TW201610028A - Active-energy-ray-curable composition - Google Patents

Abstract

The purpose of the present invention is to provide an active-energy-ray-curable composition capable of improving surface curing properties and imparting flexibility without compromising the good adhesion to a substrate and surface hardness of a polyester (meth)acrylate. The present invention is an active-energy-ray-curable composition including components (A), (B), and (C) in a specific ratio. Component (A): a compound (A1) having two or more (meth)acryloyl groups obtained from a polyol in which 3-18 moles of ethylene oxide are added to dipentaerythritol, and/or a compound (A2) having two or more (meth)acryloyl groups obtained from a polyol in which 2-6 moles of ethylene oxide are added to pentaerythritol. Component (B): a reaction product of a polyhydric alcohol, a divalent carboxylic acid or an acid anhydride thereof, and (meth)acrylic acid. Component (C): a compound having one ethylenically unsaturated group and/or a compound other than component (A) and component (B) and having two or more ethylenically unsaturated groups.

Description

Active energy ray-hardening composition Field of invention

The present invention relates to an active energy ray-curable composition. The composition of the present invention has rapid curability, and the obtained cured film can have excellent surface hardness and flexibility, and can be suitably used as a coating agent.

Further, in the present specification, an acrylonitrile group and/or a methacryl fluorenyl group are shown as a (meth) acrylonitrile group, an acrylate and/or a methacrylate is a (meth) acrylate, and an acrylic acid is used. And/or methacrylic acid is shown as (meth)acrylic acid.

Background of the invention

In the active energy ray-curable coating composition, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hereinafter referred to as "DPHA") as a main component is known ( Patent Document 1). Since the cured film obtained from this composition is difficult to be scratched due to its high surface hardness, it is widely used for hard coat applications.

However, as long as the cured film of the composition has a problem that the film is greatly bent at the time of curing and the film is easily deformed, there is a problem that the film is easily broken and the film substrate to which the hard coat layer is applied is likely to be bent, cracked, or peeled off.

In addition to DPHA, it is used in various applications such as coating and coating. Polyester (meth) acrylate is known as one of polyfunctional (meth) acrylates. It is known that a polyester (meth) acrylate can be obtained by an esterification reaction of a polybasic acid or an anhydride thereof (hereinafter referred to as a polybasic acid (anhydride)), a polyhydric alcohol, and a (meth)acrylic acid, by combining these. In the constituent component, the volume shrinkage at the time of hardening can be controlled to be low, and further, the adhesion to the substrate can be further improved (Patent Document 2).

However, such a polyester (meth) acrylate is known to be easily hindered by hardening due to oxygen in the air, and once it is used as a main component of a coating or a coating agent, it is easy to harden due to insufficient hardenability. The problem of residual stickiness on the film surface.

Advanced technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. Hei 6-248008

Patent Document 2: Japanese Patent Laid-Open Publication No. 63-241016

Summary of invention

The present inventors have intensively studied to find the active energy ray-curable composition as follows: without impairing the good surface hardness of the polyester (meth) acrylate and the adhesion to the substrate, An active energy ray-curable composition which is soft and can improve surface hardenability.

In order to solve the above problems, the present inventors have found that the addition of 3 to 18 moles of ethylene oxide from dipentaerythritol is used in combination. a compound having a (meth) acrylonitrile group obtained by a diol and/or two or more (meth) propylene obtained from a polyol having 2 to 6 moles of ethylene oxide added to neopentyl alcohol a compound of a mercapto group, and a composition of a polyol, a divalent carboxylic acid or an anhydride thereof, and a reaction product (polyester (meth) acrylate) with (meth)acrylic acid, which has good surface hardenability and a cured film The present invention has been completed by being excellent in physical properties such as hardness and flexibility.

That is, the present invention relates to an active energy ray-curable coating composition which is a composition containing the following components (A), (B) and (C), and in (A), (B) and 100% by weight of the component C) contains 10 to 70% by weight of the component (A), 30 to 90% by weight of the component (B), and 0 to 30% by weight of the component (C).

