KR20240021744A - Curable composition, active energy ray curable composition, and active energy ray curable coating composition - Google Patents

Abstract

[Problem] Providing a curable composition containing a multifunctional urethane (meth)acrylate adduct that has low viscosity and whose cured film has a good balance between surface hardness, scratch resistance and flexibility, and has excellent curling properties, preferably using active energy Providing a pre-curable composition, particularly a composition that can be suitably used as a coating agent.
[Solution] A curable composition containing the following component (A).
(A) Component: A mixture of at least one compound selected from the group consisting of glycerin (meth)acrylate and diglycerin (meth)acrylate, with a hydroxyl value of 20 to 300 mgKOH/g (mixture) Reactant of a1) with organic polyisocyanate

Description

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

The present invention relates to urethane (meth)acrylate [ Hereinafter, it relates to a curable composition containing “polyfunctional urethane (meth)acrylate adduct”], and preferably to an active energy ray-curable composition.

The composition of the present invention can be used for various purposes, and in particular, has lower viscosity and faster curing properties than conventional multifunctional urethane (meth)acrylate adducts, and is used as a raw material for hard coating agents. When used, a composition with a good balance of elastic modulus and flexibility of the resulting cured film can be obtained, and therefore can be preferably used as a coating composition, and belongs to these technical fields.

In addition, in this specification, acryloyl group and/or methacryloyl group is replaced with (meth)acryloyl group, acrylate and/or methacrylate is (meth)acrylate, acrylic acid and/or methacrylic acid is (meth)acrylic acid. Let's call it that.

Multifunctional urethane (meth)acrylate adduct is a polyfunctional (meth)acrylate having one or more hydroxyl groups and two or more (meth)acryloyl groups and an organic polyisocyanate having two or more isocyanate groups. It is a compound obtained by reacting anate, and has excellent curability, tensile strength, elongation, and toughness of the cured film, so it can be used in various curable compositions such as coatings, inks, adhesives, adhesives, and sealants, and is especially active. It is used in energy ray curable compositions.

An example of an application in which the multifunctional urethane (meth)acrylate adduct is widely used is a hard coating agent for plastics.

Plastic substrates are lightweight and have excellent impact resistance and ease of molding, but have the disadvantage of significantly damaging the appearance if used as is because the surface is prone to scratches and has low hardness. For this reason, it is required to paint the surface of the plastic substrate with a coating composition and apply a so-called hard coating to provide scratch resistance and improve surface hardness.

Conventionally, polyfunctional urethane (meth)acrylate adducts having 10 or more (meth)acryloyl groups in one molecule are used as raw materials for hard coating agents.

Patent Document 1 contains a reaction product between dipentaerythritol pentaacrylate and aliphatic divalent isocyanate, that is, a polyfunctional urethane (meth)acrylate adduct having 10 (meth)acryloyl groups in one molecule. An active energy ray-curable composition is disclosed.

However, although the composition of the patent was excellent in cured film hardness, scratch resistance, and adhesion to the substrate, it was prone to cracking or peeling when the hard coating-treated film substrate was bent, and did not have sufficient flexibility. On the other hand, when trying to improve bending resistance, the cured film hardness and scratch resistance became insufficient, making it difficult to achieve both physical properties. In addition, there was a problem that the film subjected to the hard coating treatment was prone to curling and deteriorated the appearance quality.

In addition, the polyfunctional urethane (meth)acrylate adduct of the patent has a high viscosity, and when used as a solvent-free composition that does not use a diluting solvent, there was a problem that the viscosity was very high and the coatability was poor. .

Patent Document 2 refers to a reaction product between dipentaerythritol pentaacrylate and trivalent isocyanate having an isocyanuric skeleton, that is, polyfunctional urethane (meth)acrylic having 15 (meth)acryloyl groups in one molecule. An active energy ray-curable composition containing a rate adduct is disclosed.

However, although the composition of the patent was excellent in cured film hardness, scratch resistance, and restoration, it was prone to cracking or peeling when the hard coating-treated film substrate was bent, and did not have sufficient flexibility. In addition, when trying to improve flexibility as in Patent Document 1, the hardness and scratch resistance of the cured film became insufficient, making it difficult to achieve both physical properties. In addition, as in Patent Document 1, there is a problem that the film subjected to the hard coating treatment is prone to curling and deteriorates the appearance quality. Furthermore, the patent's multifunctional urethane (meth)acrylate adduct also had a problem of high viscosity.

In this way, the conventional multifunctional urethane (meth)acrylate adduct used as a raw material for a hard coating agent had a problem in that increasing the number of (meth)acryloyl groups in the molecule improved the hardness of the cured film, but worsened the flexibility. In addition, there was a problem that coatability deteriorated because the viscosity of the multifunctional urethane (meth)acrylate adduct was high.

Patent Document 1: Japanese Patent Publication No. 2011-12099 Patent Document 2: International Publication No. 2012/86551 Pamphlet

In order to find a curable composition containing a polyfunctional urethane (meth)acrylate adduct, the present inventors have a low viscosity, the cured film has a good balance between surface hardness, scratch resistance and flexibility, and has excellent curling properties, preferably A thorough study was conducted to find an active energy ray-curable composition, especially a composition that can be suitably used as a coating agent.

In order to solve the above problem, the present inventors have proposed a polyfunctional urethane ( The present invention was completed by discovering that an active energy ray-curable composition containing a meta)acrylate adduct as an essential ingredient has a low viscosity and that the cured film has excellent hardness, scratch resistance, flexibility, and curling properties.

Hereinafter, the present invention will be described in detail.

According to the composition of the present invention, it has a low viscosity, the cured film can simultaneously satisfy the balance between surface hardness, scratch resistance, and flexibility, and has excellent curling properties.

Therefore, 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.

The present invention relates to the following curable composition.

[1] A curable composition containing the following component (A).

(A) Component: A mixture of at least one compound selected from the group consisting of glycerin (meth)acrylate and diglycerin (meth)acrylate, with a hydroxyl value ) is a reaction product of mixture (a1) having 20-300 mgKOH/g and organic polyisocyanate (polyisocyanate)

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

[3] The method of [1] or [2], wherein the mixture (a1) has glycerin or diglycerin (diglycerin) and one (meth)acryloyl group in the presence of the following catalysts A (meth)acrylate mixture obtained by transesterifying a compound [hereinafter referred to as “monofunctional (meth)acrylate”], a curable type having a hydroxyl value of 20 to 300 mgKOH/g. Composition.

Catalyst or one or more compounds selected from the group consisting of complexes and phosphine or salts or complexes thereof.

Catalyst Y: Compound containing zinc.

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

[5] The method of [3] or [4], wherein the catalyst Or a curable composition that is one or more compounds selected from the group consisting of complexes.

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

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

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

(B) Component: Compounds having ethylenically unsaturated groups other than component (A)

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

[10] The activity according to [9], further comprising 0.1 to 10 parts by weight of a photopolymerization initiator based on 100 parts by weight of the total amount of component (A) or 100 parts by weight of the total amount of component (A) and component (B). Energy radiation curable composition.

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

Hereinafter, component (A), curable composition, method of use, and purpose will be described.

1. (A) Ingredient

Component (A) of the present invention 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 20 to 300 mgKOH/g. It is a reaction product of phosphorus mixture (a1) [hereinafter referred to as “mixture (a1)”] and organic polyisocyanate [hereinafter referred to as “compound (a2)”].

Hereinafter, the manufacturing method of mixture (a1), compound (a2), and component (A) will be described.

1-1. mixture (a1)

Mixture (a1) is a mixture of at least one compound selected from the group consisting of glycerin (meth)acrylate and diglycerin (meth)acrylate, and is a mixture having a hydroxyl value of 20 to 300 mgKOH/g. .

When mixture (a1) is a mixture of glycerin (meth)acrylate, a mixture containing glycerin diacrylate as a main component is preferable because it has excellent reactivity with compound (a2).

