CN117120496A

CN117120496A - Curable composition, active energy ray curable composition, and active energy ray curable coating agent composition

Info

Publication number: CN117120496A
Application number: CN202280027850.3A
Authority: CN
Inventors: 大房一树; 桥本直树
Original assignee: Toagosei Co Ltd
Current assignee: Toagosei Co Ltd
Priority date: 2021-04-23
Filing date: 2022-04-22
Publication date: 2023-11-24
Also published as: JPWO2022225041A1; KR20240021744A; TW202309124A; WO2022225041A1

Abstract

The present invention provides a curable composition containing a multifunctional urethane (meth) acrylate adduct, which has a low viscosity, and which has a cured film having a good balance between surface hardness, scratch resistance and bendability and excellent curling properties, and preferably provides an active energy ray curable composition, particularly a composition which can be preferably used as a coating agent. A curable composition comprising the following component (A): component (A): the mixture (a 1) is a mixture of at least one compound selected from the group consisting of glycerin (meth) acrylate and diglycerin (meth) acrylate, and has a hydroxyl value of 20mgKOH/g to 300mgKOH/g.

Description

Curable composition, active energy ray curable composition, and active energy ray curable coating agent composition

Technical Field

The present invention relates to a curable composition, preferably an active energy ray curable composition, wherein the curable composition comprises a urethane (meth) acrylate as a urethane reactant of a compound having one or more hydroxyl groups and two or more (meth) acryloyl groups and an organic polyisocyanate [ hereinafter, referred to as "multifunctional urethane (meth) acrylate adduct ].

The composition of the present invention can be used for various applications, and particularly has a low viscosity and a rapid hardening property as compared with conventional multifunctional urethane (meth) acrylate adducts, and when used as a raw material for a hard coating agent, a composition having a good balance between the elastic modulus and the bendability of the resulting cured film can be obtained, and therefore, can be preferably used as a coating agent composition, and belongs to these technical fields.

In the present specification, an acryl group and/or a methacryl group is referred to as a (meth) acryl group, an acrylate and/or a methacrylate is referred to as a (meth) acrylate, and acrylic acid and/or methacrylic acid is referred to as a (meth) acrylic acid.

Background

The multifunctional urethane (meth) acrylate adduct is a compound obtained by reacting a multifunctional (meth) acrylate having one or more hydroxyl groups and two or more (meth) acryloyl groups with an organic polyisocyanate having two or more isocyanate groups, and is used in various curable compositions such as coating agents, inks, adhesives, and sealants, particularly in active energy ray curable compositions, because of excellent curability, tensile strength, elongation, and toughness of the cured film.

As the application in which the multifunctional urethane (meth) acrylate adduct is widely used, a hard coating agent for plastics is exemplified.

Plastic substrates are lightweight and excellent in impact resistance, formability, etc., but have a disadvantage that the surface is easily damaged and the hardness is low, so that the appearance is remarkably impaired when they are used as they are. Therefore, it is required to coat the surface of a plastic substrate with a coating composition, perform a so-called hard coat treatment, impart scratch resistance, and improve surface hardness.

Conventionally, as a raw material for a hard coat agent, a polyfunctional urethane (meth) acrylate adduct having ten or more (meth) acryloyl groups in one molecule has been used.

Patent document 1 discloses an active energy ray-curable composition comprising a reactant of dipentaerythritol pentaacrylate and an aliphatic divalent isocyanate, that is, a multifunctional urethane (meth) acrylate adduct having ten (meth) acryloyl groups in one molecule.

However, the composition of the above patent is excellent in hardness of a cured film, scratch resistance and adhesion to a substrate, but when a film substrate subjected to a hard coat layer treatment is bent, cracking or peeling is likely to occur, and the bending property is insufficient. On the other hand, when the bending resistance is to be improved, the hardness and scratch resistance of the cured film are insufficient, and it is difficult to achieve both of these properties. In addition, there is a problem that the film subjected to the hard coat layer treatment is liable to curl, and the appearance quality is impaired.

In addition, the multifunctional urethane (meth) acrylate adducts of the above-mentioned patent have a high viscosity, and if a solvent-free composition is prepared without using a diluting solvent, the viscosity becomes extremely high, and there is also a problem of poor coatability.

Patent document 2 discloses an active energy ray-curable composition comprising a reactant of dipentaerythritol pentaacrylate and a trivalent isocyanate having an isocyanato skeleton, that is, a urethane (meth) acrylate adduct having 15 (meth) acryloyl groups in one molecule.

However, although the composition of the above patent is excellent in hardness, scratch resistance and recovery of the cured film, when the film base material subjected to the hard coat layer treatment is bent, cracking or peeling is likely to occur, and the bending property is insufficient. In addition, as in patent document 1, when the bending property is to be improved, the hardness and scratch resistance of the cured film become insufficient, and it is difficult to achieve both of these properties. In addition, as in patent document 1, the film subjected to the hard coat layer treatment is liable to curl, and there is also a problem that the appearance quality is impaired. Furthermore, the multifunctional urethane (meth) acrylate adducts of said patent also have the problem of high viscosity.

As described above, the conventional multifunctional urethane (meth) acrylate adduct used as a raw material of the hard coat agent has a problem that the flexibility is deteriorated although the hardness of the cured film is improved by increasing the number of (meth) acryloyl groups in the molecule. In addition, the multifunctional urethane (meth) acrylate adduct has a problem of poor coatability because of its high viscosity.

[ Prior Art literature ]

[ patent literature ]

Patent document 1: japanese patent laid-open publication No. 2011-12099

Patent document 2: international publication No. 2012/86551 handbook

Disclosure of Invention

[ problem to be solved by the invention ]

The present inventors have conducted intensive studies in order to find a curable composition containing a multifunctional urethane (meth) acrylate adduct which has a low viscosity and is excellent in the balance between the surface hardness and scratch resistance of a cured film and the bendability, and to find a composition preferably curable with an active energy ray, particularly a composition preferably used as a coating agent.

[ means of solving the problems ]

The present inventors have found that an active energy ray-curable composition containing a polyfunctional urethane (meth) acrylate adduct obtained by a urethanization reaction between a specific glycerin (meth) acrylate and/or diglycerin (meth) acrylate and an organic polyisocyanate has a low viscosity and is excellent in the hardness, scratch resistance, bending property and curling property of a cured film, in order to solve the above-mentioned problems, and have completed the present invention.

The present invention will be described in detail below.

[ Effect of the invention ]

The composition of the present invention has low viscosity, and the cured film can satisfy the balance of surface hardness, scratch resistance and bending property, and has excellent curling property.

Thus, the composition of the present invention can be preferably used as a coating agent, and can be more preferably used as a hard coating agent.

Detailed Description

The present invention relates to the following curable compositions.

[1] A curable composition comprising the following component (A),

(A) The components are as follows: the mixture (a 1) is a mixture of at least one compound selected from the group consisting of glycerin (meth) acrylate and diglycerin (meth) acrylate, and has a hydroxyl value of 20mgKOH/g to 300mgKOH/g.

[2] The curable composition according to [1], wherein the organic polyisocyanate is an aliphatic polyisocyanate or an alicyclic polyisocyanate.

[3] The curable composition according to [1] or [2], wherein the mixture (a 1) is a (meth) acrylate mixture obtained by transesterification of glycerin or diglycerin with a compound having one (meth) acryloyl group [ hereinafter referred to as "monofunctional (meth) acrylate" ] in the presence of the following catalyst X and catalyst Y, and has a hydroxyl value of 20mgKOH/g to 300mgKOH/g.

Catalyst X: one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof, and a phosphine or a salt or complex thereof.

Catalyst Y: zinc-containing compounds.

[4] The curable composition according to [3], wherein the monofunctional (meth) acrylate is an alkoxyalkyl (meth) acrylate.

[5] The curable composition according to [3] or [4], wherein the catalyst X is one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, and a compound having a pyridine ring or a salt or complex thereof.

[6] The curable composition according to any one of [3] to [5], wherein the catalyst Y is zinc organic acid or/and zinc dikeenolate (zinc diketone enolate).

[7] The curable composition according to any one of [1] to [6], wherein the weight average molecular weight of the component (A) is 500 to 10,000.

[8] The curable composition according to any one of [1] to [7], further comprising the following component (B),

(B) The components are as follows: (A) A compound having an ethylenically unsaturated group other than the component (A).

[9] An active energy ray-curable composition comprising the composition according to any one of [1] to [8 ].

[10] The active energy ray-curable composition according to [9], further comprising a photopolymerization initiator in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total of the components (A) and (B), or based on 100 parts by weight of the total of the components (A) and (B).

[11] An active energy ray-curable coating agent composition comprising the composition according to [9] or [10 ].

The component (A), the curable composition, the method of use and the use will be described below.

