2018021352A1 JP 2017026931 W JP2017026931 W JP 2017026931W WO 2018021352 A1 WO2018021352 A1 WO 2018021352A1
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WIPO (PCT)
Prior art keywords
component
meth
acrylate
compound
curable
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PCT/JP2017/026931
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English (en)
Japanese (ja)
Inventor
和正 稲田
橋本　直樹
谷内　健太郎
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東亞合成株式会社
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Priority to JP2018530313A priority Critical patent/JP7022348B2/ja
Publication of WO2018021352A1 publication Critical patent/WO2018021352A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q3/00—Manicure or pedicure preparations
    • A61Q3/02—Nail coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives

Definitions

  • the present invention relates to a curable composition, and preferably to an active energy ray curable composition.
  • the curable composition of the present invention when used as an active energy ray curable composition, is excellent in fast curability, low yellowing, high flexibility and low curl properties, and the light source is an ultraviolet light emitting diode (Hereinafter referred to as “UV-LED”), which exhibits excellent curability and is difficult to achieve both curability and low yellowing, high flexibility, and low curl properties. It can be preferably used for coating agents and inks.
  • UV-LED ultraviolet light emitting diode
  • the active energy ray curable composition is widely used as an ink for clear coating of paper and film, offset printing, and the like because it has advantages such as energy saving and space saving of equipment used and high productivity.
  • High-pressure mercury lamps and metal halide lamps are widely used as light sources for active energy rays, particularly UV light sources, but in recent years, the introduction of UV-LEDs as a light source that promotes the advantages of energy saving and space saving has been studied.
  • a composition having excellent curability with respect to a UV-LED light source has been studied.
  • the conventional active energy ray curable composition is applied as it is as a UV-LED curable composition, there is often a problem that the curability deteriorates.
  • the problem of curability deterioration due to the introduction of a UV-LED light source is particularly serious in clear coating applications that do not contain pigments, such as coating varnishes.
  • the reason is that if a photopolymerization initiator system sensitive to UV-LED light (usually 385 nm or 365 nm) is used, the light absorption of the cured film inevitably reaches the visible light region, and the cured film turns yellow. Because.
  • Patent Document 1 discloses a UV-LED curable coating varnish containing an amine-modified acrylate, an acylphosphine oxide polymerization initiator, and a fluorescent brightening agent.
  • Patent Document 2 discloses an ultraviolet curable coating varnish composition containing a urethane acrylate obtained by reacting a diisocyanate having a ring structure and pentaerythritol triacrylate, and a polymerizable acrylate monomer.
  • Patent Document 3 discloses a clear ink composition for inkjet printing that has low UV viscosity and excellent UV-LED curability.
  • a composition containing a fluorescent brightening agent may cause discoloration in a cured film.
  • the base material is a plastic film
  • the cured film may feel both yellow and blue, and when the base material is paper, the white color of the paper may feel unnatural.
  • the coating varnish composition described in Patent Document 2 the compatibility between UV-LED curability and low yellowing was insufficient.
  • the ink composition described in Patent Document 3 the compatibility between UV-LED curability and low yellowing was insufficient.
  • a composition excellent in UV-LED curability and low yellowing is desired for the UV-LED curable composition.
  • the UV-LED curable composition is used as a coating agent, there is a composition having a low curl property in which the cured film is not easily cracked when the substrate is bent, so-called high flexibility and warping is small. It is requested.
  • the problem to be solved by the present invention is to provide a curable composition which is fast-curing and whose cured film is excellent in low yellowing, high flexibility and low curling property, preferably active energy ray curable. It is to provide a composition.
  • the present inventors have used a specific basic catalyst or a phosphine-based catalyst and a zinc-based catalyst in combination, a polyglycerin having a hydroxyl value of 700 to 1,200 mgKOH / g, and 1
  • the inventors have found that a curable composition containing a mixture of compounds having a (meth) acryloyl group obtained by subjecting a compound having one (meth) acryloyl group to a transesterification reaction is effective, and completed the present invention.
  • the present invention will be described in detail.
  • an acryloyl group and / or a methacryloyl group is represented as a (meth) acryloyl group
  • an acrylate and / or methacrylate is represented as a (meth) acrylate
  • acrylic acid and / or methacrylic acid is represented by (meth) acrylic acid. It expresses.
  • the active energy ray curable composition preferably the active energy ray curable composition, it is fast-curing, and the cured film is excellent in low yellowing, high flexibility and low curling property. Furthermore, even if the light source is a UV-LED, it exhibits excellent curability, and it is difficult to achieve both curability and low yellowing, high flexibility, and low curl properties.
  • the present invention relates to a compound having a hydroxyl value of 700 to 1,200 mgKOH / g (hereinafter simply referred to as “polyglycerin”) and one (meth) acryloyl group in combination with the following catalysts X and Y (Hereinafter referred to as “monofunctional (meth) acrylate”) relates to a curable composition containing a mixture (A) of a compound having a (meth) acryloyl group obtained by transesterification.
  • Catalyst X a kind 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 The above compound.
  • Catalyst Y Compound containing zinc.
  • Component (A) is a mixture of (meth) acrylate obtained by transesterification of polyglycerol and monofunctional (meth) acrylate in the presence of catalysts X and Y.
  • this may be referred to as polyglycerin poly (meth) acrylate.
  • polyglycerol, monofunctional (meth) acrylate, catalyst X, catalyst Y, a method for producing component (A), and preferred forms of component (A) will be described.
  • the polyglycerin used as a raw material for the polyglycerin (A) component is a polyether polyol having a structure in which glycerin or glycidol is polymerized.