(A) component: a compound (A1) having two or more (meth) acrylonitrile groups obtained by adding a polyol having 3 to 18 moles of ethylene oxide to diheptaerythritol, and/or from a compound (A2) having two or more (meth) acrylonitrile groups obtained by adding a polyol having 2 to 6 moles of ethylene oxide to pentaerythritol; (B) component: polyol, divalent carboxyl group An acid or an anhydride thereof, and a reaction product with (meth)acrylic acid; (C) component: a compound having one ethylenically unsaturated group, and/or a component (A) having two or more ethylenically unsaturated groups and B) Compounds other than the ingredients.

Hereinafter, the present invention will be described in detail.

According to the composition of the present invention, it has rapid curability, and the obtained cured film can have both surface hardness, flexibility, and adhesion.

Therefore, the composition of the present invention can be suitably used as a coating agent.

Form for implementing the invention

The present invention relates to an active energy ray-curable coating composition which is a composition containing the components (A), (B) and (C) and which is relative to the components (A), (B) and (C) 100 parts by weight of the total amount is contained in an amount of 10 to 70 parts by weight of the component (A), 30 to 90 parts by weight of the component (B), and 0 to 30 parts by weight of the component (C).

Hereinafter, the components (A) to (C), other components, and methods of use will be described.

1. (A) component

The component (A) is obtained by adding a polyol having 3 to 18 moles of ethylene oxide (hereinafter referred to simply as "polyol (1)") to dipentaerythritol, and having two or more (meth) groups. A propylene group-based compound (A1) (hereinafter referred to as "(A1) component"), and/or a polyol having 2 to 6 moles of ethylene oxide added to neopentyl alcohol (hereinafter referred to as "multiple" The compound (A2) having two or more (meth) acrylonitrile groups obtained by the alcohol (2)") (hereinafter referred to as "(A2) component").

The polyol (1) of the starting material compound in the component (A1) is a compound having 6 hydroxyl groups in one molecule, and is a compound having 3 to 18 moles of ethylene oxide added to diheptaerythritol, and is preferably For the addition of compounds with 4 to 12 moles of ethylene oxide.

In the case where the addition of ethylene oxide has a molar number of less than 3, the properties of the cured film become indistinguishable from DPHA and are operative due to high viscosity. There is a problem with handling and there is a problem in the softness of the cured film. On the other hand, in the case where the addition of ethylene oxide to the compound having a molar number of more than 18, the hardness of the cured film is reduced, and the performance as a coating agent may not be obtained.

The polyol (2) of the starting material compound in the component (A2) is a compound having four hydroxyl groups in one molecule, and is a compound in which 2 to 6 moles of ethylene oxide is added to pentaerythritol, and is preferably added. A compound of 3 to 5 moles of ethylene oxide.

In the case where the addition of ethylene oxide to the compound having a molar number of less than 2, the properties of the cured film become indistinguishable from the neopentyl glycol tetraacrylate (PETTA), and the composition becomes easy to crystallize, and therefore, in addition to the operation In addition to the decrease in properties, there is also a problem in the softness of the cured film. On the other hand, in the case where the addition of ethylene oxide to the compound having a molar number of more than 6, the hardness of the cured film is reduced, and the performance as a coating agent may not be obtained.

Further, in the case of the component (A1) or the component (A2), since the alkylene oxide adduct other than ethylene oxide has a slow curing rate, it tends to remain sticky on the surface of the cured film.

The hydroxyl group (1) of the component (A1) preferably has a hydroxyl group value of 290 to 820 mgKOH/g, and preferably 300 to 800 mgKOH/g.

The polyol (2) of the component (A2) preferably has a hydroxyl group value of 500 to 1,000 mgKOH/g, and preferably 600 to 900 mgKOH/g.

The component (A1) is a compound having two or more (meth) acrylonitrile groups, and is preferably a compound having 5 or 6 (meth) acrylonitrile groups.