1. (A) Composition of the components

The component (A) of the present invention is a reactant of a mixture (a 1) [ hereinafter referred to as "mixture (a 1)") and an organic polyisocyanate [ hereinafter referred to as "compound (a 2)", wherein the mixture (a 1) is a mixture of at least one compound selected from the group consisting of glycerin (meth) acrylate and diglycerin (meth) acrylate, and has a hydroxyl value of 20mgKOH/g to 300mgKOH/g.

Hereinafter, a method for producing the mixture (a 1), the compound (a 2) and the component (a) will be described.

1-1 mixture (a 1)

The mixture (a 1) is a mixture of at least one compound selected from the group consisting of glycerin (meth) acrylate and diglycerin (meth) acrylate, and has a hydroxyl value of 20mgKOH/g to 300 mgKOH/g.

In the case of the mixture (a 1) being a mixture of glycerin (meth) acrylate, a mixture containing glycerin diacrylate as a main component is preferable in terms of excellent reactivity with the compound (a 2).

In the case of a mixture of diglycerol (meth) acrylates, a mixture containing diglycerol triacrylate as a main component is preferable in terms of excellent reactivity with the compound (a 2).

The mixture (a 1) can be obtained by transesterification of glycerin and/or diglycerin (hereinafter, these will be also collectively referred to as "(poly) glycerin) with a monofunctional (meth) acrylate (a compound having one (meth) acryloyl group). The mixture (a 1) can also be obtained by a dehydration-esterification reaction of (poly) glycerol with (meth) acrylic acid.

In the case of using glycerin as a raw material, the mixture (a 1) is a mixture of mono (meth) acrylate, di (meth) acrylate, and tri (meth) acrylate of glycerin. When diglycerol is used as a raw material, the mixture (a 1) is a mixture of a mono (meth) acrylate of diglycerol, and a di (meth) acrylate, tri (meth) acrylate, and tetra (meth) acrylate of diglycerol.

The mixture (a 1) is a mixture of at least one compound selected from the group consisting of glycerin (meth) acrylate and diglycerin (meth) acrylate, and has a hydroxyl value of 20mgKOH/g to 300mgKOH/g. The hydroxyl value of the mixture (a 1) is preferably 30 to 290mgKOH/g, more preferably 40 to 280mgKOH/g.

When the hydroxyl value of the mixture (a 1) is less than 20mgKOH/g, the hardness of the cured film of the composition containing the obtained component (A) is lowered. If the hydroxyl value exceeds 300mgKOH/g, the component (A) obtained has a high viscosity.

The hydroxyl value in the present invention is a value measured according to a method specified in Japanese Industrial Standard (Japanese Industrial Standards, JIS) K0070-1992.

Further, the mixture of glycerin (meth) acrylate is more preferably a mixture containing glycerin di (meth) acrylate (hereinafter also referred to as "GLY-DA").

GLY-DA is a compound represented by the following formula (1) or (2).

[ chemical 1]

[ in the formula (1), R ¹ R is R ² Each independently represents a hydrogen atom or a methyl group. A kind of electronic device

[ chemical 2]

[ in the formula (2), R ³ R is R ⁴ Each independently represents a hydrogen atom or a methyl group. A kind of electronic device

The GLY-DA is not particularly limited as long as it is obtained as a mixture of the compound represented by the formula (1) and the compound represented by the formula (2) at the time of production, and therefore, it is only necessary to use these as it is, in particular, the mixing ratio of the compound represented by the formula (1) and the compound represented by the formula (2) is not limited, and it is not problematic to use them in any ratio.

The purity of GLY-DA contained in the mixture (a 1) is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more, as determined by using the following formula (3). By setting the purity of GLY-DA to 30% or more, the surface hardness and bending modulus of the component (a) as a reactant with the compound (a 2) can be made excellent.

Purity (%) = [ (d×2)/M of GLY-DA +D/2+T/3) × 100. Formula (3)

D, M, T in the formula (3) refers to the following value obtained by analyzing the mixture (a 1) using a high performance liquid chromatograph (hereinafter, also referred to as "HPLC (high performance liquid chromatograph)") including an Ultraviolet (UV) detector.

D: peak area of GLY-DA at 210nm

M: peak area of glycerol mono (meth) acrylate at 210nm

T: peak area of glycerol tri (meth) acrylate at 210nm

The peak area measured by HPLC means a value measured under the following conditions.

Detector: UV detector for detecting wavelength of 210nm

Type of column: column filled with a carbon number 18 alkyl modified silica gel

Specifically, the Aquinidine (ACQUITY) UPLC BEH C18 (Part No.) 186002350, manufactured by Waters (Waters) (Strand), inner diameter of the column 2.1mm, length of the column 50mm

Temperature of the column: 40 DEG C

Composition of eluent: 0.03 wt% aqueous trifluoroacetic acid solution and methanol mixed solution

Flow of eluent: 0.3 mL/min

As the mixture (a 1), a mixture obtained by various production methods can be used.

For example, a compound obtained by transesterification of (poly) glycerin with a monofunctional (meth) acrylate in the presence of a transesterification catalyst, a compound obtained by dehydration esterification of (poly) glycerin with (meth) acrylic acid in the presence of an acidic catalyst, or the like can be cited.

In the above-described production method, the compound obtained by the transesterification reaction of (poly) glycerin with a monofunctional (meth) acrylate is preferable because the compound can obtain the target (meth) acrylate with less impurities.

Further, the transesterification reaction is preferably a transesterification reaction between (poly) glycerol and a monofunctional (meth) acrylate in the presence of the following catalyst X and catalyst Y.

Catalyst X: one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof (hereinafter, also referred to as an "azabicyclo compound"), an amidine or a salt or complex thereof (hereinafter, also referred to as an "amidine compound"), a compound having a pyridine ring or a salt or complex thereof (hereinafter, also referred to as a "pyridine compound"), and a phosphine or a salt or complex thereof (hereinafter, also referred to as a "phosphine compound").

Catalyst Y: zinc-containing compounds.

Examples of the monofunctional (meth) acrylate include: methyl (meth) acrylate, ethyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and other alkyl (meth) acrylates having an alkyl group of 1 to 8 carbon atoms, alkoxyalkyl (meth) acrylates such as 2-methoxyethyl acrylate, N-dimethylaminoethyl (meth) acrylate and the like.

The monofunctional (meth) acrylate is preferably an alkoxyalkyl (meth) acrylate having an alkyl group having 1 to 2 carbon atoms, which promotes dissolution of (poly) glycerin and exhibits extremely good reactivity, and more preferably 2-methoxyethyl (meth) acrylate.

In addition, as the monofunctional (meth) acrylate, an acrylate is particularly preferable because of its excellent reactivity.

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. These compounds have excellent catalyst activity, and it is preferable to produce the mixture (a 1) and form a complex with the catalyst Y described later after the completion of the reaction, so that the complex can be easily removed from the reaction solution after the completion of the reaction by a simple method such as adsorption. In particular, the complex of the azabicyclo compound and the catalyst Y is insoluble in the reaction solution, and thus can be removed more easily by filtration, adsorption, or the like.

As the catalyst X, quinuclidine (quinuclidine), 3-quinuclidine, 3-hydroxyquinuclidine, triethylenediamine (alias: 1, 4-diazabicyclo [2.2.2] octane; hereinafter also referred to as "DABCO"), N-methylimidazole, 1, 8-diazabicyclo [5.4.0] undec-7-ene (hereinafter also referred to as "DBU"), and 1, 5-diazabicyclo [4.3.0] non-5-ene (hereinafter also referred to as "DBN") are preferable, and N, N-dimethyl-4-aminopyridine (hereinafter also referred to as "DMAP") is preferable as an example of an azabicyclo compound.

Of these compounds, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU and DMAP which are easily available and which exhibit good reactivity to most of the polyhydric alcohols are more preferable.

As the catalyst Y, various compounds can be used as long as they are zinc-containing compounds, and zinc organic acid and zinc diketonate are preferable in terms of excellent reactivity.

The catalyst Y is preferably zinc acetate, zinc propionate, zinc acrylate or zinc methacrylate, which are examples of zinc organic acid, and zinc acetylacetonate, which is an example of zinc diketonate, is preferred.

Among these compounds, zinc acetate, zinc acrylate and zinc acetylacetonate, which exhibit good reactivity to most of the polyol and are easily obtained, are particularly preferable as the catalyst Y.

The ratio of the catalyst X and the catalyst Y used in the method for producing the mixture (a 1) is not particularly limited, but is preferably 0.005 mol to 10.0 mol, more preferably 0.05 mol to 5.0 mol, based on 1 mol of the catalyst Y. By using 0.005 mol or more of the catalyst X with respect to 1 mol of the catalyst Y, the amount of the target polyfunctional (meth) acrylate produced can be increased, and by setting the amount to 10.0 mol or less, the formation of by-products and coloration of the reaction solution can be suppressed, and the purification step after the completion of the reaction can be simplified.