  • the hydroxyl value which means the average degree of polymerization of polyglycerol, is 700 to 1,200 mg KOH / g, preferably 800 to 1,150 mg KOH / g, more preferably 850 to 1,100 mg KOH / g, and still more preferably 900 to 1,050 mg KOH / g. If the hydroxyl value of polyglycerol exceeds 1,200 mgKOH / g, the low curl property of the cured film of the composition is inferior.
  • hydroxyl value of polyglycerin is related to the average degree of polymerization. For example, when the average degree of polymerization is 6, it is approximately 970 mgKOH / g.
  • polyglycerin and one or more polyhydric alcohols other than polyglycerin 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 parts by weight or less is preferable with respect to 100 parts by weight of the total polyglycerol.
  • 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) Compounds.
  • 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 functional groups described in JP-A-2017-39916, JP-A-2017-39917 or International Publication No. 2017/033732. It is done.
  • 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 and alkoxyalkyl (meth) acrylates such as 2-methoxyethyl acrylate, and N, N-dimethylaminoethyl (meth) acrylate are preferred, particularly for polyglycerol A (meth) acrylate having an alkyl group having 1 to 4 carbon atoms and an alkoxyalkyl (meth) acrylate having an alkyl group having 1 to 2 carbon atoms, which shows good reactivity and is easily available, are prefer
  • alkoxyalkyl (meth) acrylates having an alkyl group having 1 to 2 carbon atoms that promote dissolution of polyglycerol and exhibit very good reactivity are more preferred, and 2-methoxyethyl (meth) acrylate is particularly preferred.
  • monofunctional (meth) acrylate acrylate is particularly preferable because of its excellent reactivity.
  • the ratio of the polyglycerin and monofunctional (meth) acrylate used in the method for producing the component (A) is not particularly limited, but 0.4 to 10 monofunctional (meth) acrylate is added to 1 mol of total hydroxyl groups in the polyglycerin.
  • the amount is preferably 0.0 mol, more preferably 0.6 to 5.0 mol.
  • the transesterification catalyst in the method for producing the catalyst (A) component since there are few side reactions, a mixture of polyglycerin (meth) acrylates having excellent curability and scratch resistance can be produced. And Y are used in combination.
  • 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 component (A), and also form a complex with catalyst Y described later after completion of the reaction, and the complex can be easily obtained from the reaction solution after completion of the reaction by a simple method such as adsorption. Can be removed.
  • 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 reaction is completed 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 compounds described in JP-A-2017-39916, JP-A-2017-39917 or 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, or 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 compound examples include compounds described in JP 2017-39916 A, JP 2017-39917 A, or 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 amount 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 a total of 1 mol of hydroxyl groups in polyglycerol.
  • the amount is preferably 0.0005 to 0.2 mol.
  • 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: It is preferable because polyglycerol poly (meth) acrylate 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 aforementioned compounds can be used directly, but these compounds can also be generated and used in the reaction system.
  • the method of reacting other zinc compounds with organic acid, zinc diketone enolate examples include a method of reacting other zinc compounds with acetylacetylacetone.
  • the organic acid zinc and zinc diketone enolate in the catalyst Y the aforementioned compounds can be used directly, but these compounds can also be generated and used in the reaction system.
  • raw zinc compounds such as metal zinc, zinc oxide, zinc hydroxide, zinc chloride and zinc nitrate
  • raw zinc compounds are used as raw materials.
  • organic acid zinc 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 amount of catalyst Y used in the method for producing component (A) is not particularly limited, but it is preferable to use 0.0001 to 0.5 mol of catalyst Y with respect to 1 mol of total hydroxyl groups in polyglycerin, The amount is preferably 0.0005 to 0.2 mol.
  • the production amount of polyglycerin poly (meth) acrylate can be increased, and by setting it to 0.5 mol or less, by-product formation and reaction liquid coloring And the purification process after completion of the reaction can be simplified.
  • Component (A) is produced by subjecting polyglycerol and a monofunctional (meth) acrylate to an ester exchange reaction in the presence of 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 production amount of the target polyfunctional (meth) acrylate can be increased, and by making it 10.0 mol or less, the generation of by-products and coloring of the reaction liquid are suppressed.
  • the purification process after completion of the reaction can be simplified.
  • 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.
  • this combination is excellent in color tone after the reaction is finished (small yellowishness), so colorless transparency such as clear varnish and hard coat is regarded as important. It can be used suitably for a certain application.
  • the catalyst 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 to 180 ° C, more preferably 60 to 160 ° C.
  • 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 a predetermined reaction temperature can be maintained, and may be performed in a reduced pressure state or in a pressurized state.
  • the 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 polyglycerin 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 polyglycerol 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
  • 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 exerted, and by setting it to 30,000 wtppm or less, coloring of the reaction solution can be suppressed, and the purification step after completion of the reaction can be simplified. Moreover, the fall of the cure rate of the (A) component obtained can be prevented.
  • the reaction time in the method for producing the component (A) varies depending on the type and amount of the catalyst used, the reaction temperature, the 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.
  • a batch system polyglycerol, 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.
  • the component (A) is a mixture of (meth) acrylate obtained by transesterification of polyglycerol and monofunctional (meth) acrylate, and the number of (meth) acryloyl groups is different (meth) A mixture of acrylates.
  • the hydroxyl value of the component (A) is preferably 80 to 600 mgKOH / g, more preferably 100 to 500 mgKOH / g, and particularly preferably 120 to 400 mgKOH / g.
  • the hydroxyl value of the component (A) is 80 mgKOH / g or more, the cured film of the composition is excellent in low curl properties, and when the hydroxyl value is 600 mgKOH / g or less, the composition is excellent in curability. Become.
  • the polydispersity (Mw / Mn) of the main peak by gel permeation chromatography is preferably 1.0 to 2.5. 1.0 to 2.0 is more preferable, and 1.0 to 1.5 is particularly preferable.
  • Mw means a weight average molecular weight and Mn means a number average molecular weight.