The component (A1) is usually obtained as a mixture of a compound having a plurality of (meth)acrylonitrile groups, and the (meth)acrylonitrile group is preferably in the range of 115 to 270 g/eq.

The component (A1) is preferably a reaction of a polyol having 3 to 18 moles of ethylene oxide with (meth)acrylic acid added to diheptaerythritol.

The component (A2) is a compound having two or more (meth) acrylonitrile groups, and is preferably a compound having 3 or 4 (meth) acryl fluorenyl groups.

The component (A2) is usually obtained as a mixture of a compound having a plurality of (meth) acrylonitrile groups, and the (meth) acrylonitrile group is preferably in the range of from 108 to 180 g/eq.

Further, in the present invention, the (meth) acrylonitrile equivalent means the value obtained by measuring bromination.

1) Manufacturing method

The component (A) can be produced by a usual method, and specifically, a production method in which a polyol (1) or a polyol (2) is esterified with (meth)acrylic acid, and a plurality of components are used. The alcohol (1) or the polyol (2) is produced by a transesterification reaction or the like.

(1) Esterification reaction

The esterification reaction can be carried out according to a usual method, and a method of heating and stirring a polyol and (meth)acrylic acid in the presence of an acid catalyst.

In order to be the target (meth) acrylate, the ratio of (meth)acrylic acid can be adjusted with respect to the total hydroxyl group of the polyol, preferably 0.8 to 2.0 moles and preferably 1.0 to 1.4 moles. .

Examples of the acid catalyst include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and fluorinated boric acid; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid; and strongly acidic cationic ion exchange resins.

Relative to the molar number of alcoholic hydroxyl groups, the acid catalyst should be used in a proportion of 0.05 mol%~10 mol%.

The esterification reaction can be carried out in accordance with a usual method.

The reaction temperature can be appropriately set depending on the raw materials and purpose to be used, and it is preferably from 65 to 140 ° C and from 75 to 120 ° C from the viewpoint of shortening the reaction time and preventing polymerization. When the reaction temperature is 65 ° C or higher, the esterification reaction proceeds rapidly, and the decrease in the yield can be suppressed. On the other hand, by setting the reaction temperature to 140 ° C or lower, the (meth)acrylic acid can be inhibited or formed. Thermal polymerization of (meth) acrylate.

In the esterification reaction, it is preferred to promote dehydration by azeotroping the water formed in the esterification reaction with the organic solvent.

Suitable organic solvents include aromatic hydrocarbon compounds such as toluene, benzene, and xylene; aliphatic hydrocarbon compounds such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and trichloroethylene and tetra A chlorine-based hydrocarbon compound such as vinyl chloride; a ketone such as methyl ethyl ketone or the like.

The organic solvent is used in an amount of 10 to 75% by weight, and preferably 15 to 55% by weight, based on the total amount of the polyol and the (meth)acrylic acid.

The progress of the esterification reaction is judged as follows: the amount of water generated by the esterification reaction, that is, the amount of dehydration is monitored; the concentration of the acid in the reaction solution is analyzed; the composition of the product (meth) acrylate is analyzed, and it is confirmed whether The composition of the target.

In the esterification reaction, in order to suppress polymerization of the (meth)acrylic acid or the obtained (meth)acrylate of the raw material, a polymerization inhibitor is preferably used.

The polymerization inhibitor may be hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, tert-butylcatechol, phenolthiophene , N-nitrosodiphenylamine and copper salts.

Further, another effective method for suppressing polymerization is a reaction in an environment containing a gas containing oxygen, or a method in which a gas containing oxygen is introduced into a reaction liquid.

(2) transesterification reaction

The transesterification reaction may be carried out by a usual method, such as heating or stirring a polyol (1) or a polyol (2) with an alkyl (meth)acrylate in the presence of a catalyst.

The alkyl (meth)acrylate may be one having a carbon number of 8 or less, and preferably 4 or less.

Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, and methyl)acrylic acid. Hexyl ester, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like.