In the case of a mixture of diglycerol (meth)acrylate, a mixture containing diglycerol triacrylate as a main component is preferred because it has excellent reactivity with compound (a2).

Mixture (a1) consists of glycerin and/or diglycerin (hereinafter, collectively referred to as “(poly)glycerin”) and monofunctional (meth)acrylate [one (meth)acryloyl group). It can be obtained through a transesterification reaction between [compounds having]. Additionally, mixture (a1) can also be obtained through a dehydration esterification reaction between (poly)glycerin and (meth)acrylic acid.

When using glycerin as a raw material, mixture (a1) is a mixture of mono(meth)acrylate, di(meth)acrylate, and tri(meth)acrylate of glycerin. When using diglycerin as a raw material, mixture (a1) includes mono(meth)acrylate of diglycerin, di(meth)acrylate, tri(meth)acrylate, and tetra(meth)acrylate of diglycerin. It is a mixture of meta)acrylates.

The mixture (a1) 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 20 to 300 mgKOH/g. The hydroxyl value of the mixture (a1) is preferably 30 to 290 mgKOH/g, and more preferably 40 to 280 mgKOH/g.

When the hydroxyl value of mixture (a1) is less than 20 mgKOH/g, the hardness of the cured film of the composition containing component (A) obtained decreases. Additionally, when the hydroxyl value exceeds 300 mgKOH/g, the obtained component (A) becomes highly viscous.

In addition, in the present invention, the hydroxyl value means a value measured according to the method specified in JIS K0070-1992.

Furthermore, as a mixture of glycerin (meth)acrylate, a mixture containing glycerin di(meth)acrylate (hereinafter also referred to as “GLY-DA”) is more preferable.

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

[In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group.]

[In the above formula (2), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group.]

Unless specifically purified, GLY-DA is obtained as a mixture between the compound represented by formula (1) and the compound represented by formula (2) during production, so it can be used as is. In particular, the compound represented by formula (1) There are no restrictions on the mixing ratio of the compound and the compound represented by formula (2), and there is no problem even if it is used in any ratio.

The purity of GLY-DA contained in mixture (a1), when calculated using the following formula (3), is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. By setting the purity of GLY-DA to 30% or more, component (A), which is a reactant with compound (a2), can be made to have excellent surface hardness and bending ratio.

Purity of GLY-DA (%)

=〔(DХ2)/(M+D/2+T/3)〕Х100 … Equation (3)

D, M, and T in the calculation formula (3) refer to the following values obtained by analyzing mixture (a1) using a high-performance liquid chromatograph (hereinafter also referred to as “HPLC”) equipped with an ultraviolet (UV) detector. do.

·D: Peak area of GLY-DA at 210 nm

·M: Peak area at 210 nm of glycerin mono(meth)acrylate

·T: Peak area of glycerin tri(meth)acrylate at 210 nm

The peak area by HPLC refers to the value measured under the following conditions.

Detector: UV detector, detection wavelength 210 nm

Type of column: Column filled with silica gel modified with an alkyl group of 18 carbon atoms

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

·Column temperature: 40℃

Composition of eluent: 0.03% by weight trifluoroacetic acid (trifluoroacetic acid) aqueous solution and methanol mixed solution

·Flow rate of eluent: 0.3 mL/min

As mixture (a1), those obtained by various production methods can be used.

For example, those obtained by transesterification between (poly)glycerin and monofunctional (meth)acrylate in the presence of a transesterification catalyst, or (poly)glycerin in the presence of an acidic catalyst. Examples include those obtained by dehydration esterification between serine and (meth)acrylic acid.

Among the above-mentioned production methods, mixture (a1) is obtained by transesterification between (poly)glycerin and monofunctional (meth)acrylate, because it contains fewer impurities and allows the desired (meth)acrylate to be obtained. desirable.

Furthermore, the transesterification reaction between (poly)glycerol and monofunctional (meth)acrylate in the presence of the following catalysts X and Y is preferable.

Catalyst ), a compound having a pyridine ring or a salt or complex thereof (hereinafter also referred to as “pyridine-based compound”), and phosphine or a salt or complex thereof (hereinafter also referred to as “phosphine-based compound”). or more compounds.

Catalyst Y: Compound containing zinc.

Monofunctional (meth)acrylates include 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 carbon atoms, such as alkoxyalkyl (meth)acrylates such as 2-methoxyethyl acrylate, and N, N-dimethylaminoethyl (meth)acrylate. An example can be given.

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

Additionally, acrylates are particularly preferred as monofunctional (meth)acrylates because they have excellent reactivity.

The catalyst These compounds have excellent catalytic activity, and in addition to being able to suitably prepare mixture (a1), they form a complex with catalyst Y described later after completion of the reaction, and the complex is formed in a simple method such as adsorption. It can be easily removed from the liquid. In particular, azabicyclo compounds can be more easily removed through filtration and adsorption because the complex with catalyst Y is poorly soluble in the reaction solution.

Catalyst (1,4-diazabicyclo[2.2.2]octane). Hereinafter also referred to as “DABCO”), N-methylimidazole, 1,8-diazabicyclo[5.4.0]undeca-7-ene (hereinafter also referred to as “DBU”) and 1,5-diazabicyclo[4.3.0]nona-5-ene (hereinafter also referred to as “DBN”) and N,N-dimethyl-4, which are examples of amidine compounds. -Aminopyridine (hereinafter also referred to as “DMAP”) is preferred.

Among these compounds, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU and DMAP, which exhibit good reactivity with most polyhydric alcohols and are readily available, are more preferable.

As catalyst Y, various compounds can be used as long as they contain zinc, but organic acid zinc and zinc diketone enolate are preferred because they have excellent reactivity.

The catalyst Y is preferably zinc acetate, zinc propionate, zinc acrylate, and zinc methacrylate, which are examples of organic zinc acids, and zinc acetylacetonate, which is an example of zinc diketone enolate.

Among these compounds, zinc acetate, zinc acrylate, and zinc acetylacetonate are particularly preferred as catalyst Y because they exhibit good reactivity toward most polyhydric alcohols and are easy to obtain.

There is no particular limitation on the usage ratio of catalyst It is more preferable. By using 0.005 mole or more of catalyst It can be suppressed and the purification process after completion of the reaction can be easily performed.

The combination of catalyst X and catalyst Y is preferably a combination in which catalyst Particularly desirable.

In addition to this combination being able to efficiently obtain mixture (a1), the color tone after completion of the reaction is excellent (e.g., little yellowness), so it is used for applications where colorless transparency is important, such as clear varnish and hard coating. It can be used appropriately. Furthermore, the above-mentioned catalyst is available relatively inexpensively, making it an economically advantageous production method.

The reaction temperature in the method for producing mixture (a1) is preferably 40 to 180°C, more preferably 60 to 160°C. By setting the reaction temperature to 40°C or higher, the reaction rate can be accelerated, and by setting the reaction temperature to 180°C or lower, thermal polymerization of the (meth)acryloyl group in the raw material or product can be suppressed, coloring of the reaction solution can be suppressed, and the reaction is completed. The subsequent purification process can be easily performed.

The reaction pressure in the method for producing mixture (a1) is not particularly limited as long as the predetermined reaction temperature can be maintained, and may be carried out under reduced pressure or under increased pressure. The reaction pressure is preferably 0.000001 to 10 MPa (absolute pressure).

In the method for producing mixture (a1), monohydric alcohol derived from monofunctional (meth)acrylate may be produced as a by-product as the transesterification reaction progresses.

When converting a portion (for example, about 50 mol%) of the hydroxyl group of (poly)glycerin into (meth)acrylate, the monohydric alcohol is coexisted in the reaction system to create an equilibrium state, and the catalyst is removed by adsorption or deactivated ( After the extraction operation, the monohydric alcohol and the monofunctional (meth)acrylate of the raw material are distilled off, so that a product with a controlled acrylation rate can be stably produced.