  • Mw / Mn of 2.5 or less means that there are few high molecular weight bodies (henceforth "side reaction high molecular weight body") by side reactions (Michael addition etc.) other than (meth) acrylate formation. It is preferable because of its excellent curability.
  • polyglycerin (meth) acrylate obtained by dehydration esterification reaction contains a large amount of side reaction high molecular weight compared with polyglycerin (meth) acrylate obtained by transesterification reaction, and Mw / Mn exceeds 2.5, and the curability is insufficient.
  • (Meth) acrylate is preferably an acrylate from the viewpoint of fast curability.
  • Curable composition TECHNICAL FIELD This invention relates to the curable composition containing the said (A) component.
  • a production method for producing the composition including a step of producing a mixture of polyglycerin (meth) acrylate by transesterifying polyglycerin and monofunctional (meth) acrylate in the presence of the catalysts X and Y is preferable.
  • the side reaction high molecular weight product in the component (A) to be obtained is small, it is easy to handle with a low viscosity, and it is preferable because it is excellent in curability and scratch resistance. What is necessary is just to follow the manufacturing method of above-described (A) component as the said process.
  • the component (A) and other components may be stirred and mixed.
  • the content ratio of the component (A) is such that the composition becomes rapidly curable, and the resulting cured film is excellent in low yellowing, high flexibility and low curling properties, and the total amount of the curable components is 100% by weight.
  • the amount is preferably 20 to 100% by weight, more preferably 30 to 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.
  • a compound having a polymerizable functional group other than the components (A) and (D) such as a cationic curable compound (for example, an epoxy compound or an oxetane compound) (hereinafter referred to as “other polymerizable component”) is blended.
  • a cationic curable compound for example, an epoxy compound or an oxetane compound
  • other polymerizable component a compound having a polymerizable functional group other than the components (A) and (D)
  • 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 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 (B) photopolymerization initiator
  • component (C) thermal polymerization initiator
  • ethylenic polymer other than the component (A) 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 Examples thereof include inorganic fine particles [hereinafter referred to as “(G) component”] and polymers [hereinafter referred to as “(H) component”].
  • component (D) Compound having saturated group
  • component (E) pigment or dye
  • component (F) organic solvent or water
  • colloidal Examples thereof include inorganic fine particles [hereinafter referred to as “(G) component”] and polymers [hereinafter referred to as “(H) component”].
  • 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.
  • Acetophenone compounds of Benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1- [4- (4-benzoylphenylsulfanyl) phenyl ] -2-Methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone and 4-methoxy-4 ′ -Benzophenone compounds such as dimethylaminobenzophenone; Such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzo
  • Examples of other compounds include benzyl, ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate, methyl phenylglyoxylate, ethyl anthraquinone, phenanthrenequinone, camphorquinone, and the like.
  • component (B) when a UV-LED is used as an ultraviolet light source will be described.
  • component (B-1) an acylphosphine oxide compound
  • the component (B-1) is more preferable for the use of a UV-LED curable clear coating agent.
  • Specific examples of the component (B-1) include the compounds described above.
  • the component (B) contains a thioxanthone compound (hereinafter referred to as “component (B-2)”) in order to further enhance the UV-LED curability.
  • component (B-3) 4,4′-bis (dialkylamino) benzophenone [hereinafter referred to as “component (B-3)”].
  • component (B-2) and the component (B-3) may be used in combination.
  • the component (B-1) can be used in combination.
  • a tertiary amine compound in order to increase the efficiency of hydrogen abstraction and active radical generation by the exposed component (B-2).
  • a tertiary amine compound an amine compound having an aromatic ring such as ethyl 4-dimethylaminobenzoate is preferable.
  • Specific examples of the component (B-2) include the compounds described above.
  • component (B-3) examples include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and the like.
  • the content ratio of the component (B) is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the total of the curable components, from the viewpoint that both curability of the composition and low yellowing of the cured film can be achieved. 18 parts by weight is more preferable, and 3 to 15 parts by weight is still more preferable.
  • the content ratio of the component (B-1) is 1 to 15 parts by weight with respect to 100 parts by weight of the curable components in total. Preferably, 3 to 12 parts by weight is more preferable.
  • the component (B-2) is preferably not contained in an amount of 2 parts by weight or more, more preferably 1 part by weight or more, from the viewpoint that the cured film can be low yellowing.
  • the component (B-3) is preferably not contained in an amount of 1 part by weight or more, more preferably 0.5 parts by weight or more, from the viewpoint that the cured film can be made low yellowing.
  • the content ratio of the component (B-2) and / or the component (B-3) is 100 parts by weight in total of the curable components. On the other hand, it is preferably 1 to 15 parts by weight, and more preferably 2 to 12 parts by weight.
  • the component (B-1) is preferably contained in an amount of 1 to 15 parts by weight. More preferably, it contains 10 parts by weight.
  • the total amount of the component (B) is preferably 20 parts by weight or less with respect to 100 parts by weight of the curable component.
  • thermosetting type composition a thermal-polymerization initiator can be mix
  • Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.
  • 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-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl- , 5-di (m
  • azo compound examples include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. Azodi-t-octane, and azodi-t-butane. 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) (D) component, the (A) an ethylenically unsaturated compound other than the component is formulated for the purpose of imparting various properties to the cured film 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
  • ⁇ functional means a compound having ⁇ ethylenically unsaturated groups
  • polyfunctional means a compound having ⁇ ethylenically unsaturated groups
  • the component (D) include (meth) acrylate, (meth) acrylamide, vinyl ether, maleimide and the like, and (meth) acrylate is preferable.