The combination of the catalyst X and the catalyst Y is preferably a combination in which the catalyst X is an azabicyclo compound and the catalyst Y is zinc organic acid, and particularly preferably a combination in which the azabicyclo compound is DABCO and the zinc organic acid is zinc acetate and/or zinc acrylate.

The above combination is preferable for applications such as transparent varnish and hard coat layer in which the color tone after the completion of the reaction is excellent (for example, yellow feeling is small) in addition to the mixture (a 1) being obtained in good yield. Further, the catalyst can be obtained relatively inexpensively, and is therefore an economically advantageous production process.

The reaction temperature in the production process of the mixture (a 1) is preferably 40 to 180 ℃, more preferably 60 to 160 ℃. The reaction rate can be increased by setting the reaction temperature to 40 ℃ or higher, and the thermal polymerization of the (meth) acryloyl group in the raw material or the product can be suppressed by setting the reaction temperature to 180 ℃ or lower, whereby the coloring of the reaction solution can be suppressed, and the purification step after the completion of the reaction can be simplified.

The reaction pressure in the method for producing the mixture (a 1) is not particularly limited as long as the reaction pressure can be maintained at a predetermined reaction temperature, and the reaction may be carried out under reduced pressure or under increased pressure. The reaction pressure is preferably 0.000001MPa to 10MPa (absolute pressure).

In the method for producing the mixture (a 1), a monohydric alcohol derived from a monofunctional (meth) acrylate is produced as the transesterification reaction proceeds.

When a part (for example, about 50 mol%) of the hydroxyl groups of (poly) glycerin is (meth) acrylated, the monoalcohol is allowed to coexist in the reaction system to be in an equilibrium state, and after the adsorption removal or deactivation operation of the catalyst, the monoalcohol and the monofunctional (meth) acrylate as a raw material are distilled off, whereby a product having a controlled acrylation rate can be stably produced.

In the method for producing the mixture (a 1), the reaction can be carried out without using a solvent, and the solvent can be used as needed.

Specific examples of the solvent include: hydrocarbons, ethers, crown ethers, esters, ketones, carbonate compounds, sulfones, sulfoxides, ureas or derivatives thereof, phosphinoxides, ionic liquids, silicone oils, water and the like.

Among these solvents, hydrocarbons, ethers, carbonate compounds and ionic liquids are preferable.

These solvents may be used alone or in combination of two or more kinds thereof as a mixed solvent.

In the method for producing the mixture (a 1), an inert gas such as argon, helium, nitrogen, or carbon dioxide gas may be introduced into the system for the purpose of maintaining the color tone of the reaction solution, or an oxygen-containing gas may be introduced into the system for the purpose of preventing the polymerization of the (meth) acryloyl group. Specific examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium. The method of introducing the oxygen-containing gas may be a method of dissolving in the reaction liquid or blowing into the reaction liquid (so-called bubbling).

In the method for producing the mixture (a 1), it is preferable to add a polymerization inhibitor to the reaction solution for the purpose of preventing polymerization of the (meth) acryloyl group.

Examples of the polymerization inhibitor include an organic polymerization inhibitor, an inorganic polymerization inhibitor, and an organic salt polymerization inhibitor.

Specific examples of the organic polymerization inhibitor include: phenolic compounds such as hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2, 6-di-tert-butyl-4-methylphenol, 2,4, 6-tri-tert-butylphenol, and 4-tert-butylcatechol; quinone compounds such as benzoquinone; phenothiazine; N-nitroso-N-phenylhydroxylamine ammonium, N-oxy compounds, and the like.

Examples of the N-oxy compound include: 2, 6-tetramethylpiperidin-1-yloxy, 4-hydroxy-2, 6-tetramethylpiperidin-1-yloxy 4-oxo-2, 6-tetramethylpiperidin-1-oxy, 4-methoxy-2, 6-tetramethylpiperidin-1-oxy, and the like.

Among the above-mentioned compounds, an N-oxyl compound is preferably used as the polymerization inhibitor. As the N-oxyl compound, the compound is preferable.

Further, as the polymerization inhibitor, it is preferable to use an N-oxy compound in combination with other polymerization inhibitors. The polymerization inhibitor other than the N-oxyl compound in this case is preferably a phenol compound or a phenothiazine, and more preferably a phenol compound.

The polymerization inhibitor may be added singly or in any combination of two or more, and may be added from the beginning or the middle of the production process of the mixture (a 1). The desired amount of the additive may be added at one time or may be added separately. In addition, the addition may be continuous via a rectifying column.

The addition ratio of the polymerization inhibitor is preferably 5wtppm to 30,000wtppm, more preferably 25wtppm to 10,000wtppm, based on the total weight of the reaction solution. The polymerization inhibitor can exhibit the polymerization inhibiting effect by setting the addition ratio to 5wtppm or more, and by setting the addition ratio to 30,000wtppm or less, the coloring of the reaction solution can be inhibited, the purification step after the completion of the reaction can be simplified, or the lowering of the hardening rate of the obtained mixture (a 1) can be inhibited.

1-2 Compounds (a 2)

As another raw material compound of the component (A), namely, the compound (a 2) [ organic polyisocyanate ], various compounds can be used.

The compound (a 2) includes diisocyanate, triisocyanate and the like.

Examples of the compound (a 2) include aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates.

Specific examples of the aliphatic polyisocyanate include: hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and the like, biuret and isocyanurate of these compounds, and reactants with polyols such as trimethylolpropane, and the like.

Specific examples of the alicyclic isocyanate include: isophorone diisocyanate, norbornane diisocyanate, 2,5 (2, 6) -bis (isocyanatomethyl) bicyclo [2, 1] heptane, hydrogenated toluene diisocyanate, hydrogenated 4,4' -diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, and the like, as well as biuret, cyanurate, and reactants with polyols such as trimethylolpropane, and the like of these compounds.

Specific examples of the aromatic isocyanate include: toluene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and the like, biuret, isocyanurate, and reactants with polyols such as trimethylolpropane, and the like of these compounds.

The compound (a 2) is preferably an aliphatic polyisocyanate or an alicyclic polyisocyanate for the reason of excellent light resistance.

The compound (a 2) is more preferably an aliphatic polyisocyanate, and particularly preferably hexamethylene diisocyanate in view of the low viscosity of the composition and the excellent hardness and bendability of the cured film.

1-3 Process for producing component (A)

(A) The component (a) can be produced by heating and stirring the mixture (a 1) and the compound (a 2) in the presence of a catalyst and a solvent, if necessary, to carry out urethanization.

The reaction ratio of the compound (a 2) to the mixture (a 1) is preferably a ratio of 0.3 to 1.3 mol, more preferably a ratio of 0.5 to 1.2 mol, and particularly preferably a ratio of 0.9 to 1.1 mol, based on 1 mol of the total of hydroxyl groups of the mixture (a 1).

In this case, the mixture (a 1) and the compound (a 2) may be added together to react, but since there is a problem that the heat release during the reaction increases, it is preferable to add the compound (a 2) successively in the presence of the mixture (a 1) to react. In addition, it is also preferable to add the mixture (a 1) successively in the presence of the compound (a 2).

The reaction proceeds even without a catalyst, but in order to advance the reaction efficiently in a short period of time, a catalyst generally used in urethanization reaction can be used as the catalyst in synthesis.

Specific examples of the catalyst include: tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctanoate and dibutyltin diacetylacetonate; bismuth compounds such as bismuth dioctanoate; iron compounds such as iron acetylacetonate; zinc compounds such as zinc acetylacetonate; amine compounds such as triethylamine, and the like.

The catalyst may be used alone or in combination of two or more.

The amount of the catalyst to be blended may be, for example, preferably 0.01wtppm to 1,000wtppm, more preferably 0.1wtppm to 1,000wtppm, relative to the reaction solution. The urethanization reaction is preferably carried out by setting the blending amount of the catalyst to 0.01wtppm or more, and the coloration of the component (A) obtained can be suppressed by setting the blending amount to 1,000wtppm or less.

The reaction mixture containing the component (a) may have a high viscosity and may be difficult to stir, and therefore, a solvent may be blended with the reaction component.

The solvent is preferably a solvent which does not participate in the urethanization reaction, and examples thereof include: aromatic solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.

The amount of the organic solvent to be blended is preferably 0 to 70% by mass based on the viscosity of the component (A) to be produced.

Here, the reaction solution refers to the total amount of the raw material compounds when only the raw material compounds are used, and includes the total amount of the raw material compounds when the reaction solvent or the like is used in addition to the raw material compounds. Specifically, the compound (a 2) is used in the meaning of a solution in which the mixture (a 1), the compound (a 2), and optionally a catalyst, a solvent, a polymerization inhibitor, and the like are mixed.