In the method for producing mixture (a1), the reaction may be carried out without using a solvent, but a solvent may be used as needed.

Specific examples of solvents include hydrocarbons, ethers, crown ethers, esters, ketones, carbonate compounds, sulfones, sulfoxides, ureas or their derivatives, phosphine oxides, and ionic liquids. , silicone oil, and water.

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

These solvents may be used individually, or two or more types may be arbitrarily combined and used as a mixed solvent.

In the method for producing mixture (a1), an inert gas such as argon, helium, nitrogen, or carbon dioxide may be introduced into the system for the purpose of maintaining a good color tone of the reaction solution, but polymerization of the (meth)acryloyl group may be performed. For the purpose of prevention, oxygen-containing gas may be introduced into the system. Specific examples of oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium. Methods for introducing oxygen-containing gas include dissolving it in the reaction solution or blowing it into the reaction solution (so-called bubbling).

In the method for producing mixture (a1), 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 polymerization inhibitors include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors.

Specific examples of organic polymerization inhibitors include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butyl. Phenol-based compounds such as phenol and 4-tert-butylcatechol, quinone compounds such as benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium and N-oxyl compounds, etc. can be mentioned.

N-oxyl compounds include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-oxo. Examples include -2,2,6,6-tetramethylpiperidine-1-oxyl and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl.

As a polymerization inhibitor, it is preferable to use an N-oxyl compound among the above-mentioned compounds. As the N-oxyl compound, the above-mentioned compounds are preferable.

Furthermore, as a polymerization inhibitor, it is preferable to use a combination of an N-oxyl compound and a polymerization inhibitor other than this. In that case, as polymerization inhibitors other than the N-oxyl compound, phenol-based compounds and phenothiazines are preferable, and phenol-based compounds are more preferable.

The polymerization inhibitor may be added individually or in any combination of two or more types, and may be added from the beginning or halfway through the method for producing mixture (a1). Additionally, the desired amount can be added all at once, or it can be added in divided amounts. Additionally, it can be added continuously via a rectification tower.

The addition ratio of the polymerization inhibitor is preferably 5 to 30,000 wtppm, more preferably 25 to 10,000 wtppm, based on the total weight of the reaction solution. By setting the addition ratio of the polymerization inhibitor 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, the purification process after completion of the reaction can be simplified, and the resulting mixture ( A decrease in the curing speed of a1) can be suppressed.

1-2. Compound (a2)

As compound (a2) [organic polyisocyanate], which is another raw material compound of component (A), various compounds can be used.

Examples of compound (a2) include diisocyanate and triisocyanate.

Examples of compound (a2) include aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate.

Specific examples of aliphatic polyisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate (lysine diisocyanate), etc. Examples include the biuret form of the compound, the isocyanurate form, and reactants with polyhydric alcohols such as trimethylolpropane.

Specific examples of alicyclic isocyanates include isophorone diisocyanate, norbornane diisocyanate, and 2,5(2,6)-bis(isocyanate methyl). Bicyclo[2,2,1]heptane, hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate), hydrogenated Xylylene diisocyanate (xylylene diisocyanate) and 1,3-bis (isocyanate methyl) cyclohexane (1,3-bis (isocyanate methyl) cyclohexane), etc., and biuret and iso forms of these compounds. Reactants with polyhydric alcohols such as cyanurate and trimethylolpropane can be mentioned.

Specific examples of aromatic isocyanate include tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate, and the biuret and isocyanate forms of these compounds. Reactants with polyhydric alcohols such as cyanurate and trimethylolpropane can be mentioned.

Moreover, as compound (a2), aliphatic polyisocyanate and alicyclic polyisocyanate are preferred because they have excellent light resistance.

As the compound (a2), aliphatic polyisocyanate is more preferable, and hexamethylene diisocyanate is particularly preferable because the composition has a low viscosity and the cured film has excellent hardness and flexibility.

1-3. (A) Method of producing ingredients

Component (A) can be prepared by urethanizing mixture (a1) and compound (a2) by heating and stirring in the presence of a catalyst and solvent, if necessary.

The reaction ratio of compound (a2) to mixture (a1) is preferably 0.3 to 1.3 mole of the total isocyanate group of compound (a2) relative to 1 mole of hydroxyl group of mixture (a1), and more preferably. Typically, the ratio is 0.5 to 1.2 mol, and particularly preferably, the ratio is 0.9 to 1.1 mol.

In this case, it is possible to react by adding mixture (a1) and compound (a2) all at once, but since there is a problem of increased heat generation during the reaction, it is preferable to add compound (a2) sequentially in the presence of mixture (a1) and react. . Additionally, it is equally preferred to sequentially add mixture (a1) in the presence of compound (a2).

The above reaction can be carried out without a catalyst, but in order to proceed efficiently in a short time, a catalyst commonly used in urethanation reaction can be used during synthesis.

Specific examples of catalysts include tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, and dibutyltin diacetylacetonate, bismuth compounds such as bismuth dioctate, and acetylaceto. iron compounds such as iron nate, zinc compounds such as zinc acetylacetonate; Amine compounds, such as triethylamine, etc. are mentioned.

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

The mixing amount of the catalyst may be any catalytic amount. For example, 0.01 to 1,000 wtppm is preferable, and 0.1 to 1,000 wtppm is more preferable relative to the reaction solution. By setting the amount of the catalyst to 0.01 wtppm or more, the urethanation reaction can proceed suitably, and by setting it to 1,000 wtppm or less, coloring of the obtained component (A) can be suppressed.

The reaction mixture containing component (A) may have a high viscosity, making stirring difficult. Therefore, a solvent may be added to the reaction components.

The solvent is preferably one that does not participate in the urethanization reaction, and examples include aromatic solvents such as toluene and xylene (xylene), and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone (methyl isobutyl ketone). Organic solvents, such as a solvent, are mentioned.

When using an organic solvent, the compounding amount may be appropriately set depending on the viscosity of component (A) to be produced, etc., and is preferably set to 0 to 70% by mass in the reaction solution.

Here, the reaction solution means the total amount of the raw material compounds when only the raw material compounds are used, and when a reaction solvent, etc. is used in addition to the raw material compounds, it means the total amount including these. Specifically, it is used to mean a solution combining mixture (a1), compound (a2), and a catalyst, solvent, polymerization inhibitor, etc. used as necessary.

As a solvent, (meth)acrylate may be blended together with or instead of the organic solvent.

Examples of (meth)acrylates include compounds having an ethylenically unsaturated group other than the component (A) described later (hereinafter referred to as "component (B)").

A urethanization reaction can be performed in the presence of these (meth)acrylates, and a curable composition containing the obtained component (A) and (meth)acrylate can be manufactured. This composition is preferable because, unlike the case of mixing the organic solvent, there is no need to dry after applying the composition.

When mixing (meth)acrylate used as a solvent into the reaction solution, the mixing amount can be set appropriately according to the ratio of other (meth)acrylates ultimately mixed into the composition. For example, the reaction solution It is preferable to set it to 0 to 70% by mass, and further to 0 to 50% by mass.

In the urethanization reaction, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization of the (meth)acryloyl group of the raw material or product, and furthermore, oxygen-containing gas can be introduced into the reaction solution. Examples of oxygen-containing gases include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium.

Examples of polymerization inhibitors include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors. Specific examples of organic polymerization inhibitors include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol. , phenolic compounds such as 4-tert-butylcatechol, quinone compounds such as benzoquinone, galvinoxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2 , 2,6,6-tetramethylpiperidine-1-oxyl, stable radicals such as phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, etc. Specific examples of inorganic polymerization inhibitors include copper chloride, copper sulfate, and iron sulfate. Specific examples of organic salt-based polymerization inhibitors include N-nitroso-N-phenylhydroxylamine·ammonium salt, nitroso compounds such as ammonium N-nitrosophenylhydroxylamine, and dibutyl dithiocarbamate. (carbamic acid) (dibutyldithiocarbamic acid) copper can be mentioned. These may be used alone or two or more types may be used together.