  • acrylate, acrylamide, and vinyl ether are preferable from the viewpoint of curability, and acrylate is 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 () of aliphatic diols such as (meth) acrylate and nonanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, norbornane dimethylol di (meth) acrylate, and tricyclodecane dimethylol di (meth) acrylate (Meth) acrylate; Polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate; Di (meth) acrylate,
  • 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) acrylates such as methanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and dipropylene glycol divinyl ether are also included.
  • the polyalkylene glycol di (meth) acrylate (D-1-1) [hereinafter referred to as “(D-1) -1) component ”].
  • the viscosity can be reduced and the flexibility can be further improved without greatly reducing the excellent rapid curability of the component (A).
  • a diacrylate of polyethylene glycol (average degree of polymerization 2 to 10) is preferable in that the composition has a low viscosity and excellent curability, and the cured film has excellent flexibility.
  • the preferable content varies depending on the use of the composition of the present invention. It also varies depending on the type of component (D-1-1).
  • the content of the component (D-1-1) 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. It is more preferable.
  • 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, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri- or tetra (meth) acrylate, ditrimethylolpropane tri- or tetra- (meta) ) Acrylate, diglycerin tri or tetra (meth) acrylate, dipentaerythritol tri, tetra, penta or hexa (meth) acrylate and tripentaerythritol tri, tetra, penta, hexa, hepta or octa (meth) Polyol poly (meth) acrylates, such as acrylates; Tri (meth) acrylate of glycerin alkylene oxide adduct, tri (meth) acrylate of trimethylolpropane alkylene oxide adduct, tri or tetra
  • 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.
  • the composition of the present invention is used as a hard coat
  • the component (D-2) dipentaerythritol poly (meth) acrylate (D-2-1) [hereinafter referred to as “(D-2-1) component”
  • component (D-2) dipentaerythritol poly (meth) acrylate (D-2-1) [hereinafter referred to as “(D-2-1) component”
  • component (D-2) dipentaerythritol poly (meth) acrylate (D-2-1) [hereinafter referred to as “(D-2-1) component”
  • component (D-2) dipentaerythritol poly (meth) acrylate (D-2-1) [hereinafter referred to as “(D-2-1) component”
  • component (D-2) dipentaerythritol poly (meth) acrylate (D-2-1) [hereinafter referred to as “(D-2-1) component”
  • component (D-2) dipentaerythrito
  • 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. May be included. In this case, the fast curability is impaired, but the curability is improved as compared with the composition not using the component (A).
  • 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 requiring scratch resistance and colorless transparency such as hard coats, and specifically, silica, titania, zinc oxide, tin oxide, and indium oxide are preferred. Silica is preferred.
  • 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) colloidal inorganic particles having an ethylenically unsaturated group or photoreactive group bonded to the surface (hereinafter referred to as “(G-1) component”), an ethylenically unsaturated group or photoreactive property. And colloidal inorganic particles having no 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) an ethylenically unsaturated group or photoreactive group-bonded polymer (hereinafter referred to as “(H-1) component”) and a polymer having no ethylenically unsaturated group or photoreactive group [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.
  • 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, and thermal radical polymerization initiators. Some of these will be briefly explained below.
  • 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.
  • 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 phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
  • 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 antioxidant include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphite, and triaryl phosphite.
  • Examples of commercially available products of these derivatives include Adeka Co., Ltd., Adeka Stab PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, and 3010 etc. are mentioned.
  • 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.
  • examples of 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 ethylenically unsaturated group, and is a compound different from the component (D-3). Adhesion may be improved without having an ethylenically 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 superimposed. Particles other than the component (G) may be blended.
  • the particle size of the particles varies depending on the application, but in general, particles having a size of 0.2 to 100 ⁇ m can be preferably used.
  • the particles may be inorganic or organic. Examples of the inorganic 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; Polymeric antistatic agents such as polyetheresters, polyetheresteramides, polystyrene sulfonates, (meth) acrylate polymers including tetraspherical ammonium salts, and polyetherpolysilicones; Monomers having acidic
  • 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, and leather.
  • the composition of the present invention does not cause curling when the composition is cured, and is excellent in the flexibility of the cured film, so it is preferably applied to thin substrates such as paper and plastic films. can do.
  • 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.
  • Even when the water content is high for example, when it contains 50% by weight or more of the whole), when 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 is obtained. There are cases where it is possible.
  • 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 clear varnish using a 365-nm UV-LED is preferably 365 to 100 to 1,000 mJ / cm 2 and more preferably 200 to 700 mJ / cm 2 .
  • the curable composition of the present invention is preferably used as an active energy ray curable composition, and exhibits the effects of fast curing, low yellowing, high flexibility and low curl as described above. Can be used for various purposes. Examples of preferred applications include clear coating agents and coating agents such as paint, inks such as offset ink and inkjet ink, adhesives, resists, and molding materials. Applications in which the composition of the present invention is particularly useful include clear coating such as UV-LED curable clear varnish, UV-LED curable ink, hard coat, inkjet ink, nail paint and the like.
  • the active energy ray-curable composition exhibits the following effects in each application in addition to the above-mentioned fast curing, low yellowing, high flexibility and low curling properties.
  • the active energy ray curable clear coating agent (including clear varnish) composition exhibits excellent curability even when the light source is a UV-LED, and low yellowing and high bending, which are difficult to achieve with curability. And low curling property.
  • the active energy ray-curable ink composition exhibits excellent curability even when the light source is a UV-LED, and can be excellent in high flexibility and low curl properties.
  • the composition for active energy ray-curable hard coat can be excellent in scratch resistance, high flexibility and low curl properties.
  • the active energy ray-curable water-based ink jet composition does not contain an organic solvent, or even if it contains a small amount of an almost harmless organic solvent such as ethanol, and has a low viscosity, fast curability, low It can be excellent in yellowing and high flexibility.
  • the active energy ray-curable nail coating composition does not contain an organic solvent, or even if it contains a small amount of an almost harmless organic solvent such as ethanol. It can be excellent in low yellowing.