As the solvent, a (meth) acrylate may be formulated together with the organic solvent or in place of the organic solvent.

The (meth) acrylic acid ester may be a compound having an ethylenically unsaturated group other than the component (A) described below [ hereinafter, referred to as the component (B) ").

By carrying out a urethanization reaction in the presence of these (meth) acrylates, a curable composition containing the obtained component (A) and (meth) acrylate can be produced. The composition is preferable because it does not need to be dried after being applied, unlike the case of preparing the organic solvent.

The amount of the (meth) acrylate to be blended in the reaction solution as a solvent may be appropriately set according to the proportion of the other (meth) acrylate to be finally blended in the composition, and is preferably, for example, 0 to 70% by mass, and more preferably, 0 to 50% by mass in the reaction solution.

In the urethanization reaction, it is preferable to use a polymerization inhibitor in order to prevent polymerization of the (meth) acryloyl group of the raw material or the product, and further, an oxygen-containing gas may be introduced into the reaction liquid. Examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium.

Examples of the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors. Specific examples of the organic polymerization inhibitor include: phenol compounds such as hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2, 6-di-tert-butyl-4-methylphenol, 2,4, 6-tri-tert-butylphenol, and 4-tert-butylcatechol; quinone compounds such as benzoquinone; a galvinoxy radical (galvinoxy); stable free radicals such as 2, 6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2, 6-tetramethylpiperidine-1-oxyl, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium and the like. Specific examples of the inorganic polymerization inhibitor include: copper chloride, copper sulfate and iron sulfate. Specific examples of the organic salt-based polymerization inhibitor include: nitroso compounds such as N-nitroso-N-phenylhydroxylamine-aluminum salt and ammonium N-nitrosophenylhydroxylamine, copper dibutyldithiocarbamate. These may be used alone or in combination of two or more.

The proportion of the polymerization inhibitor in the reaction solution is preferably 5wtppm to 20,000wtppm, more preferably 25wtppm to 3,000wtppm.

The reaction temperature is appropriately set depending on the raw materials used and the structure or molecular weight of the target component (A), and is usually preferably 25℃to 150℃and more preferably 30℃to 120 ℃. The reaction time is also appropriately set depending on the structures, molecular weights, and the like of the raw materials to be used and the target component (a), and is usually preferably 1 to 70 hours, more preferably 2 to 30 hours.

The weight average molecular weight (hereinafter referred to as "Mw") of the component (A) in the present invention is preferably 500 to 10,000, more preferably 500 to 5,000, and still more preferably 500 to 2,000, from the viewpoint of improving the coatability and adhesion of the composition.

In the present invention, mw refers to a value obtained by converting a molecular weight polystyrene measured by gel permeation chromatography (hereinafter, referred to as "GPC (Gel Permeation Chromatography)"), and also refers to a value obtained by measuring under the following conditions.

Detector: differential Refractive Index (RI) detector

Type of column: cross-linked polystyrene series pipe column

Temperature of the column: 40 DEG C

Eluent: tetrahydrofuran (THF)

Molecular weight standard: polystyrene

As the component (a), only one kind may be used alone, or two or more kinds may be used in combination.

2. Hardening composition

The present invention relates to a curable composition containing the component (A).

The composition may be produced by a conventional method, for example, by stirring and mixing the component (a) with other components as necessary.

In this case, heating may be performed as needed. The heating temperature is appropriately set depending on the components contained in the composition to be used, the substrate to be coated with the composition, the purpose of use, and the like, and is preferably 30 to 80 ℃.

When the component (A) is contained in the composition in a proportion of (B) other than the component (A), the total amount of the component (A) and the component (B) is preferably 1 to 90% by weight, more preferably 10 to 80% by weight, and still more preferably 20 to 60% by weight, based on 100% by weight of the total amount of the components (A) and (B).

When the proportion of the component (a) is 1% by weight or more, warping (curling) of the cured film of the composition can be prevented, and the adhesive strength of the cured film of the composition can be made excellent, and when the proportion is 90% by weight or less, the composition can be suppressed from having a high viscosity, and the coatability can be made preferable.

The viscosity of the composition is appropriately set according to the purpose, and is preferably 1 to 100,000 mPas.

In the present invention, the viscosity means a value measured at 25℃using an E-type viscometer (cone-plate type viscometer).

The composition of the present invention can be used as an active energy ray-curable composition and a thermosetting composition, and is preferably used as an active energy ray-curable composition.

The composition of the present invention contains the component (A) as an essential component, and various components can be formulated according to the purpose.

Examples of the other components include component (B) [ a compound having an ethylenically unsaturated group other than component (A) ], a photopolymerization initiator [ hereinafter referred to as component (C) ], a thermal polymerization initiator, an organic solvent, an antioxidant, an ultraviolet absorber, a pigment and dye, a leveling agent, a silane coupling agent, a surface modifier, a polymer, and the like.

These components will be described below.

The other components described below may be used alone or in combination of two or more kinds.

1) Component (B)

(B) The component (a) is an ethylenically unsaturated compound other than the component (a) and is formulated for the purpose of imparting various physical properties to the cured film of the composition.

Examples of the ethylenically unsaturated group in the component (B) include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, and a (meth) allyl group, and (meth) acryloyl group is preferable.

In the following description, "monofunctional" refers to a compound having one ethylenically unsaturated group, "o-functional" refers to a compound having o-ethylenically unsaturated groups, and "multifunctional" refers to a compound having two or more ethylenically unsaturated groups.

Examples of the component (B) include a compound having one ethylenically unsaturated group (hereinafter referred to as "monofunctional unsaturated compound"), a compound having two (meth) acryloyl groups (hereinafter referred to as "difunctional (meth) acrylate"), and a compound having three or more (meth) acryloyl groups (hereinafter referred to as "trifunctional or more (meth) acrylate").

(B) Specific examples of the monofunctional unsaturated compound in the component (a) include: a compound having a (meth) acryloyl group, a compound having a monofunctional (meth) acrylamide, and a vinyl group.

Examples of the compound having a (meth) acryloyl group include:

compounds having a carboxyl group and an ethylenic unsaturated group, such as (meth) acrylic acid, a Michael addition type dimer of acrylic acid, ω -carboxyl-polycaprolactone mono (meth) acrylate, and monohydroxyethyl (meth) acrylate phthalate;

Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate;

(meth) acrylic esters having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;

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

monofunctional (meth) acrylates having an aromatic group such as benzyl (meth) acrylate, a (meth) acrylate of an alkylene oxide adduct of phenol, a (meth) acrylate of an alkylene oxide adduct of alkylphenol, a (meth) acrylate of an alkylene oxide adduct of para-cumylphenol, o-phenylphenol (meth) acrylate, a (meth) acrylate of an alkylene oxide adduct of o-phenylphenol, and 2-hydroxy-3-phenoxypropyl (meth) acrylate;

monofunctional (meth) acrylates having an alicyclic group such as cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and tricyclodecane trimethylol (meth) acrylate; and

And monofunctional (meth) acrylates having a heterocycle such as tetrahydrofurfuryl (meth) acrylate, (meth) acryloylmorpholine, N- (2- (meth) acryloyloxyethyl) hexahydrophthalimide, and N- (2- (meth) acryloyloxyethyl) tetrahydrophthalimide.

Examples of the monofunctional (meth) acrylamide include: n-alkyl (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, (meth) acryloylmorpholine, N-methyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-sec-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, and N-hexyl (meth) acrylamide;

n-hydroxyalkyl (meth) acrylamides such as N-hydroxyethyl (meth) acrylamide; and

n, N-dialkyl (meth) acrylamides such as N, N-dimethylaminoethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-di-N-propyl (meth) acrylamide, N-diisopropyl (meth) acrylamide, N-di-N-butyl (meth) acrylamide, and N, N-dihexyl (meth) acrylamide.

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

Specific examples of the difunctional (meth) acrylate include: aliphatic diol di (meth) acrylates such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol di (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; and

and di (meth) acrylates of alkylene oxide adducts of bisphenol a, di (meth) acrylates of alkylene oxide adducts of diols having a bisphenol skeleton such as di (meth) acrylates of alkylene oxide adducts of bisphenol F.

As the difunctional (meth) acrylate, in addition to the above-mentioned compounds, epoxy (meth) acrylates having a bisphenol skeleton, or a polyether skeleton, or a polyalkylene skeleton, urethane (meth) acrylates having a polyester skeleton, polyether skeleton, or polycarbonate skeleton, and oligomers such as polyester (meth) acrylates may be used.