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

The reaction temperature may be set appropriately depending on the raw materials used and the structure and molecular weight of the target component (A), and is usually preferably 25 to 150°C, and more preferably 30 to 120°C. The reaction time may also be set appropriately depending on the raw materials used and the structure and molecular weight of 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 component (A) in the present invention is preferably 500 to 10,000, more preferably 500 to 5,000, from the viewpoint of improving the coatability and adhesion of the composition, It is more preferable that it is 500 to 2,000.

In addition, in the present invention, Mw is a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as "GPC") into polystyrene (polystyrene), and means the value measured under the following conditions.

Detector: Differential refractometer (RI detector)

·Type of column: Cross-linked polystyrene column

·Column temperature: 40℃

·Eluent: Tetrahydrofuran

·Molecular weight standard material: polystyrene

(A) One type of component may be used alone or two or more types may be used in combination.

2. Curable composition

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

The composition may be manufactured by following a conventional method, for example, by stirring and mixing component (A) and other (other) components as necessary.

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

The content ratio of component (A) in the composition is 100% by weight of the total amount of component (A) and component (B) in the case of containing component (B) described later [compound having an ethylenically unsaturated group other than component (A)]. Among them, 1 to 90% by weight is preferable, more preferably 10 to 80% by weight, and even more preferably 20 to 60% by weight.

By setting the ratio of component (A) to 1% by weight or more, the occurrence of bending (curling) of the cured film of the composition can be prevented, and the adhesion of the cured film of the composition can be excellent, and by setting it to 90% by weight or less, the composition can be High viscosity can be suppressed and coatability can be made desirable.

The viscosity of the composition can be set appropriately depending on the purpose, and is preferably 1 to 100,000 mPa·s.

In addition, in the present invention, viscosity refers to a value measured at 25°C 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 can be preferably used as an active energy ray-curable composition.

The composition of the present invention contains the above (A) as an essential component, but various components can be mixed depending on the purpose.

Other components include (B) component [compound having an ethylenically unsaturated group other than component (A)], photopolymerization initiator [hereinafter referred to as “component (C)”], thermal polymerization initiator, organic solvent, antioxidant, and ultraviolet ray. Examples include absorbents, pigments/dyes, leveling agents, silane coupling agents, surface modifiers, and polymers.

Hereinafter, these components will be described.

In addition, as for the other ingredients described later, only one type of the exemplified compounds may be used, or two or more types may be used in combination.

1) (B) Ingredient

Component (B) is an ethylenically unsaturated compound other than the component (A), and is blended 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 (meth)acryloyl group, (meth)acrylamide group ((meth)acrylamide group), vinyl group (vinyl group), and (meth)allyl group. and (meth)acryloyl group is preferred.

In addition, in the following, "monofunctional" refers to a compound having one ethylenically unsaturated group, "○functional" refers to a compound having ○ ethylenically unsaturated groups, and "polyfunctional" refers to a compound having two or more ethylenically unsaturated groups. refers to a compound that has

(B) Components include a compound having one ethylenically unsaturated group (hereinafter referred to as “monofunctional unsaturated compound”) and a compound having two (meth)acryloyl groups (hereinafter referred to as “bifunctional (meth)acrylate”) ) and compounds having three or more (meth)acryloyl groups (hereinafter referred to as “trifunctional or higher (meth)acrylates”).

In component (B), specific examples of the monofunctional unsaturated compound include compounds having a (meth)acryloyl group, monofunctional (meth)acrylamide, and compounds having a vinyl group.

Examples of compounds having a (meth)acryloyl group include (meth)acrylic acid, a dimer of the Michael addition type of acrylic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, and phthalic acid monohydroxyethyl (meth)acrylate. Compounds having a carboxyl group (carboxyl group) and an ethylenically unsaturated group;

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

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

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

Benzyl (meth)acrylate, (meth)acrylate of alkylene oxide adduct of phenol, (meth)acrylate of alkylene oxide adduct of alkylphenol, (meth)acrylate of alkylene oxide adduct of paracumylphenol, ortho Monofunctional (meth)acrylates with an aromatic group, such as phenylphenol (meth)acrylate, (meth)acrylate of the alkylene oxide adduct of orthophenylphenol, and 2-hydroxy-3-phenoxypropyl (meth)acrylate. ;

Cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate (dicyclopentenyl (meth)acrylate), die Monofunctional (meth)acrylates having an alicyclic group such as cyclopentenyloxyethyl (meth)acrylate and tricyclodecanemethylol (meth)acrylate; and

Tetrahydrofurfuryl (meth)acrylate, (meth)acryloylmorpholine, N-(2-(meth)acryloxyethyl)hexahydrophthalimide and N-(2 -Monofunctional (meth)acrylates having a heterocycle, such as (meth)acryloxyethyl)tetrahydrophthalimide, etc. are mentioned.

Monofunctional (meth)acrylamides include N,N-dimethyl(meth)acrylamide, (meth)acryloylmorpholine, N-methyl(meth)acrylamide, N-n-propyl(meth)acrylamide, and N-iso. N-alkyl (meth)acrylamide, such as propyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-sec-butyl (meth)acrylamide, N-t-butyl (meth)acrylamide, and N-n-hexyl (meth)acrylamide. meta)acrylamide;

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

N,N-dimethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide Amide, N,N-di-n-propyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di-n-butyl(meth)acrylamide and N,N-di Examples include N,N-dialkyl (meth)acrylamide such as hexyl (meth)acrylamide.

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

Bifunctional (meth)acrylates specifically include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, and hexane diacrylate. Di(meth)acrylates of aliphatic diols such as alldi(meth)acrylate (hexanedioldi(meth)acrylate) and nonanedioldi(meth)acrylate (nonanedioldi(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

Di(meth)acrylates of alkylene oxide adducts of diols having a bisphenol skeleton, such as di(meth)acrylates of alkylene oxide adducts of bisphenol A and di(meth)acrylates of alkylene oxide adducts of bisphenol F, etc. Examples include:

In addition to the above-mentioned compounds, bifunctional (meth)acrylates include epoxy (meth)acrylates having a bisphenol skeleton, polyether skeleton, or polyalkylene skeleton, and oils having a polyester skeleton, polyether skeleton, or polycarbonate skeleton. Oligomers such as lethane (meth)acrylate and polyester (meth)acrylate can be used.

Examples of trifunctional or higher (meth)acrylates include various compounds as long as they have three or more (meth)acryloyl groups, for example, glycerin tri(meth)acrylate, diglycerin tetra. (meth)acrylate, trimethylolpropane tri(meth)acrylate, tri or tetra(meth)acrylate of pentaerythritol, tri or tetra(meth)acrylate of ditrimethylolpropane and dipentaerythritol Polyol poly(meth)acrylates such as tri, tetra, penta, or hexa(meth)acrylate;

Tri or tetra(meth)acrylate of pentaerythritol alkylene oxide adduct, tri or tetra(meth)acrylate of ditrimethylolpropane alkylene oxide adduct, tri, tetra, penta or pentaerythritol alkylene oxide adduct. Poly(meth)acrylate of polyol alkylene oxide adduct such as hexa(meth)acrylate;

Tri(meth)acrylate of isocyanuric acid (isocyanuric acid) alkylene oxide adduct; and

and urethane (meth)acrylate, which is a reaction product between a compound having a hydroxyl group such as pentaerythritol tri(meth)acrylate and three or more (meth)acryloyl groups, and an organic polyisocyanate.

Examples of the alkylene oxide adduct in the above include ethylene oxide adduct, propylene oxide adduct, and ethylene oxide and propylene oxide adduct.