  • the active energy ray curable clear coating agent composition, the active energy ray curable ink composition, the active energy ray curable hard coat composition, and the solventless active energy ray curable composition will be described in detail.
  • Active energy ray curable clear coating agent composition As an active energy ray curable clear coating agent composition (including clear varnish), when used as a UV-LED curable clear coating agent, (B) component (B) -1) A composition containing a component (acylphosphine oxide compound) is preferred. In the case of the use, a composition containing (D-1) component (compound having two ethylenically unsaturated groups) as component (D) is preferred, and (D-1) component is D-1-1) A composition containing the component [polyalkylene glycol di (meth) acrylate] is preferred.
  • Active energy ray curable ink composition when used as a UV-LED curable ink composition, as component (B), component (B-2) (thioxanthone compound) And / or (B-3) component [4,4′-bis (dialkylamino) benzophenone] is preferred.
  • Active energy ray-curable hard coating composition The active energy ray-curable composition of the present invention is excellent in rapid curability, low yellowing, high flexibility, low curl properties, and also excellent in scratch resistance. It can be preferably used for a hard coat composition.
  • Japanese Patent Application Laid-Open No. 2012-229412 discloses that a composition containing a specific urethane (meth) acrylate is excellent in scratch resistance, pencil hardness and low curl property, but its performance is insufficient.
  • JP-A-2013-23585 discloses that a composition containing urethane (meth) acrylate and tripentaerythritol octa (meth) acrylate has low curl, high hardness, and high flexibility. There is a need for improvement.
  • Japanese Patent Laid-Open No. 2016-6161 discloses that a composition containing two specific types of urethane (meth) acrylates is excellent in terms of scratch resistance, high flexibility, and hardness. Is unknown.
  • (meth) acrylate (A) and urethane (meth) acrylate (B) having a structure in which alkylene oxide is added to polyglycerin is 95/5 to 50 (A) / (B). It is shown that the composition contained in the range of / 50 is excellent in scratch resistance and substrate followability (flexibility). However, further performance improvement is required.
  • polyglycerin (meth) acrylate polyglycerin (meth) acrylate to which no alkylene oxide is added
  • Japanese Patent Application Laid-Open No. 2015-44955 describes a (meth) acrylate of polyglycerin, but its acryloyl group addition rate is low and its physical properties are unknown.
  • Japanese Patent Application Laid-Open No. 2006-182725 describes a production process that undergoes acetalization of polyglycerin. However, since the hydroxyl value is high, the (meth) acrylate conversion rate is considered to be low.
  • polyglycerin (meth) acrylate is fast in curability and excellent in flexibility, but its scratch resistance is unknown.
  • polyglycerin (meth) acrylate obtained by a conventional production method is suitable as a blending raw material for obtaining a composition excellent in curability and / or scratch resistance.
  • the inventors of the present invention provide a composition containing tetra (meth) acrylate obtained from a polyol obtained by adding 4 to 8 moles of ethylene oxide to diglycerin, and penta and hexa (meth) acrylates of dipentaerythritol in a specific ratio. Although it is disclosed that the cured film is excellent in all points of scratch resistance, high flexibility and low curl properties (Japanese Patent Laid-Open No. 2016-23203), further performance improvement is required.
  • composition for hard coat of the present invention the above-mentioned problems can be solved, and it is excellent in fast curability, low yellowing, high bendability, low curl properties, and excellent in scratch resistance. be able to.
  • a composition containing (D-2) component compound having 3 or more ethylenically unsaturated groups
  • component (D) a composition containing (D-2) component (compound having 3 or more ethylenically unsaturated groups) is preferable as component (D), and as component (D-2), , (D-2-1) component [dipentaerythritol poly (meth) acrylate] and / or (D-2-2) component [urethane (meth) acrylate having three or more (meth) acryloyl groups]
  • Compositions are preferred.
  • Solvent-free active energy ray-curable composition The active energy ray-curable composition of the present invention does not contain an organic solvent, or even if it contains a small amount of an organic solvent such as ethanol, or a water-based composition. It can be used for a certain low viscosity solventless active energy ray-curable composition.
  • the composition can be further used for an active energy ray-curable inkjet composition having a low environmental load and an active energy ray-curable nail coating composition that is an aesthetic coating material applied to nails.
  • 2- (vinyloxyethoxy) ethyl acrylate has attracted attention as a monomer that is excellent in all of low viscosity, fast curability, and high flexibility (for example, Japanese Patent No. 5790234).
  • This monomer also has an aspect of improving curability by a combination of a compatible photopolymerization initiator such as a thioxanthone photopolymerization initiator, but yellowing is a problem due to a combination with a photopolymerization initiator that improves curability. There is a problem that the curability is still insufficient.
  • the active energy ray-curable nail coating composition that is an aesthetic paint to be applied to nails.
  • it is necessary to have a low viscosity in order to be applied to the nail, and in order not to adversely affect the human body, it is also necessary to be able to be cured with a UV-LED having a long wavelength and low illuminance. Sunlight may be used instead of the UV-LED.
  • the conventional active energy ray-curable nail paint often uses a (meth) acrylate monomer having a strong odor in order to reduce the viscosity without using a solvent (for example, JP 2013-43853 A). There were concerns about the health of the workers.
  • the above-mentioned problems can be solved, and even if it does not contain an organic solvent or is an aqueous composition, it is fast-curing, low yellowing, high flexibility and low It can be excellent in curling property.
  • parts means parts by weight.