Examples of the trifunctional or higher (meth) acrylate include various compounds as long as they are compounds containing three or more (meth) acryloyl groups, and examples thereof include: polyol poly (meth) acrylates such as glycerol tri (meth) acrylate, diglycerol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, di-trimethylolpropane tri or tetra (meth) acrylate, and dipentaerythritol tri, tetra, penta, or hexa (meth) acrylate;

poly (meth) acrylates of polyol alkylene oxide adducts such as tri or tetra (meth) acrylates of pentaerythritol alkylene oxide adducts, tri or tetra (meth) acrylates of di-trimethylolpropane alkylene oxide adducts, tri, tetra, penta or hexa (meth) acrylates of dipentaerythritol alkylene oxide adducts;

tri (meth) acrylates of isocyanatoalkylene oxide adducts; and

urethane (meth) acrylates that are reactants of compounds having three or more (meth) acryloyl groups and organic polyisocyanates, such as pentaerythritol tri (meth) acrylate.

As examples of the alkylene oxide adducts, there may be mentioned: ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts, and the like.

The organic polyisocyanate may be: hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated 4,4 '-diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, trimers of hexamethylene diisocyanate, and the like.

The content ratio of the component (B) is preferably 0 to 60% by weight, more preferably 0 to 30% by weight, based on 100 parts by weight of the total amount of the component (a) and the component (B) (hereinafter, the component (a) and the component (B) are collectively referred to as "curable components").

If the content of the component (B) exceeds 60% by weight, the cured film may become brittle, particularly in the case of a polyfunctional ethylenically unsaturated compound.

2) Component (C)

When the composition of the present invention is used as an active energy ray-curable composition and further as an electron beam-curable composition, it is possible to cure the composition by an electron beam without containing the component (C) (photopolymerization initiator).

When the composition of the present invention is used as an active energy ray-curable composition, particularly when ultraviolet rays and visible rays are used as active energy rays, it is preferable that the composition further contains component (C) in view of ease of curing and cost.

In the case of using an electron beam as the active energy beam, the blending is not necessarily required, but a small amount of blending may be required in order to improve the hardenability.

Specific examples of the component (C) include: benzyl dimethyl ketal, benzyl, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propane-1-one, oligo [ 2-hydroxy-2-methyl-1- [4-1- (methylvinyl) phenyl ] acetone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] -phenyl } -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) ] phenyl ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butane-1-one, 3, 6-bis (2-methyl-propionyl) -benzyl ] -phenyl } -2-methyl-1-methyl-2-morpholin-4-yl-methyl-phenyl) -n-octyl-methyl-9-phenylmethyl-n-octyl-carbazol, aromatic ketone compounds such as ethyl anthraquinone and phenanthrenequinone;

Benzophenone-based compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylmethane, methyl-2-benzophenone, 1- [4- (4-benzoylphenylmercapto) phenyl ] -2-methyl-2- (4-methylphenylsulfanyl) propan-1-one, 4' -bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, and 4-methoxy-4 ' -dimethylaminobenzophenone;

acyl phosphine oxide compounds such as bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, ethyl (2, 4, 6-trimethylbenzoyl) phenylphosphinate, and bis (2, 6-dimethoxybenzoyl) -2, 4-trimethylpentylphosphine oxide;

thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3, 4-dimethyl-9-oxo-9H-thioxanthone-2-yl-oxy ] -2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone.

Among these compounds, α -hydroxy phenyl ketone is excellent in surface hardening property even in a film coating under the atmosphere, and more specifically, 1-hydroxy cyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propane-1-one are more preferable.

In the case where it is necessary to thicken the film thickness of the cured film, for example, it is necessary to set the film thickness to 50 μm or more, or in the case where an ultraviolet absorber or pigment is used in combination, it is preferable to use bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, an acyl phosphine oxide compound such as ethyl- (2, 4, 6-trimethylbenzoyl) -phenylphosphine or bis (2, 6-dimethoxybenzoyl) -2, 4-trimethylpentylphosphine oxide, or 2-methyl-1- [4- (methylthio) ] phenyl ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one, or the like.

The content ratio of the component (C) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total curable component. When the proportion of the component (C) is 0.1 part by weight or more, the composition can be made to have good light hardenability and excellent adhesion, and when it is 10 parts by weight or less, the cured film can be made to have good internal hardenability and adhesion to a substrate.

3) Thermal polymerization initiator

In the case of using the composition as a thermosetting composition, a thermal polymerization initiator may be formulated.

The composition of the present invention may be formulated with a thermal polymerization initiator to be heat-cured.

As the thermal polymerization initiator, various compounds, preferably organic peroxides and azo-based initiators, can be used.

Specific examples of the organic peroxide include: 1, 1-bis (t-butylperoxy) 2-methylcyclohexane, 1-bis (t-hexylperoxy) -3, 5-trimethylcyclohexane, 1-bis (t-hexylperoxy) cyclohexane, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) cyclohexane 2, 2-bis (4, 4-di-butylcyclohexyl-peroxy) propane, 1-bis (t-butylperoxy) cyclododecane, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxymaleate, t-butyl peroxy-3, 5-trimethylhexanoate tert-butyl laurate peroxide, 2, 5-dimethyl-2, 5-di (m-toluoyl peroxide) hexane, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, 2, 5-dimethyl-2, 5-di (benzoyl peroxide) hexane, tert-butyl peroxyacetate, 2-bis (tert-butyl peroxy) butane, tert-butyl peroxybenzoate, n-butyl-4, 4-bis (tert-butyl peroxy) valerate, di-tert-butyl peroxyisophthalate, alpha, alpha' -bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1, 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, and the like.

Specific examples of the azo compound include: 1,1' -azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2, 4-dimethylvaleronitrile, azobis-t-octane, azobis-t-butane, and the like.

These may be used alone or in combination of two or more. In addition, the organic peroxide may be subjected to a redox reaction by combination with a reducing agent.

The amount of these thermal polymerization initiators used is preferably not more than 10 parts by weight per 100 parts by weight of the total curable components.

In the case of using the thermal polymerization initiator alone, the polymerization may be carried out according to a conventional method of usual radical thermal polymerization, or may be carried out in combination with a photopolymerization initiator in order to further increase the reaction rate after the photo-curing.

4) Organic solvents

For the purpose of improving the coatability to a substrate or the like, the composition of the present invention may use a composition containing an organic solvent.

Specific examples of the organic solvent include: alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetol such as diacetone alcohol; aromatic compounds such as benzene, toluene and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, and the like; ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether compounds such as dibutyl ether; n-methylpyrrolidone, etc.

Of these, alkylene glycol monoether compounds and ketone compounds are preferable, and alkylene glycol monoether compounds are more preferable.

The content ratio of the organic solvent is preferably 10 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, and even more preferably 50 to 300 parts by weight, relative to 100 parts by weight of the total amount of the curable components. If the viscosity is within the above range, the composition can be made to have a viscosity suitable for application, and the composition can be easily applied by a known application method described later.

5) Antioxidant agent

Antioxidants are formulated for the purpose of improving the durability of cured films such as heat resistance and weather resistance.

Examples of the antioxidant include phenol antioxidants, phosphorus antioxidants, and sulfur antioxidants.

Examples of the phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. As commercial products, there may be mentioned AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, etc. manufactured by Ai Dike (ADEKA) (Stroke).

Examples of the phosphorus antioxidant include phosphines such as trialkylphosphine and triarylphosphine; trialkyl phosphites, triaryl phosphites, and the like. Examples of the commercial products of these derivatives include Addisos Taber (ADEKASTAB) PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010, etc. manufactured by Ai Dike (ADEKA) (Stra).

Examples of the sulfur-based antioxidant include a sulfide compound, and commercial products include AO-23 and AO-412S, AO-503A manufactured by Ai Dike (ADEKA) (Stra).

One kind of these may be used, or two or more kinds may be used. Preferable combinations of these antioxidants include a combination of a phenolic antioxidant and a phosphorus antioxidant, and a combination of a phenolic antioxidant and a sulfur antioxidant.

The content 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, based on 100 parts by weight of the total amount of the curable components.

The durability of the composition can be improved by setting the content ratio to 0.1 part by weight or more, while the hardenability and adhesion can be improved by setting the content ratio to 5 parts by weight or less.

6) Ultraviolet absorber

The ultraviolet absorber is formulated for the purpose of improving the light resistance of the cured film.

Examples of the ultraviolet absorber include triazine ultraviolet absorbers such as poncir (TINUVIN) 400, poncir (TINUVIN) 405, poncir (TINUVIN) 460, and poncir (TINUVIN) 479 manufactured by BASF corporation; benzotriazole-based ultraviolet absorbers such as crowing stability (TINUVIN) 900, crowing stability (TINUVIN) 928, crowing stability (TINUVIN) 1130, and the like.

The content 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, based on 100 parts by weight of the total amount of the curable components. The light resistance of the cured film can be kept good by setting the content ratio to 0.01 wt% or more, and a compound having excellent curability of the composition can be produced by setting the content ratio to 5 wt% or less.