In addition, the organic polyisocyanate includes hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and isophorone diisocyanate. Nate, norbornene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-diisocyanate Examples include cyclohexylmethane diisocyanate and trimer of hexamethylene diisocyanate.

The content ratio of component (B) is 0 to 60% by weight based on 100 parts by weight of the total amount of component (A) and component (B) (hereinafter, component (A) and component (B) are collectively referred to as “curable components”). It is preferable to include it, and more preferably, it is 0 to 30% by weight.

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

2) (C) component

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

When using the composition of the present invention as an active energy ray curable composition, especially when ultraviolet rays and visible rays are used as active energy rays, it is preferable to additionally contain component (C) from the viewpoint of ease of curing and cost. do.

When using an electron beam as an active energy ray, it is not necessary to mix it, but it may be mixed in small amounts as needed to improve curability.

(C) Specific examples of components include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexylphenyl ketone, 2-hyde. Roxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, Oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]propanone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropione 1) benzyl] phenyl}-2-methylpropane-1-one, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin- 4-yl-phenyl)butane-1-one, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-octylcarbazole, phenylglyoxylic acid (phenylglyoxylic acid) ) Aromatic ketone compounds such as methyl, ethylanthraquinone, and phenanthrenequinone;

Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-(methylphenylthio)phenylphenylmethane, Methyl-2-benzophenone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propane-1-one, 4,4'-bis( Benzophenone-based compounds such as dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone;

Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphine oxide and bis Acylphosphine oxide compounds such as (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide;

Thioxanthone (thioxanthone), 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropyl thioxanthone, 1-chloro-4-propyl thioxanthone, 3-[3,4- thioxanthone-based compounds such as dimethyl-9-oxo-9H-thioxanthone-2-yl-oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride and fluorothioxanthone, etc. I can hear it.

Among these compounds, α-hydroxyphenylketones are preferred because they have good surface hardening properties even when coated as a thin film in the air, and specifically, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1-phenyl-prop. Payne-1-one is more preferred.

In addition, when it is necessary to increase the thickness of the cured film, for example, to 50 μm or more, for the purpose of improving the curability inside the cured film, or when using a UV absorber or pigment together, bis (2, 4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine and bis(2) Acylphosphine oxide compounds such as ,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide or 2-methyl-1-[4-(methylthio)]phenyl]-2-mo Polinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-dimethylamino-2-(4-methylbenzyl) It is preferable to use -1-(4-morpholin-4-yl-phenyl)-butane-1-one, etc. in combination.

The content ratio of 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 amount of curable components. By setting the ratio of component (C) to 0.1 parts by weight or more, the photocurability of the composition can be improved and adhesion can be excellent, and by setting the ratio of component (C) to 10 parts by weight or less, the internal curing property of the cured film can be improved, and the composition has good adhesion. Adhesion can be improved.

3) Thermal polymerization initiator

When using the composition as a thermosetting composition, a thermal polymerization initiator can be added.

The composition of the present invention can also be cured by mixing a thermal polymerization initiator and heating.

A variety of compounds can be used as the thermal polymerization initiator, and organic peroxides and azo-based initiators are preferred.

Specific examples of organic peroxides include 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-view) Tylperoxy) cyclohexane, 2,2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane (1,1-bis ( t-butylperoxy)cyclododecane), t-hexylperoxyisopropylmonocarbonate, t-butylperoxymaleic acid (t-butylperoxymaleic acid), t-butylperoxy-3,5,5-tri Methylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxyisopropylmonocarbonate, t-butylperoxide Oxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-di-methyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis( t-butylperoxy)butane (2,2-bis(t-butylperoxy)butane), t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate , di-t-butylperoxyisophthalate, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-view) Tylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide (p-menthane hydroperoxide), 2,5-dimethyl-2,5-di( t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumene Hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, etc. can be mentioned.

Specific examples of azo compounds include 1,1'-azobis(cyclohexane-1-carbonitrile) (1,1'-azobis(cyclohexane-1-carbonitrile)), 2-(carbamoylazo) Isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, azodi-t-butane, etc. are mentioned.

These may be used individually or two or more types may be used together. Additionally, organic peroxides can be combined with a reducing agent to undergo an oxidation-reduction (redox) reaction.

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

When the thermal polymerization initiator is used alone, it can be carried out according to the usual methods of normal radical thermal polymerization. In some cases, it can be used in combination with a photopolymerization initiator and photocured for the purpose of further improving the reaction rate. Heat curing can also be performed.

4) Organic solvent

The composition of the present invention can be used as a composition containing an organic solvent for purposes such as improving coatability on a substrate.

Specific examples of organic solvents 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; Acetone alcohol 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-methylpyrrolidone.

Among 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, based on 100 parts by weight of the total amount of the curable component. Within the above range, the composition can be made to have a viscosity suitable for coating, and the composition can be easily applied by a known application method described later.

5) Antioxidants

Antioxidants are mixed for the purpose of improving durability, such as heat resistance and weather resistance, of the cured film.

Antioxidants include, for example, phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

Examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. Examples of 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 phosphorus-based antioxidants include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphite and triaryl phosphite. These derivatives and commercially available products include, for example, Adekastab PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, manufactured by Adeka Co., Ltd. Examples include 1500, 135A, 3010, etc.

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

These may be used as one type or as two or more types. Preferred combinations of these antioxidants include, for example, the combined use of a phenolic antioxidant and a phosphorus-based antioxidant, and the combined use of a phenolic antioxidant and a sulfur-based antioxidant.

The content ratio of the antioxidant may be appropriately set depending on 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.

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

6) UV absorber

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

Examples of ultraviolet absorbers include triazine-based ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole-based ultraviolet absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.

The content ratio of the ultraviolet absorber may be appropriately set depending on 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 component. By setting the content ratio to 0.01% by weight or more, the light resistance of the cured film can be improved. On the other hand, by setting the content ratio to 5% by weight or less, the curability of the composition can be excellent.

7) Pigment/dye

Examples of pigments 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 Lithol Red, Helio Bordeaux, Pigment Scarlet Red, and Permanent Red 2B; Derivatives from vat dyes such as alizarin, indanthrone and Thioindigo Maroon; Phthalocyanine-based organic pigments such as Phthalocyanine Blue and Phthalocyanine Green; Quinacridone-based organic pigments such as Quinacridone Red and Quinacridone Magenta, perylene-based organic pigments such as Perylene Red and Perylene Scalet; Isoindolinone-based organic pigments such as Isoindolinone Yellow and Isoindolinone Orange; Pyranthrone-based organic pigments such as Pyranthrone Red and Pyranthrone Orange; thioindigo-based organic pigments; Condensed azo-based organic pigments; Benzimidazolone-based organic pigments; Quinophthalone-based organic pigments such as Quinophthalone Yellow, isoindoline-based organic pigments such as Isoindoline Yellow; And other pigments include Flavanthrone Yellow, Acylamide Yellow, Nickel Azo Yellow, Copper Azomethine Yellow, Perinone Orange, Examples include Anthrone Orange, Dianthraquinolyl Red, and Dioxazine Violet.

In addition, specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, Bengala (red iron (III) oxide), cadmium red ( Examples include red, ultramarine blue, royal blue, chromium oxide rust, cobalt rust, amber, titanium black, and synthetic iron black. In addition, the carbon black exemplified in the above filler can also be used as an inorganic pigment.

As dyes, various conventionally known compounds can be used.

8) Silane coupling agent

Silane coupling agents are formulated 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 improving adhesion to the substrate.

Silane coupling agents specifically include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane). , 3-Glycidoxypropylmethyldiethoxysilane, 3-Glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane Toxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldime Examples include toxysilane and 3-mercaptopropyltrimethoxysilane.

The mixing ratio of the silane coupling agent may be appropriately set depending on 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.