  • Production example 1-1) Production Example 1 [Production of component (A), hydroxyl value: 299 mgKOH / g] Into a 1 liter flask equipped with a stirrer, thermometer, gas introduction tube, and cooling tube, polyglycerin [polyglycerin 06 manufactured by Daicel Corporation, hydroxyl value 960 mgKOH / g (17.1 meq / g), hereinafter “D -PGL6 "), 146 g (2.5 mol as a hydroxyl group), 2-methoxyethyl acrylate (hereinafter referred to as” MEA ”) 585 g (4.5 mol), and catalyst X as a DABCO 1.4 g (0.0125) Mol), as catalyst Y, zinc acrylate (hereinafter referred to as “ZnAc”) 5.2 g (0.025 mol), hydroquinone monomethyl ether (hereinafter referred to as “MQ”) 0.35 g, and phenothiazine 0.012 g
  • the obtained filtrate was put into a flask connected with a stirrer, a thermometer, a gas introduction tube, a distillation cooling tube, and a decompression tube, and the temperature was 90 to 100 ° C. and the pressure was 0.01 to 200 mmHg.
  • the mixture was stirred for 13 hours while bubbling dry air, and unreacted MEA and by-product 2-methoxyethanol were distilled off to obtain polyglycerol acrylate as a reaction product.
  • the residual amount of MEA in the product was 100 ppm or less. No odor was felt in the product.
  • the obtained polyglycerin acrylate had a viscosity of 7.3 Pa ⁇ s (25 ° C.) and a hydroxyl value of 299 mgKOH / g.
  • the polystyrene-reduced Mw, Mn, and polydispersity (Mw / Mn) of the main peak by GPC were 1,291, 1,016, and 1.3, respectively.
  • the polyglycerin acrylate of Production Example 1 is referred to as pGlyAc-1.
  • hydroxyl value and GPC were measured as follows. ⁇ Hydroxyl value measurement conditions Add acetylating reagent to the sample and heat-treat in a hot tub. 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. ⁇ GPC measurement conditions and equipment: GPC system name manufactured by Waters Co., Ltd. 1515 2414 717P 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.
  • RI Differential refractive index
  • the pressure in the reaction system is adjusted in the range of 150 to 300 mmHg while heating and stirring in the reaction liquid temperature range of 115 to 125 ° C., and the mixture of 2-methoxyethanol and MEA by-produced as the transesterification proceeds.
  • the liquid was extracted from the reaction system via a rectification column and a cooling pipe.
  • MEA of the same weight as the extracted liquid was added to the reaction system as needed. After 9 hours of heating and stirring while reducing the pressure, the pressure in the reaction system was returned to normal pressure, and the extraction was completed.
  • the product 2-methoxyethanol was distilled off to obtain polyglycerol acrylate as a reaction product.
  • the residual amount of MEA in the product was 100 ppm or less. No odor was felt in the product.
  • the obtained polyglycerin acrylate had a viscosity of 4.2 Pa ⁇ s (25 ° C.) and a hydroxyl value of 114 mgKOH / g.
  • the polystyrene-reduced Mw, Mn, and polydispersity (Mw / Mn) of the main peak by GPC were 1,417, 1,098, and 1.3, respectively.
  • the polyglycerin acrylate of Production Example 2 is hereinafter referred to as pGlyAc-2.
  • the obtained polyglycerin acrylate had a viscosity of 29.4 Pa ⁇ s (25 ° C.) and a hydroxyl value of 367 mg KOH / g.
  • the polystyrene-reduced Mw, Mn, and polydispersity (Mw / Mn) of the main peak by GPC were 1,407, 1,054, and 1.3, respectively.
  • the polyglycerin acrylate of Production Example 3 is hereinafter referred to as pGlyAc-3.
  • the pressure in the reaction system is adjusted in the range of 55 to 700 mmHg while heating and stirring at a reaction solution temperature in the range of 80 to 130 ° C., and a mixture of 2-methoxyethanol and MEA by-produced as the transesterification proceeds.
  • the liquid was extracted from the reaction system via a rectification column and a cooling pipe.
  • MEA of the same weight as the extracted liquid was added to the reaction system as needed.
  • the pressure in the reaction system was returned to normal pressure, and the extraction was completed.
  • the acrylate conversion ratio of the hydroxyl group by transesterification from the amount of 2-methoxyethanol produced by liquid chromatography it was 42 mol%.
  • the polystyrene-reduced Mw, Mn and polydispersity (Mw / Mn) of the main peak by GPC were 1,038, 849 and 1.2, respectively.
  • the polyglycerol acrylate of Production Example 4 is referred to as pGlyAc-4.
  • the temperature of the reaction liquid changed in the range of 109 to 115 ° C.
  • the heating of the reaction liquid was completed, and the pressure in the reaction system was returned to normal pressure to complete the extraction.
  • the esterification reaction rate of the hydroxyl group determined from the amount of water extracted from the reaction system was 44 mol%.
  • the reaction solution was transferred to a separatory funnel and extracted and purified to remove unreacted acrylic acid. 205 g of n-hexane was added and shaken vigorously, and then allowed to stand.
  • the liquid after standing was separated into two layers, and the upper liquid contained n-hexane, toluene and acrylic acid, but the trace amount of the target polyglycerol acrylate was contained.
  • n-hexane was added again and the same extraction and purification operation was performed.
  • the neutralization operation for removing PTS was performed.
  • 2070 g of tetrahydrofuran and 207 g of magnesium oxide were added and stirred at room temperature for 1 hour, followed by pressure filtration. By this operation, a neutralized salt of PTS and magnesium oxide was removed as a residue as a filtration residue, and a filtrate containing the target polyglycerol acrylate was obtained.
  • the polystyrene-reduced Mw, Mn, and polydispersity (Mw / Mn) of the main peak by GPC were 6,245, 2,002, and 3.1, respectively.
  • the polyglycerin acrylate of Comparative Production Example 1 is hereinafter referred to as pGlyAc-5.
  • the cured state of the coating film was confirmed with a finger, and when it was not cured, another one-pass ultraviolet irradiation was performed.