The catalyst is usually a user in the transesterification reaction, and examples thereof include a titanium catalyst, a tin catalyst, and sulfuric acid.

The catalyst is preferably used in an amount of from 0.05 mol% to 20 mol%, based on the moles of the alcoholic hydroxyl group.

In the transesterification reaction, since a (meth)acrylic acid alkyl ester having a high radical polymerizable property is used for the raw material, it is preferred to use a polymerization inhibitor in order to suppress polymerization during the transesterification reaction, and the same compound as mentioned above can be used. .

Further, another effective method for suppressing polymerization is a reaction in an environment containing a gas containing oxygen, or a method in which a gas containing oxygen is introduced into a reaction liquid.

In the transesterification reaction, by using the raw material (meth) propylene in excess The alkyl olefinate can be carried out without using a reaction solvent.

However, a solvent may be used for the purpose of effectively removing the alcohol to the outside of the system or uniformly dissolving the raw materials or products. At this time, it is preferred to use a reaction solvent which can azeotrope with the produced alcohol and dissolve the polyfunctional (meth) acrylate of the product. Examples of the reaction solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane; aliphatic hydrocarbons such as n-hexane and n-heptane; and methyl ethyl ketone and methyl isobutylene. Ketones and other ketones.

The transesterification reaction is preferably carried out by distilling off the produced alcohol to the outside of the system under reflux.

The reaction temperature depends on the formation of an alcohol or a raw material (meth)acrylic acid alkyl ester, a reaction solvent, etc., and is preferably adjusted to be higher than the boiling point of the resulting alcohol. The reaction temperature can be adjusted to some extent depending on the selection of the alkyl (meth) acrylate or the reaction solvent, and the pressure control (pressurization or depressurization). A suitable reaction temperature is 60 to 160 ° C, and preferably 80 to 150 ° C. When the reaction temperature is less than 60 ° C, the reaction rate is slow; if it exceeds 160 ° C, coloring or gelation is likely to occur.

2) Content ratio

In the total amount of 100% by weight of the components (A), (B) and (C) (hereinafter referred to as "curable component"), the content of the component (A) is 10 to 70% by weight, and preferably 15 ~60% by weight.

When the content ratio of the component (A) is less than 10% by weight, the curability is insufficient, and when it exceeds 70% by weight, the flexibility or adhesion to the substrate is insufficient.

2. (B) ingredients

The component (B) is a polyhydric alcohol, a divalent carboxylic acid or an anhydride thereof (hereinafter simply referred to as "two a carboxylic acid (anhydride)"), a reaction with (meth)acrylic acid. This compound is a compound which is commonly sold as a polyester (meth) acrylate.

1) Polyol

In the case of a polyhydric alcohol, various compounds can be used in the case of an alcohol having a valence of 2 or more.

The divalent alcohol may be ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3 - an aliphatic diol such as butylene glycol, neopentyl glycol, 1,4-butanediol or 1,6-hexanediol; hydrogenated bisphenol A, 1,2-cyclohexanediol, 1,3-ring Hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, dicyclohexyl-4,4'-diol, 2,6-decalinol and 2,7-ten An alicyclic diol such as hydrogenated naphthalenediol; an aromatic diol such as p-benzenedimethanol or the like.

The alcohol having a valence of 3 or more may, for example, be glycerin, trimethylolpropane, trimethylolethane, tris(2-hydroxyethyl) isocyanate, neopentyl alcohol, ditrimethylolpropane and Neopentyl alcohol and the like.

The alkylene oxide adducts of these compounds can be used in the case of polyols. Specific examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide.

In the present invention, when a polyol having an alkylene oxide is used, the alkylene oxide added per 1 equivalent of the polyol is preferably 20 moles or less, and the alkylene oxide is added per 1 mole of the polyol. The total amount should be below 40 mu. The obtained (meth) acrylate can be suppressed by setting the molar number of alkylene oxide to be less than 20 moles per 1 equivalent of the polyol, or 40 moles or less per 1 mole of the polyol. The viscosity is increased, and it is excellent in the water resistance of the cured product.