The adhesion of the composition can be improved by setting the mixing ratio to 0.1 parts by weight or more, and on the other hand, by setting the mixing ratio to 10 parts by weight or less, it is possible to prevent changes in adhesion over time.

9) Surface modifier

A surface modifier may be added to the composition of the present invention for the purpose of improving leveling properties during application or for the purpose of improving scratch resistance by increasing the slipperiness of the cured film.

Examples of surface modifiers include surface modifiers, surfactants, leveling agents, antifoaming agents, slipperiness imparting agents, and antifouling agents, and these known surface modifiers can be used.

Among them, silicone-based surface modifiers and fluorine-based surface modifiers can be cited as suitable examples. Specific examples include silicone-based polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone-based polymers and oligomers having a silicone chain and a polyester chain, and fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkyleneoxide chain. and fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain.

Additionally, for the purpose of increasing the durability of slipperiness, a surface modifier having an ethylenically unsaturated group, preferably a (meth)acryloyl group, in the molecule 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 component. If it is within the above range, the surface smoothness of the coating film is excellent.

10) Polymer

The composition of the present invention may further contain a polymer for the purpose of further improving the curling resistance of the resulting cured film.

Suitable polymers include (meth)acrylic polymers, and suitable constituent monomers include methyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate, and N. Examples include -(2-(meth)acryloxyethyl)tetrahydrophthalimide. In the case of a polymer copolymerized with (meth)acrylic acid, a (meth)acryloyl group may be introduced into the polymer chain by adding glycidyl (meth)acrylate.

The polymer content is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the curable component. Within the above range, the curling resistance of the obtained cured film is more excellent.

3. How to use

The method of using the composition of the present invention may follow a commercial method.

For example, a method of applying the composition to a substrate and then curing it by irradiating active energy rays or heating is included.

Specifically, in the case of applications such as coatings and adhesives, the composition is applied to the applied substrate by a normal coating method, and then in the case of an active energy ray curable composition, a method of curing by irradiating active energy rays, and also a heat curing type In the case of compositions, examples include a method of curing by heating. In the case of use as a molding material, a method of injecting the composition into a predetermined mold and then curing it by irradiating active energy rays in the case of an active energy ray-curable composition, and a method of curing it by heating in the case of a heat-curable composition, etc. An example can be given.

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

Additionally, a method of improving adhesion to the substrate can be adopted by using component (C) (photopolymerization initiator) and a thermal polymerization initiator together in the composition, irradiating the composition with active energy rays, and then heating and curing the composition.

The substrate to which the composition of the present invention can be applied can be applied to a variety of materials, and examples include plastic, wood, metal, inorganic materials, and paper.

Specific examples of plastic include polyvinyl alcohol, cellulose acetate resin such as triacetylcellulose and diacetylcellulose, acrylic resin, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone (polyethersulfone), norbornene, etc. Cyclic polyolefin resins containing cyclic olefins as monomers, polyvinyl chloride, epoxy resins, and polyurethane resins may be included.

Examples of wood include natural wood and synthetic wood.

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

Examples of inorganic materials include glass, mortar, concrete, and stone.

Among these, plastic substrates are particularly preferable.

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

The coating method for the base material of the composition of the present invention may be appropriately set depending on the purpose, and may include bar coater, applicator, doctor blade, dip coater, and roll coater. coater, spin coater, flow coater, knife coater, comma coater, reverse roll coater, die coater, lip coater ( Examples include coating methods using a lip coater, gravure coater, and micro gravure coater.

Examples of active energy rays for curing the composition of the present invention include ultraviolet rays, visible rays, and electron rays, and ultraviolet rays are preferred.

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

The irradiation energy should be set appropriately depending on the type of active energy ray and the composition, but for example, when using a high-pressure mercury lamp, the irradiation energy in the UV-A region is preferably 10 to 10,000 mJ/cm ² , and 100 ~2,000 mJ/cm ² is more preferred.

4. Uses

The composition of the present invention can be used for various purposes, and specific examples include coating agents such as hard coating, inks such as offset printing, adhesives, adhesives, and sealants.

The composition of the present invention can preferably be used as an active energy ray-curable composition, and the cured film has an excellent balance between surface hardness, scratch resistance, and flexibility, and has excellent curling properties, so it can be more preferably used as a hard coating agent.

Suitable uses for hard coatings include, for example, front panels for display boards, building materials, lighting fixtures, displays and cases for mobile phones, smartphones, and tablet terminals, and cases for home appliances. and various lenses such as glasses.

Specific examples of front boards for display boards include electronic bulletin boards, displays, signs, advertisements, and signs.

Examples of using wood as a substrate include woodworking products such as stairs, floors, and furniture. Examples of using metal as a base material include metal products such as kitchen panels and stainless steel sinks.

Example

Examples and comparative examples will be shown below and the present invention will be described in more detail.

In addition, hereinafter, “part” means part by weight.

1. Manufacturing example

1) Preparation Example 1 [Preparation of mixture (a1)]

Glycerin (purified glycerin manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was placed in a 3-liter flask equipped with a stirrer, thermometer, gas introduction pipe, rectifier column, and cooling pipe. product name). 302.75 parts (3.29 mol) of 2-methoxyethyl acrylate (hereinafter referred to as “MCA”), 2312.84 parts (17.77 mol) of 2-methoxyethyl acrylate (hereinafter referred to as “MCA”), and 6.51 parts (0.06 mol) of DABCO as catalyst mol), as catalyst Y, 24.07 parts (0.12 mol) of zinc acrylate, 1.19 parts (0.01 mol) of hydroquinone monomethyl ether (hereinafter referred to as “MEHQ”), and 0.21 parts (0.002 mol) of phenothiazine were added. , oxygen-containing gas (oxygen at 5% by volume and nitrogen at 95% by volume) was bubbled into the liquid.

While heating and stirring the reaction solution at a temperature in the range of 100 to 130°C, the pressure in the reaction system was adjusted to a range of 110 to 760 mmHg, and 2-methoxyethanol (hereinafter referred to as "MEL"), which was produced by-product as the transesterification reaction with MCA progressed, was heated and stirred. ) was extracted from the reaction system through a rectifier tower and cooling pipe. Additionally, MCA of the same weight as the extracted liquid was added to the reaction system at any time. 18 hours after the start of heating and stirring, the pressure in the reaction system was returned to normal pressure and extraction was completed.

The acrylation rate of the hydroxyl group of GLY was determined from the amount of MEL produced, and was found to be 57 mol%.

The reaction solution is cooled to room temperature, the precipitate is separated by filtration, and then aluminum silicate (manufactured by Kyowa Chemical Industry Co., Ltd.) is used to adsorb and remove catalyst KYOWAAD 700SEN-S (product name). Hereinafter referred to as “700SEN-S”], 58.7 parts were added and stirred, and further heated and stirred in the range of 70 to 100°C for 1 hour. After the aluminum silicate after the adsorption treatment is separated by filtration, the filtrate is placed in a flask connected to a stirrer, thermometer, gas introduction tube, distillate cooling tube, and pressure reduction tube, and the temperature is 70 to 100°C. , reduced pressure distillation was performed for 10 hours while bubbling dry air at a pressure in the range of 0.001 to 100 mmHg, and the effluent containing unreacted MCA was separated. Diatomaceous earth (RADIOLITE (brand name) manufactured by Showa Chemical Industry Co., Ltd.) was added to the kiln liquid. Hereinafter referred to as "radiolite"] was added in an amount of 5.0 parts and pressure filtration was performed, and the obtained filtrate was used as mixture (a1). The yield of mixture (a1) was 647 parts. Hereinafter, this is referred to as mixture (a1-1).

When all 302.75 parts of GLY added are converted to glycerinda diacrylate (hereinafter referred to as “GLY-DA”), the quantity is 658 parts, but the yield of the mixture (a1-1) calculated based on this is 98%. It was.