7) Pigment-dye

Examples of the pigment include organic pigments and inorganic pigments.

Specific examples of the organic pigment include: insoluble azo pigments such as toluidine red, toluidine chestnut, hansa Yellow (Hansa Yellow), benzidine Yellow, pyrazolone red, and the like; soluble azo pigments such as Lithol Red (lithio Red), purplish Red (Helio Bordeaux), scarlet pigment and permanent Red 2B; derivatives derived from architectural dyes such as alizarin, indanthrone (indanthrone), thioindigochestnut, and the like; phthalocyanine-based 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 isoindolinone yellow and isoindolinone orange; pyranthrone Red (Pyranthrone Red), pyranthrone orange and other Pyranthrone-based organic pigments; thioindigo-based organic pigments; condensed azo organic pigments; benzimidazolone organic pigments; quinophthalone-based organic pigments such as quinophthalone yellow, and isoindoline-based organic pigments such as isoindoline yellow; yellow solenoidal yellow, acyl amide yellow, nickel azo yellow, copper azo methine yellow, purple ring ketone orange, anthrone orange, bianthraquinone red, dioxazine violet (dioxazine violet), and the like as other pigments.

Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III)), cadmium red, ultramarine, prussian blue, chromium oxide green, cobalt green, ocher pigment, titanium black, and synthetic iron black. The carbon black exemplified in the filler may be used as an inorganic pigment.

As the dye, various compounds known previously can be used.

8) Silane coupling agent

The silane coupling agent is formulated for the purpose of improving the interfacial adhesion strength between the cured film and the substrate.

The silane coupling agent is not particularly limited as long as it can contribute to the improvement of adhesion to the substrate.

Specific examples of the silane coupling agent include 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-glycidoxypropyl triethoxysilane, N-2- (aminoethyl) -3-aminopropyl methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl trimethoxysilane, N-2- (aminoethyl) -3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilane-N- (1, 3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyl trimethoxysilane, 3-mercaptopropyl methyldimethoxysilane, and 3-mercaptopropyl trimethoxysilane.

The proportion of the silane coupling agent to be blended 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, based on 100 parts by weight of the total amount of the curable components.

By setting the blending ratio to 0.1 part by weight or more, the adhesion of the composition can be improved, while by setting it to 10 parts by weight or less, the adhesion can be prevented from changing with time.

9) Surface modifying agent

The composition of the present invention may contain a surface modifier for the purpose of improving leveling property at the time of coating, or for the purpose of improving abrasion resistance for the purpose of improving smoothness of a cured product.

The surface modifier may be a surface modifier, a surfactant, a leveling agent, a defoaming agent, a slip agent, a stain-proofing agent, or the like, and these known surface modifiers may be used.

Among these, silicone-based surface modifiers and fluorine-based surface modifiers are preferably exemplified. Specific examples thereof include silicone polymers and oligomers having silicone chains and polyalkylene oxide chains, silicone polymers and oligomers having silicone chains and polyester chains, fluorine polymers and oligomers having perfluoroalkyl groups and polyalkylene oxide chains, fluorine polymers and oligomers having perfluoroalkyl ether chains and polyalkylene oxide chains, and the like.

In addition, for the purpose of improving the sustained force of smoothness and the like, a surface modifier having an ethylenically unsaturated group in the molecule, preferably having a (meth) acryloyl group, may be used.

The content ratio of the surface modifier is preferably 0.01 to 1.0 parts by weight based on 100 parts by weight of the total amount of the curable components. When the amount is within the above range, the coating film has excellent surface smoothness.

10 Polymer(s)

The composition of the present invention may further contain a polymer for the purpose of further improving the curl resistance of the obtained cured film, and the like.

The preferable polymer includes a (meth) acrylic polymer, and preferable structural monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, acrylic acid, glycidyl (meth) acrylate, and N- (2- (meth) acryloyloxyethyl) tetrahydrophthalimide. In the case of a polymer obtained by copolymerizing a polymer of (meth) acrylic acid, glycidyl (meth) acrylate may be added to introduce a (meth) acryloyl group into a polymer chain.

The content of the polymer is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the curable components. When the amount is within the above range, the resulting cured film is more excellent in curl resistance.

3. Application method

The method of using the composition of the present invention may be any method as long as it is a conventional method.

For example, a method of applying the composition to a substrate and then irradiating the substrate with an active energy ray or heating the substrate to cure the substrate may be mentioned.

Specifically, in the case of application of a coating agent, an adhesive agent, or the like, a method of applying a composition to a substrate to be applied by a usual coating method, and then curing the composition by irradiation with an active energy ray in the case of an active energy ray curing composition, or a method of curing the composition by heating in the case of a thermally curing composition, or the like can be mentioned. In the case of use of a molding material or the like, there are: a method of injecting the composition into a predetermined mold frame and then curing the composition by irradiation with an active energy ray in the case of an active energy ray curing composition, a method of curing the composition by heating in the case of a heat curing composition, and the like.

The irradiation method or the heating method of the active energy ray may be a general method known as a conventional curing method.

In addition, the following method may be employed: a method of improving adhesion to a substrate by applying an active energy ray to a composition by using a component (C) (photopolymerization initiator) and a thermal polymerization initiator in combination and then curing the composition by heating.

The substrate to which the composition of the present invention can be applied can be used for various materials, and examples thereof include plastics, wood, metals, inorganic materials, and papers.

Specific examples of the plastic include: cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose; an acrylic resin; cyclic polyolefin resins having cyclic olefins such as polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, norbornene and the like as monomers; polyvinyl chloride, epoxy resins, polyurethane resins, and the like.

Examples of the wood include natural wood and synthetic wood.

Examples of the metal include steel sheet, aluminum, chromium, and other metals; zinc oxide (ZnO), metal oxides such as Indium Tin Oxide (ITO), and the like.

Examples of the inorganic material include glass, mortar, concrete, and stone.

Among these, a plastic substrate is particularly preferable.

The film thickness of the cured composition film relative to the substrate may be appropriately set according to the purpose. The thickness of the cured film may be selected according to the substrate used or the use of the substrate having the cured film to be produced, and is preferably 1 μm to 500 μm, more preferably 5 μm to 200 μm.

The method of applying the composition of the present invention to a substrate may be appropriately set according to the purpose, and examples thereof include a method of applying the composition by a bar coater, an applicator, a blade, a dip coater, a roll coater, a spin coater, a flow coater, a blade coater, a comma coater, a reverse roll coater, a die coater, a lip coater, a gravure coater, a micro gravure coater, and the like.

The active energy ray used for curing the composition of the present invention includes ultraviolet rays, visible rays, electron beams, and the like, and ultraviolet rays are preferable.

As the ultraviolet irradiation device, a high-pressure mercury lamp, a metal halide lamp, an Ultraviolet (UV) electrodeless lamp, a Light Emitting Diode (LED), and the like can be cited.

The irradiation energy is appropriately set according to the type of active energy ray or the composition to be blended, and when Sup>A high-pressure mercury lamp is used as an example, the irradiation energy in the UV-A region is preferably 10mJ/cm ² ～10,000mJ/cm ² More preferably 100mJ/cm ² ～2,000mJ/cm ² 。

4. Use of the same

The composition of the present invention can be used for various purposes, and specifically, it is exemplified by: coating agents such as hard coat layers, inks for lithography, adhesives, sealants, and the like.

The composition of the present invention is preferably used as an active energy ray-curable composition, and a cured film thereof is excellent in surface hardness and a balance between scratch resistance and bendability, and thus is also excellent in curling properties, and thus can be more preferably used as a hard coating agent.

Examples of preferred applications of the hard coat agent include front surface plates for display panels, building material applications, lighting devices, mobile phones, smart phones, displays or housings for flat terminals, housings for home electric appliances, and various lenses such as glasses.

Specific examples of the front surface plate for a display panel include an electro-optical bulletin board, a display, a signboard, an advertisement, and a sign.

Examples of the use of wood as a base material include wood products such as stairs, floors, and furniture. Examples of the use of metal as a base material include kitchen panels for kitchens, metal products such as stainless steel water tanks, and the like.

Examples (example)

The present invention will be described in more detail below with reference to examples and comparative examples.

Hereinafter, "parts" refers to parts by weight.