  • the surface of the cured film was rubbed with a non-woven fabric (Bencot manufactured by Asahi Kasei) with a force of about 1 kg / cm 2 .
  • wound was attached even after 10-pass ultraviolet irradiation, "10 ⁇ " was evaluated.
  • hardenability was evaluated by the frequency
  • the flexibility is obtained by winding a PET film having a cured film on a core rod having a diameter of 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, and 8 mm (the cured film is on the outside).
  • the minimum diameter at which peeling does not occur is indicated.
  • a test for bending the film without a core rod was also conducted, and when cracks did not occur, it was evaluated as 0 mm because there was no core rod.
  • Component (D) ⁇ M-240 Polyethylene glycol (average polymerization degree 4) diacrylate, Aronix M-240 manufactured by Toagosei Co., Ltd.
  • SP-1509 Epoxy acrylate having a structure in which acrylic acid is added to bisphenol A type epoxy resin, Lipoxy SP-1509 manufactured by Showa Denko K.K. (component (D-1)) (Other ingredients) 8019add: silicone leveling agent, 8019ADDITIVE manufactured by Toray Dow Corning
  • A Even if the fold is strongly compressed with a nail after the sample is completely bent, there is no crack.
  • B There was no crack even when the sample was completely bent, but cracking sometimes occurred when the crease was strongly compressed with a nail.
  • C Even if it is wound around a 2 mm ⁇ core rod, there is no cracking, but cracking occurs when it is bent completely.
  • D Cracking occurs when wound around a 2 mm ⁇ core rod. No cracking occurs at 3 mm ⁇ .
  • E Cracking occurred even when wound around a 3 mm ⁇ core rod.
  • compositions of Examples 4 and 5 which are the compositions of the present invention are UV-LED curable, low curl, high flexibility, Excellent scratch resistance and low yellowing.
  • Example 5 the flexibility was improved as compared with Example 4, and the crack was not generated even when the laminate of the cured film and the film was strongly bent.
  • the composition of Comparative Example 3 which does not contain the component (A) of the present invention was significantly inferior in curling property and flexibility as compared with the composition of Example 5, and also inferior in UV-LED curability.
  • the composition of Comparative Example 4 that did not contain the component (A) of the present invention was poorer in curability than the compositions of Example 4, Example 5, and Comparative Example 3.
  • the scratch resistance was improved immediately after UV-LED curing when left under a fluorescent lamp, but was scratched when rubbed with a force of 4 kgf / cm 2 and was inferior to the other three.
  • component DETX 2,4-diethylthioxanthone, KAYACURE DETX-s [(B-2) component] manufactured by Nippon Kayaku Co., Ltd.
  • EAB 4,4′-bis (diethylamino) benzophenone, SB-PI701 manufactured by SHUANG-BANG INDUSTRIAL [component (B-3)]
  • component -FA5375 blue pigment, C.I. I. Pigment Blue 15: 3, manufactured by DIC Corporation, Fastogen Blue FA5375 (Other ingredients) ⁇
  • EPA Ethyl-4- (dimethylamino) benzoate, manufactured by Nippon Kayaku Co., Ltd., KAYACURE EPA
  • the UV-LED curability was twice or more.
  • the composition of Example 7 showed UV-LED curability superior to that of Comparative Example 5 although the component (B) was not a combination of TPO and EAB which had excellent curability.
  • the composition of the present invention had very excellent curability even as a UV-LED curable ink composition.
  • Examples 8 to 12 Comparative Examples 6 to 8 (Hard Coat Composition-1) 5-1) Production of composition
  • the components shown in Tables 5 and 6 were blended in their respective parts and stirred and mixed in accordance with a conventional method to prepare a photocurable composition.
  • surface is synonymous with the said Table 2 and Table 3.
  • the meanings of the abbreviations of the components not listed in Tables 2 and 3 are as follows.
  • the component (G) is supplied in a state of being dispersed in the solvent as the component (F), but in Tables 5 and 6, it is described separately for each component.
  • Component (D) -M-460 tetraacrylate of diglycerin ethylene oxide 4 mol adduct, Aronix M-460 manufactured by Toagosei Co., Ltd.
  • Component (F) -PGM Propylene glycol monomethyl ether-IPA: Isopropyl alcohol-MEK: Methyl ethyl ketone
  • Component (G) AC2140: Silica content in an organosilica sol MEK-AC-2140Z (surface methacryloyl group-modified colloidal silica having an average particle size of 10 to 15 nm, dispersion medium MEK) manufactured by Nissan Chemical Industries, Ltd. [(G-1) component ⁇ . AC2140 (NET) in the table means solid content.
  • IPA-ST Silica content in the organosilica sol IPA-ST (colloidal silica with an average particle size of 10 to 15 nm and no surface modification, dispersion medium IPA) manufactured by Nissan Chemical Industries [component (G-2)].
  • IPA-ST (NET) in the table means solid content.
  • compositions of Examples 8 to the 12 a of the present invention abrasion resistance, high hardness, high flexibility, and low The curling property was balanced and high performance.
  • the compositions of Examples 8 to 12 are compared with the compositions of Comparative Examples 6 to 8 which do not contain the component (A).
  • the composition of Example 8 had the same flexibility as the composition of Comparative Example 6, the scratch resistance, pencil hardness, and low curl properties were all improved.
  • the composition of Example 8 was superior in flexibility and low curl properties to the compositions of Comparative Examples 7 and 8 while having the same scratch resistance and pencil hardness.
  • Example 9 had the same pencil hardness and flexibility as the compositions of Comparative Examples 7 and 8, the scratch resistance and the low curl property were excellent.
  • the composition of Example 10 had excellent scratch resistance and pencil hardness, and particularly excellent low curl properties.