Using HPLC equipped with a UV detector, the purity of GLY-DA contained in mixture (a1-1) was calculated from the following calculation formula (3), and the result was 63%, and glycerine triacrylate (hereinafter, "GLY-TA ") was 23%, and glycerin monoacrylate (hereinafter referred to as "GLY-MA") was 14%.

The obtained mixture (a1-1) had a viscosity of 41 mPa·s (25°C) and a hydroxyl value of 240 mgKOH/g. Mw by GPC measurement was 309.

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

◆ HPLC measurement conditions

·Device: ACQUITY UPLC manufactured by Waters Co., Ltd.

Detector: UV detector

·Detection wavelength: 210 nm

Column: ACQUITY UPLC BEH C18 manufactured by Waters Co., Ltd. (Part No. 186002350, column inner diameter 2.1 mm, column length 50 mm)

·Column temperature: 40℃

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

·Flow rate of eluent: 0.3 mL/min

◆ Method for calculating the purity of GLY-DA contained in mixture (a1-1)

Purity% of GLY-DA

=〔(D/2)/(M+D/2+T/3)〕Х100... Equation (3)

The symbols and terms in calculation formula (1) have the following meanings.

·D: Peak area of GLY-DA at 210 nm

·M: Peak area of GLY-MA at 210 nm

·T: Peak area of GLY-TA at 210 nm

◆ Viscosity measurement conditions

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

◆ Hydroxyl value measurement conditions

Measurement was made according to JIS K0070-1992. That is, an acetylation reagent is added to the sample and heat treatment is performed in a hot bath. After cooling, the hydroxyl value was obtained by titrating the acid with potassium hydroxide ethanol solution using the phenolphthalein solution as an indicator.

In addition, 5 times the amount of pyridine was used as in the method described in JIS K0070-1992.

◆ GPC measurement conditions

·Device: GPC system name 1515 2414 717P RI manufactured by Waters Co., Ltd.

·Detector: RI detector

Column: Guard Column Shodex KFG (8 μm 4.6Х10 mm) manufactured by Showa Denko Co., Ltd., 2 types of this column, styragel HR 4E THF (7.8 mm) manufactured by Waters Co., Ltd. Х300 mm)+styragel HR 1THF(7.8Х300 mm)

·Column temperature: 40℃

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

In addition, GPC measurements were performed under the same conditions in Preparation Examples 2 to 5.

2) Preparation Example 2 (Preparation of mixture (a1))

Diglycerin (Glycerin 801 (brand name) manufactured by Sakamoto Pharmaceutical Co., Ltd.) was placed in a 3-liter flask equipped with a stirrer, thermometer, gas introduction pipe, distillation column, and cooling pipe. Hereinafter referred to as “DGLY”], 249.92 parts (1.50 mol), MCA 1410.92 parts (10.84 mol), DABCO as catalyst , 0.99 parts (0.01 mol) of MEHQ and 0.45 parts (0.003 mol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl were added, and oxygen-containing gas (oxygen was added at 5% by volume). , 95% by volume nitrogen) was bubbled into the liquid.

While heating and stirring the reaction solution at a temperature in the range of 100 to 130°C, the pressure in the reaction system was adjusted in the range of 150 to 760 mmHg, and the mixed liquid of MCA and MEL by-produced as the transesterification reaction progressed was removed from the reaction system through the distillation tower and cooling tube. pulled it out In addition, MCA containing a polymerization inhibitor was added periodically to balance the weight of the extracted liquid. 20 hours after the start of heating and stirring, the pressure in the reaction system was returned to normal pressure and extraction was completed.

The acrylation rate of the hydroxyl group of DGLY was determined from the amount of MEL produced and was found to be 82 mol%.

The reaction solution was cooled to room temperature, the precipitate was separated by filtration, and then 25.0 parts of amluminium silicate (700SEN-S) was added and stirred to adsorb and remove catalyst It was heated and stirred at ℃ for 1 hour. After that, 3.7 parts of calcium hydroxide was added at an internal temperature of 20 to 40°C, stirred for 1 hour under normal pressure, and insoluble matter was separated by pressure filtration.

2.0 parts of ammonium silicate (700SEN-S) was added to the obtained filtrate, placed in a flask connected to a stirrer, thermometer, gas introduction tube, outflow cooling tube, and pressure reduction tube, and the temperature was 70 to 100°C and the pressure was 0.001. Reduced pressure distillation was performed for 10 hours while bubbling dry air in the range of ∼100 mmHg, and the effluent containing unreacted MCA was separated.

0.33 parts of DEHA was added to the obtained kiln liquid, and the mixture was stirred for 3 hours under normal pressure at an internal temperature of 70 to 90°C. After that, 5.0 parts of diatomaceous earth (radiolite) was added to the kiln liquid, pressure filtration was performed, and a filtrate was obtained. The obtained filtrate was used as mixture (a1). The quantity of mixture (a1) was 502 parts. Hereinafter, this is referred to as mixture (a1-2).

Using HPLC equipped with a UV detector, the purity of diglycerol triacrylate (hereinafter referred to as "DGLY-TA") contained in mixture (a1-2) was calculated from the following calculation formula (4), and the result was 41%. It was.

The obtained mixture (a1-2) had a viscosity of 223 mPa·s (25°C) and a hydroxyl value of 80 mgKOH/g.

◆ Method for calculating the purity of DGLY-TA contained in mixture (a1-2)

Purity% of DGLY-TA

=〔(Tri/3)/(M+D/2+Tri/3+Tetra/4)〕Х100 … Equation (4)

The symbols and terms in calculation formula (1) have the following meanings.

·Tri: Peak area at 210 nm of DGLY-TA

·M: Peak area at 210 nm of diglycerin monoacrylate

·D: Peak area at 210 nm of diglyceryl diacrylate

Tetra: Peak area at 210 nm of diglycerine tetraacrylate

3) Preparation Example 3 [Preparation of component (A)]

93.52 g of 2,6-di-t-butyl mixture (a1-1) was added to a 1L flask equipped with a stirrer, thermometer, and piping for an oxygen/nitrogen mixed gas with an oxygen concentration of 5% (hereinafter referred to as 5% ON). 0.064 g of -4-methylphenol (hereinafter referred to as BHT), di-n-butyltin dilaurate [reagent manufactured by FUJIFILM Wako Pure Chemical Corporation]. Hereinafter referred to as DBTDL] 0.064 g was added.

The contents were stirred while blowing 5% ON to bring the inside of the flask to 70°C. After that, hexamethylene diisocyanate (hereinafter referred to as HDI) was gradually added, and finally, 33.6 g of HDI [the total of isocyanate groups relative to the total of 1 mole of hydroxyl groups in mixture (a1-1) is A ratio of 0.98 mole] was added. After that, the temperature inside the flask was raised to 90°C and maintained for 5 hours to complete the reaction.

Subsequent IR measurement confirmed that the isocyanate group had disappeared, and the synthesis was completed.

The obtained reaction mixture was a tetrafunctional urethane acrylate adduct (hereinafter referred to as “A-1”) with a Mw of 0.40,000 according to GPC.

4) Preparation Example 4 [Preparation of component (A)]

112.22 g of mixture (a1-2), 0.063 g of BHT, and 0.064 g of DBTDL were added to a 1L flask equipped with a stirrer, thermometer, and 5% ON pipe.

The contents were stirred while blowing 5% ON to bring the inside of the flask to 70°C. After that, HDI was gradually added, and finally 13.5 g of HDI was added [the ratio of 0.98 mole of isocyanate groups in total to 1 mole of hydroxyl groups in the mixture (a1-2)]. After that, the temperature inside the flask was raised to 90°C and maintained for 5 hours to complete the reaction.

Subsequent IR measurement confirmed that the isocyanate group had disappeared, and the synthesis was completed.