1. Production example

1) Production example 1 [ production of mixture (a 1) ]

To a 3 liter flask equipped with a stirrer, a thermometer, a gas introduction tube, a rectifying column, and a cooling tube, 302.75 parts (3.29 moles) of glycerin (trade name) manufactured by sakazakii pharmaceutical industry (stock); hereinafter, referred to as "GLY", 2312.84 parts (17.77 mol) of 2-methoxyethyl acrylate (hereinafter, referred to as "MCA"), 6.51 parts (0.06 mol) of DABCO as catalyst X, 24.07 parts (0.12 mol) of zinc acrylate as catalyst Y, 1.19 parts (0.01 mol) of hydroquinone monomethyl ether (hereinafter, referred to as "MEHQ"), 0.21 parts (0.002 mol) of phenothiazine, and an oxygen-containing gas (oxygen: 5 vol% and nitrogen: 95 vol%) were bubbled in the liquid.

While heating and stirring the reaction mixture at a temperature of 100 to 130 ℃, the pressure in the reaction system is adjusted at a temperature of 110 to 760mmHg, and a mixed solution of MCA and 2-methoxyethanol (hereinafter referred to as "MEL") produced as the transesterification reaction proceeds is extracted from the reaction system through a rectifying column and a cooling tube. MCA having the same weight as the extract was added to the reaction system as needed. After 18 hours from the start of the heating and stirring, the pressure in the reaction system was returned to normal pressure to terminate the extraction.

The degree of acrylation of the hydroxyl groups of GLY was found to be 57 mol% from the amount of MEL produced.

After cooling the reaction solution to room temperature and separating the precipitate by filtration, 58.7 parts of aluminum silicate (Qiao Wade (Kyowa) 700SEN-S (trade name) manufactured by Kyowa chemical industry (Co., ltd.) was charged for the purpose of removing the catalyst X and the catalyst Y contained in the filtrate by adsorption; hereinafter referred to as "700SEN-S", and stirred, and further heated and stirred at 70℃to 100℃for 1 hour. After the adsorption treatment, the aluminum silicate was separated by filtration, the filtrate was placed in a flask connected to a stirrer, a thermometer, a gas introduction tube, a cooling tube for distillation, and a tube for pressure reduction, and the distillation liquid containing unreacted MCA was separated by vacuum distillation for 10 hours while bubbling dry air at a temperature of 70 to 100 ℃ and a pressure of 0.001 to 100 mmHg. To the pot liquid, 5.0 parts of diatomaceous earth (rad-line (trade name) manufactured by sho chemical industry (strand); hereinafter referred to as "rad-line (rad)") was added and pressure filtration was performed, and the obtained filtrate was used as the mixture (a 1). The yield of the mixture (a 1) was 647 parts. Hereinafter, this will be referred to as mixture (a 1-1).

The yield of the mixture (a 1-1) was calculated to be 98% based on 658 parts of the total amount of GLY 302.75 parts charged, which was converted to glycerol diacrylate (hereinafter referred to as "GLY-DA").

The purity of GLY-DA contained in the mixture (a 1-1) was calculated by using HPLC comprising a UV detector according to the following calculation formula (3), and as a result, it was 63%, glycerol triacrylate (hereinafter, referred to as "GLY-TA") was 23%, and glycerol monoacrylate (hereinafter, referred to as "GLY-MA") was 14%.

The viscosity of the obtained mixture (a 1-1) was 41 mPas (25 ℃ C.) and the hydroxyl value was 240mgKOH/g. Mw measured by GPC was 309.

Further, HPLC, viscosity, hydroxyl value and GPC were measured according to the following methods.

Conditions for HPLC measurement

Device: ultra-high performance liquid chromatography (ultra-high performance liquid chromatograph, UPLC) of Alqueti (ACQUITY) manufactured by Waters (Waters) (Strand)

Detector: UV detector

Detection wavelength: 210nm of

Tubular column: aquinidine (ACQUITY) UPLC BEH C18 (Part number 186002350, inner diameter of column 2.1mm, length of column 50 mm) manufactured by Waters (Waters) (thigh)

Column temperature: 40 DEG C

Flow of eluent: 0.3 mL/min

Method for calculating purity of GLY-DA contained in mixture (a 1-1)

Purity% GLY-DA= [ (D/2)/(M+D/2+T/3) ] x 100. Formula (3)

The symbols and expressions in the expression (1) are as follows.

D: peak area of GLY-DA at 210nm

M: peak area of GLY-MA at 210nm

T: peak area of GLY-TA at 210nm

Conditions for measuring viscosity

The viscosity at 25℃was measured using an E-type viscometer.

Conditions for measuring hydroxyl value

The measurement was carried out in accordance with JIS K0070-1992. That is, an acetylating reagent was added to the sample, and the sample was subjected to a heat treatment in a hot water bath. After cooling, the phenolphthalein solution was used as an indicator, and the hydroxyl value was determined by titrating the acid with an ethanol solution of potassium hydroxide.

Further, pyridine was used in an amount 5 times that of the method described in JIS K0070-1992.

GPC measurement conditions

Device: GPC System name 1515 2414 717P RI manufactured by Waters (Inc.)

Detector: RI detector

Tubular column: protection column (Strand) manufactured by Showa Denko (Shodex) KFG (8 μm 4.6X10 mm), style (Styragel) HR 4E THF (7.8X10 mm) +Styragel (Styragel) HR 1THF (7.8X10 mm) manufactured by Waters (Strand)

Column temperature: 40 DEG C

Composition of eluent: THF (containing 0.03% sulfur as an internal standard) at a flow rate of 0.75 mL/min

In production examples 2 to 5, GPC measurements were also performed under the same conditions.

2) Production example 2 (production of mixture (a 1))

249.92 parts (1.50 mol) of glycerin 801 (trade name) manufactured by the pharmaceutical industry (ltd) of sakazakii was charged into a 3 liter flask equipped with a stirrer, a thermometer, a gas introduction tube, a rectifying column, and a cooling tube; hereinafter, referred to as "DGLY", 1410.92 parts (10.84 mol) of MCA, 5.95 parts (0.05 mol) of DABCO as catalyst X, 22.03 parts (0.11 mol) of zinc acrylate as catalyst Y, 0.99 parts (0.01 mol) of MEHQ, 0.45 parts (0.003 mol) of 4-hydroxy-2, 6-tetramethylpiperidine-1-oxyl, and an oxygen-containing gas (oxygen: 5 vol% and nitrogen: 95 vol%) were bubbled in the liquid.

While heating and stirring the reaction mixture at a temperature of 100 to 130 ℃, the pressure in the reaction system is adjusted at a temperature of 150 to 760mmHg, and a mixed solution of MCA and MEL produced as the transesterification reaction proceeds is extracted from the reaction system through a rectifying column and a cooling pipe. Further, MCA including a polymerization inhibitor was added as needed to balance the weight of the extract. After 20 hours from the start of the heating and stirring, the pressure in the reaction system was returned to normal pressure to terminate the extraction.

The rate of acrylic acid esterification of the hydroxyl groups of DGLY was found to be 82 mol% from the amount of MEL produced.

The reaction solution was cooled to room temperature, and after separating the precipitate by filtration, 25.0 parts of aluminum silicate (700 SEN-S) was charged and stirred for adsorption to remove the catalyst X and the catalyst Y contained in the filtrate, and then heated and stirred at 70 to 100 ℃ for 1 hour. Thereafter, 3.7 parts of calcium hydroxide was added at an internal temperature of 20 to 40℃and stirred at normal pressure for 1 hour, followed by pressure filtration to separate insoluble materials.

To the obtained filtrate, 2.0 parts of aluminum silicate (700 SEN-S) was charged, and the mixture was placed in a flask connected to a stirrer, a thermometer, a gas introduction tube, a distillation cooling tube, and a pressure reduction tube, and vacuum distillation was performed for 10 hours while bubbling dry air at a temperature of 70 to 100 ℃ and a pressure of 0.001mmHg to 100mmHg, to separate a distillate containing unreacted MCA.

To the obtained pot liquid, 0.33 parts of DEHA was added, and the mixture was stirred at normal pressure for 3 hours at an internal temperature ranging from 70℃to 90 ℃. Thereafter, 5.0 parts of diatomaceous earth (rad's solution) was added to the pot liquid and the mixture was pressure-filtered to obtain a filtrate. The obtained filtrate was used as the mixture (a 1). The yield of the mixture (a 1) was 502 parts. Hereinafter, this will be referred to as mixture (a 1-2).

The purity of the diglycerol triacrylate (hereinafter referred to as "DGLY-TA") contained in the mixture (a 1-2) was calculated according to the following calculation formula (4) using HPLC including a UV detector, and was found to be 41%.

Regarding the obtained mixture (a 1-2), viscosity: 223 mPas (25 ℃ C.), and hydroxyl value: 80mgKOH/g.

Method for calculating purity of DGLY-TA contained in mixture (a 1-2)

DGLY-TA purity% = [ (Tri/3)/(M+D/2+Tri/3+tetra/4) ] x 100. Cndot. 4 ]

The symbols and expressions in the expression (1) are as follows.