  • the compositions of Example 11 and Example 12 were excellent in scratch resistance and pencil hardness, and extremely excellent in low curl properties. It should be noted that the cured films of the compositions of Examples 8 to 12 are all excellent in colorless transparency.
  • Examples 13 to 15 and Comparative Examples 9 to 10 (ink-jet composition) 6-1) Production of composition
  • the components shown in Table 7 were blended in their respective parts and stirred and mixed in accordance with a conventional method to prepare a photocurable composition.
  • the meanings of the abbreviations of the compounding components in the table are the same as those in Tables 2 to 6.
  • the meanings of the abbreviations of the components not listed in the table are as follows.
  • Component (B) Irg-2959: Irgacure 2959, manufactured by BASF, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Irg-819: BASF Irgacure 819, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide [component (B-1)]
  • Component (D) / VEEA VEEA manufactured by Nippon Shokubai Co., Ltd., 2-vinyloxyethoxyethyl (meth) acrylate [(D-1) component] ⁇ HBA: 4-HBA, 4-hydroxybutyl acrylate (component (D-3)) manufactured by Osaka Organic Chemical Industry Co., Ltd. -POA: POA manufactured by Kyoeisha Chemical Co., Ltd., phenoxyethyl acrylate [(D-3) component] (F) component EtOH: ethanol
  • the composition of Example 15 is not completely solvent-free because it contains 7% by weight of ethanol, but it contains only ethanol with a low alcohol content, so it can be used for the human body unless it is used in large quantities in a small room. It is considered harmless.
  • the composition of Example 15 was extremely excellent in terms of both low viscosity and fast curability, and was also excellent in low yellowing and bending resistance.
  • the composition of Example 13 also had the feature that there was no odor at all.
  • the composition of Example 14 had a very weak odor. This is because the hydroxyl group-containing (meth) acrylate often has a low odor and the same applies to HBA.
  • HBA is suitable as a component of a low odor inkjet composition because the skin irritation of HBA is weaker than those. is there.
  • the compositions of Example 15, Comparative Example 9 and Comparative Example 10 felt odor.
  • the composition of Comparative Example 10 had a strong odor.
  • the composition of Example 13 and Example 15 since a low molecular weight acrylate monomer is not included, it can be anticipated that skin irritation is low.
  • Examples 16 to 18 (ink-jet ink composition)
  • the composition of Example 15 was mixed with the following commercially available dye-based inkjet ink at a weight ratio of 1: 1 to prepare an inkjet ink composition.
  • Example 16 INK-E50 series (Magenta) manufactured by Sanwa Supply Co., Ltd.
  • Example 17 INK-E50 series (Cyan) manufactured by Sanwa Supply Co., Ltd.
  • Example 18 INK-E50 series (yellow) manufactured by Sanwa Supply Co., Ltd.
  • Example 19 (Nail aesthetic coating composition) When the composition of Example 4 was applied to a nail with a brush and exposed to sunlight on a sunny day in March, a cured film having a glossy feeling without tack was obtained after 1 minute. It was. No appearance defects such as cracks and turbidity were observed. Regarding the ease of peeling of the cured film, it was not peeled off by rubbing with a finger, but it was peeled off when rubbing strongly with a nail. In other words, it could be removed without using an organic solvent. For this reason, it can be said that it is a nail aesthetic composition excellent in safety and convenience (rapid curing).
  • the curable composition of the present invention can be preferably used as an active energy ray curable composition and is excellent in fast curability, low yellowing, high flexibility, and low curl properties, and therefore, as an active energy ray curable clear coating agent. It is preferable and can be used particularly preferably when the light source is a UV-LED.
  • the base material of the clear coating agent include plastic and wood protective coats and paper clear varnish.
  • the composition containing a pigment can also be suitably used as a UV-LED curable ink composition.
  • the active energy ray-curable composition of the present invention is also suitable as a hard coat because of its excellent scratch resistance, and is particularly suitable as a hard coat for plastic films because of its remarkable curl characteristics. be able to.
  • the active energy ray-curable composition of the present invention can be suitably used as a water-based inkjet ink or nail coating paint.

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Abstract

L'invention concerne une composition durcissable qui présente des propriétés de durcissement rapide et forme un film durci qui présente de faibles propriétés de jaunissement, une aptitude au pliage élevée et de faibles propriétés de gondolage. Une composition durcissable selon la présente invention contient un mélange (A) d'un composé ayant un groupe (méth)acryloyle, ledit composé étant obtenu par soumission d'un polyglycérol ayant un indice d'hydroxyle de 700 à 1 200 mg de KOH/g et d'un composé ayant un groupe (méth)acryloyle à une réaction de transestérification en présence de catalyseurs X et Y. Catalyseur X : un ou plusieurs composés sélectionnés dans le groupe constitué d'amines tertiaires cycliques ayant une structure azabicyclo et leurs sels et complexes, d'amidines et leurs sels et complexes, de composés ayant un noyau pyridine et leurs sels et complexes, et de la phosphine et de ses sels et complexes. Catalyseur Y : un composé contenant du zinc.
PCT/JP2017/026931 2016-07-29 2017-07-25 Composition durcissable WO2018021352A1 (fr)

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JP2021105081A (ja) * 2019-12-26 2021-07-26 セイコーエプソン株式会社 インクジェットインク及び記録装置
CN113755047A (zh) * 2021-09-06 2021-12-07 百草边大生物科技(青岛)有限公司 一种应用于儿童读物的含植物成分的大生物水性光油
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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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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
CN113755047A (zh) * 2021-09-06 2021-12-07 百草边大生物科技(青岛)有限公司 一种应用于儿童读物的含植物成分的大生物水性光油
CN113755047B (zh) * 2021-09-06 2022-04-01 百草边大生物科技(青岛)有限公司 一种应用于儿童读物的含植物成分的大生物水性光油

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