The obtained reaction mixture was a hexafunctional urethane acrylate adduct (hereinafter referred to as "A-2") with a Mw of 0.40,000 by GPC.

5) Preparation Example 5 [Preparation of component (A)]

278.3 g of mixture (a1-1), 0.50 g of BHT, and 0.10 g of DBTDL were added to a 1L flask equipped with a stirrer, thermometer, and 5% ON pipe.

The contents were stirred while blowing 5% ON to bring the inside of the flask to 70°C. After that, TPA-100 [isocyanate manufactured by Asahi-Kasei Chemicals Corporation. Hereinafter referred to as TPA-100] was gradually added, and finally, 221.7 g of TPA-100 [the ratio of 0.98 mole of isocyanate groups in total to 1 mole of hydroxyl groups in the mixture (a1-1)] was added. After that, the temperature inside the flask was raised to 90°C and maintained for 5 hours to complete the reaction.

Subsequent IR measurement confirmed that the isocyanate group had disappeared, and the synthesis was completed. The obtained reaction mixture was a hexafunctional urethane acrylate adduct (hereinafter referred to as "A-3") with a Mw of 0.60,000 according to GPC.

6) Comparative Production Example 1 [Manufacture of urethane acrylate adducts other than component (A)]

ARONIX M-305 [pentaerythritol tri/tetraacrylate manufactured by TOAGOSEI CO., LTD.] was placed in a 1L flask equipped with a stirrer, thermometer, and 5% ON piping. Hydroxyl value is 115 mgKOH/g. 599.4 g of [hereinafter referred to as M-305], 0.50 g of BHT, and 0.10 g of DBTDL were added.

The contents were stirred while blowing 5% ON to bring the inside of the flask to 70°C. After that, TPA-100 was gradually added, and finally 221.7 g of TPA-100 was added [the ratio of 0.98 mole of isocyanate groups in total to 1 mole of hydroxyl groups in M-305]. After that, the temperature inside the flask was raised to 90°C and maintained for 5 hours to complete the reaction.

Subsequent IR measurement confirmed that the isocyanate group had disappeared, and the synthesis was completed. The obtained reaction mixture was a nine-functional urethane acrylate adduct (hereinafter referred to as "A'-1") with a Mw of 0.80,000 by GPC.

2. Examples and comparative examples

1) Preparation of active energy ray curable composition

The compounds shown in Table 1 below were stirred and mixed at the ratio shown in Table 1 to prepare an active energy ray-curable composition.

The evaluation described below was performed using the obtained composition. Their results are shown in Table 2.

(A) (B) (C) Example 1 A-1
(50) M-930
(30) ACMO
(20) HCPK
(2) Example 2 A-2
(50) M-930
(30) ACMO
(20) HCPK
(2) Example 3 A-3
(50) M-930
(30) ACMO
(20) HCPK
(2) Comparative Example 1 UA-306H
(50) M-930
(30) ACMO
(20) HCPK
(2) Comparative Example 2 A'-1
(50) M-930
(30) ACMO
(20) HCPK
(2)

In addition, the numbers in Table 1 mean radicals, and the abbreviations mean the following.

·M-930: Glycerine triacrylate, manufactured by Doa Synthesis, “Aronics M-930”

ACMO: Acryloylmorpholine, “ACMO” manufactured by KJ Chemicals Corporation

·UA306H: tetrafunctional urethane acrylate adduct of pentaerythritol triacrylate and hexamethylene diisocyanate, “UA-306H” manufactured by Kyoeisha Chemical Co., Ltd.

HCPK: 1-hydroxycyclohexylphenyl ketone, Omnirad184 manufactured by IGM RESINS

2) Method of evaluating composition

(1) Viscosity

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

3) Cured film properties

In the following evaluation, a sample was used where the composition was cured under the same conditions as the curability test, except that the UV-A intensity was adjusted to 500 mW/cm ² and the irradiation energy was 800 mJ/cm ² per pass.

(2) Pencil hardness

Evaluation was performed with a load of 750 g according to JIS K5600-5-4.

(3) Scratch resistance

After 100 round trips with a load of 500 g using steel wool #0000, evaluation was performed at the following two levels.

○: No flaws are visible in the cured film, Х: Flaws are visible in the cured film.

(4) Flexibility

According to the Mandrel Test (JIS K5600-5-1), PET film with a cured film is wound around a mandrel with a diameter of 2 mm, 4 mm, or 6 mm, and evaluation is performed at the following two levels. did.

○: There was no cracking or peeling of the cured film, Х: There was cracking or peeling of the cured film.

(5) Curling property

The sample was cut into 6 cmХ6 cm, the raised heights of the four corners were measured and evaluated as the average value. A smaller value indicates less deformation.

viscosity
(mPa·s)
pencil hardness
scratch resistance flexibility
Curling ability
(mm) diameter
2mm diameter
4mm diameter
6 mm Example 1 120 3H ○ ○ ○ ○ 2 Example 2 160 3H ○ ○ ○ ○ 2 Example 3 3,560 5H ○ Х ○ ○ 6 Comparative Example 1 300 3H ○ Х Х ○ 8 Comparative Example 2 9,730 5H ○ Х Х Х 12

As is clear from the results of Examples 1 and 2, these compositions had low viscosity, and their cured films were excellent in hardness, scratch resistance, flexibility, and curling properties.

On the other hand, Comparative Example 1 was a composition containing a hexafunctional urethane acrylate adduct as the main component and not containing component (A), but had a high viscosity and poor flexibility and curling properties.

In addition, Example 3 is a composition containing A-3, a polyfunctional urethane acrylate adduct synthesized from TPA-100, a trifunctional isocyanate, as the main component, and the polyfunctional oil similarly synthesized from TPA-100 It had a lower viscosity than Comparative Example 2, which contains lethanacrylate adduct A'-1 as the main component, and was excellent in flexibility and curling properties.

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

Furthermore, the composition of the present invention can be used for various purposes as a coating agent such as hard coating and ink such as offset printing. In particular, it has low viscosity, and the resulting cured film satisfies hardness, scratch resistance, flexibility and curling properties at the same time. Since it can be used as a coating composition, it can be preferably used as a coating composition.

Claims (11)

A curable composition containing the following component (A).
(A) Component: A mixture of at least one compound selected from the group consisting of glycerin (meth)acrylate and diglycerin (meth)acrylate, with a hydroxyl value of 20 to 300 mgKOH/g (mixture) Reactant of a1) with organic polyisocyanate In claim 1,
A curable composition wherein the organic polyisocyanate is an aliphatic polyisocyanate or an alicyclic polyisocyanate. In claim 1 or claim 2,
The mixture (a1) is a (meth)acrylate mixture obtained by transesterifying glycerin or diglycerin and a compound having one (meth)acryloyl group in the presence of the following catalysts A curable composition that is a mixture of 20 to 300 mgKOH/g.
Catalyst One or more compounds selected.
Catalyst Y: Compound containing zinc. In claim 3,
A curable composition wherein the compound having one (meth)acryloyl group is an alkoxyalkyl (meth)acrylate. In claim 3,
The catalyst Curable composition. In claim 3,
A curable composition wherein the catalyst Y is an organic acid zinc or/and zinc diketone enolate. In claim 1 or claim 2,
(A) A curable composition in which the weight average molecular weight of the component is 500 to 10,000. In claim 1 or claim 2,
A curable composition further comprising the following component (B).
(B) Component: Compounds having ethylenically unsaturated groups other than component (A) An active energy ray-curable composition comprising the composition according to any one of claims 1 to 8. In claim 9,
An active energy ray-curable composition further comprising 0.1 to 10 parts by weight of a photopolymerization initiator based on 100 parts by weight of the total amount of component (A) or 100 parts by weight of the total amount of component (A) and component (B). An active energy ray-curable coating composition comprising the composition according to claim 9 or 10.