Tri: peak area at 210nm of DGLY-TA

M: peak area at 210nm of diglycerol monoacrylate

D: peak area at 210nm of diglycerol diacrylate

Tetra: peak area at 210nm of diglycerol tetraacrylate

3) Production example 3 production of component (A)

Into a 1L flask equipped with a stirrer, a thermometer, and a pipe for an oxygen/nitrogen mixture gas (hereinafter, referred to as 5% ON) having an oxygen concentration of 5%, 93.52g of the mixture (a 1-1), 0.064g of 2, 6-di-t-butyl-4-methylphenol (hereinafter, referred to as BHT), and 0.064g of di-n-butyltin dilaurate (Fuji film and a reagent manufactured by Wako pure chemical industries, ltd.) were charged; hereinafter, referred to as DBTDL.

The contents were stirred while blowing 5% on to bring the flask to 70 ℃. Thereafter, hexamethylene diisocyanate (hereinafter referred to as HDI) was slowly added, and 33.6g of HDI (ratio of total isocyanate groups to total 1 mol of hydroxyl groups of the mixture (a 1-1) was 0.98 mol) was finally added. Thereafter, the temperature in the flask was raised to 90℃and kept for 5 hours, thereby ending the reaction.

The subsequent IR measurement confirmed the disappearance of the isocyanate group, and the synthesis was completed.

The obtained reaction mixture was a tetrafunctional urethane acrylate adduct (hereinafter, referred to as "a-1") having an Mw of 0.4 ten thousand by GPC.

4) Production example 4 production of component (A)

Into a 1L flask equipped with a stirrer, a thermometer and a 5% ON pipe were charged 112.22g of the mixture (a 1-2), 0.063g of BHT and 0.064g of DBTDL.

The contents were stirred while blowing 5% on to bring the flask to 70 ℃. Thereafter, HDI was slowly added, and 13.5g of HDI (a ratio of 0.98 mole of the total isocyanate groups to 1 mole of the total hydroxyl groups of the mixture (a 1-2)) was finally added. Thereafter, the temperature in the flask was raised to 90℃and kept for 5 hours, thereby ending the reaction.

The obtained reaction mixture was a hexafunctional urethane acrylate adduct (hereinafter, referred to as "a-2") having an Mw of 0.4 ten thousand by GPC.

5) Production example 5 production of component (A)

Into a 1L flask equipped with a stirrer, a thermometer and a 5% ON pipe were charged 278.3g of the mixture (a 1-1), 0.50g of BHT and 0.10g of DBTDL.

The contents were stirred while blowing 5% on to bring the flask to 70 ℃. Subsequently, TAP-100 (isocyanate manufactured by Asahi chemical (stock)) was slowly added; hereinafter referred to as TPA-100), 221.7g of TPA-100 was finally added (the ratio of the total of isocyanate groups to the total of 1 mole of hydroxyl groups of the mixture (a 1-1) was 0.98 mole). Thereafter, the temperature in the flask was raised to 90℃and kept for 5 hours, thereby ending the reaction.

The subsequent IR measurement confirmed the disappearance of the isocyanate group, and the synthesis was completed. The obtained reaction mixture was a hexafunctional urethane acrylate adduct (hereinafter, referred to as "a-3") having an Mw of 0.6 ten thousand by GPC.

6) Comparative production example 1 preparation of urethane acrylate adducts other than the component (A)

Into a 1L flask equipped with a stirrer, a thermometer and a 5% ON pipe, 599.4g of Aronix (Aronix) M-305 [ pentaerythritol tri/tetra acrylate manufactured by east Asia Synthesis (Strand) ]; hydroxyl number 115mgKOH/g; hereinafter referred to as M-305), 0.50g of BHT, and 0.10g of DBTDL.

The contents were stirred while blowing 5% on to bring the flask to 70 ℃. Subsequently, TAP-100 was slowly added, and 221.7g of TPA-100 was finally added (the total amount of isocyanate groups was 0.98 mole based on 1 mole of the total of the hydroxyl groups of M-305). Thereafter, the temperature in the flask was raised to 90℃and kept for 5 hours, thereby ending the reaction.

The subsequent IR measurement confirmed the disappearance of the isocyanate group, and the synthesis was completed. The obtained reaction mixture was a nine-functional urethane acrylate adduct (hereinafter, referred to as "a' -1") having an Mw of 0.8 ten thousand by GPC.

2. Examples and comparative examples

1) Production of active energy ray-curable composition

The compounds shown in table 1 below were stirred and mixed in the proportions shown in table 1 to prepare active energy ray-curable compositions.

The obtained composition was used for the evaluation described below. The results are shown in Table 2.

TABLE 1

In Table 1, the numbers refer to parts and abbreviations refer to the following meanings.

M-930: glycerol triacrylate, "Aronix" M-930 "manufactured by east Asia Synthesis"

ACMO: acMO, manufactured by KJ Chemie "

UA306H: tetrafunctional urethane acrylate adducts of pentaerythritol triacrylate and hexamethylene diisocyanate, "UA-306H", manufactured by Zyoku Chen "

HCPK: 1-hydroxycyclohexyl phenyl ketone, amilade (Omnirad) 184 manufactured by the company Ai Jianmeng resin (IGM RESINS)

2) Method for evaluating composition

(1) Viscosity of the mixture

The viscosity of the composition obtained in Table 1 was measured at 25℃using an E-type viscometer. The results are shown in Table 2.

3) Physical Properties of cured film

In the following evaluation, the UV-A intensity was adjusted to 500mW/cm ² At each 1 pass of 800mJ/cm ² Except for the irradiation energy of (a), a sample obtained by hardening the composition was used under the same conditions as those of the hardening test.

(2) Hardness of pencil

Evaluation was performed according to JISK5600-5-4 at a load of 750 g.

(3) Scratch resistance

After 100 times reciprocation with 500g load using steel wool #0000, evaluation was performed according to the following 2 grades.

O: no flaw was found on the cured film, x: visible flaws on the cured film

(4) Flexibility of

According to the mandrel test (JIS K5600-5-1), a polyethylene terephthalate (Polyethylene Terephthalate, PET) film having a cured film formed thereon was wound around a mandrel bar having a diameter of 2mm, 4mm or 6mm, and evaluated according to the following 2 grades.

O: no cracking or peeling of the cured film, x: visible rupture or peeling of hardened films

(5) Crimping property

The sample was cut into 6cm by 6cm, and the height of the four corners of the sample was measured and evaluated as an average value. Smaller values indicate less deformation.

TABLE 2

As is clear from the results of examples 1 and 2, these compositions have low viscosity, and the cured films thereof have excellent hardness, scratch resistance, bendability, and curling properties.

In contrast, in comparative example 1, the composition containing the hexafunctional urethane acrylate adduct as the main component was free of the component (a), but the composition had high viscosity and poor bendability and crimpability.

In example 3, the composition mainly comprised a multifunctional urethane acrylate adduct synthesized from a trifunctional isocyanate, namely, TPA-100, namely, A-3, but the composition was lower in viscosity and excellent in bendability and crimpability as compared with comparative example 2 also comprised a multifunctional urethane acrylate adduct synthesized from TPA-100, namely, A' -1.

[ Industrial applicability ]

The present invention relates to a curable composition which can be preferably used as an active energy ray curable composition.

Further, as a specific application of the composition of the present invention, it can be used for various applications such as a coating agent for hard coat and the like, an ink for lithography and the like, particularly, low viscosity, and the obtained cured film can satisfy hardness, scratch resistance, bending property and curling property at the same time, and therefore, it can be preferably used as a coating agent composition.

Claims

1. A curable composition comprising the following component (A),

2. The curable composition according to claim 1, wherein the organic polyisocyanate is an aliphatic polyisocyanate or an alicyclic polyisocyanate.

3. The curable composition according to claim 1 or 2, wherein the mixture (a 1) is a (meth) acrylate mixture obtained by transesterification of glycerin or diglycerin with a compound having one (meth) acryloyl group in the presence of the following catalyst X and catalyst Y and has a hydroxyl value of 20mgKOH/g to 300mgKOH/g,

catalyst X: one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof, and a phosphine or a salt or complex thereof;

catalyst Y: a compound comprising zinc.

4. A curable composition according to claim 3, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate.

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

6. A hardening composition according to claim 3, wherein said catalyst Y is zinc organic acid or/and zinc diketonate.

7. The curable composition according to claim 1 or 2, wherein the weight average molecular weight of the component (a) is 500 to 10,000.

8. The curable composition according to claim 1 or 2, further comprising the following component (B),

9. An active energy ray hardening composition comprising the composition according to any one of claims 1 to 8.

10. The active energy ray-curable composition according to claim 9, further comprising a photopolymerization initiator in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total of the components (a) and (B), or based on 100 parts by weight of the total of the components (a) and (B).

11. An active energy ray-curable coating agent composition comprising the composition according to claim 9 or 10.