In terms of polyols, among the aforementioned compounds, alkylene glycol, dialkyl alkyl glycol, trimethylolpropane, neopentyl alcohol, and tris(2-hydroxyalkyl) isocyanurate are preferred. ester.

2) Divalent carboxylic acid (anhydride)

The divalent carboxylic acid (anhydride) may be an organic acid having two carboxyl groups per molecule or an acid anhydride thereof.

Specific examples of the compound include succinic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, citric acid, tetrahydrofurfuric acid, and hexahydrogen. Capric acid, hemic acid, and endo-chlorendic acid, and anhydrides of such compounds.

The divalent carboxylic acid (anhydride) is preferably a divalent carboxylic anhydride, and is preferably phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

3) Reaction ratio

The reaction ratio of the component (B), the polyol, the divalent carboxylic acid (anhydride), and the (meth)acrylic acid may be appropriately set according to the purpose.

As the component (B), various compounds ranging from a low molecular weight substance to a high molecular weight substance can be used, and a low molecular weight substance is preferably used.

When producing a low molecular weight substance, the following formula [1] is preferably satisfied.

1.1≦A/B and 0.5≦C/(TA-2B)[1]

However, the symbol in the formula [1] means the following.

A: Molar number of polyol, B: Molar number of divalent carboxylic acid (anhydride), C: Molar number of (meth)acrylic acid, T: Valence of polyhydric alcohol

By setting the above molar ratio A/B to 1.1 or more, it is possible to suppress the molecular weight of the reactant from becoming excessively large, and obtain a (meth) acrylate having a low viscosity. Suitable The upper limit of the molar ratio A/B is 5 or less, whereby the ratio of the reaction product composed of the two components of the polyol and the (meth)acrylic acid can be reduced, and the reactants resulting from the three components can be maintained, that is, Methyl) acrylate, excellent hardenability properties. The molar ratio A/B is preferably 4 or less.

The molar ratio A/B should be 1.1 to 2.2, and preferably 1.5 to 2.0.

By setting the above equivalent ratio C/(TA-2B) to 0.5 or more, excellent curability can be obtained from the obtained (meth) acrylate-containing composition. It is preferable to set the upper limit of the equivalent ratio C/(TA-2B) to 2 or less, whereby the unreacted (meth)acrylic acid in the reactant can be reduced, and in addition to being economical, the properties and hardening of the composition can be suppressed. The properties, the physical properties of the obtained cured product, and the like have a bad influence.

The equivalent ratio C/(TA-2B) is preferably 0.9 to 1.5, and preferably 1.0 to 1.5.

When the ratio of each raw material is reacted under the conditions of the above formula [1], the component (B) having a low viscosity and a low molecular weight substance can be easily obtained. The component (B) preferably has an average molecular weight of from 500 to 3,000.

Further, the component (B) is preferably a compound having a repeating unit number of 1 to 50 of a polyhydric alcohol and a divalent carboxylic acid (anhydride).

The number of repeating units can be calculated from the respective elution times of the peaks showing the molecular weight distribution obtained by gel permeation chromatography (hereinafter abbreviated as "GPC"). That is, it can be determined by the following measurement method: the molecular weight of the polyol (dicarboxylic acid), the divalent carboxylic acid (anhydride), and the terminal (meth)acrylic acid at the terminal are assigned, and the corresponding conversion is calculated from the standard curve. The molecular weight of each dissolution time was used to calculate the number of repeating units.

4) Manufacturing method

There is no particular limitation on the order in which the above respective raw materials are reacted. If the polyol is reacted with a divalent carboxylic acid (anhydride), then (meth)acrylic acid is reacted, or the polyol is reacted with (meth)acrylic acid, and then the divalent carboxylic acid (anhydride) is reacted. A two-stage reaction; or a method in which each raw material is reacted together in a one-stage reaction.

The two-stage reaction is preferable because it can obtain a low molecular weight distribution and a low viscosity (B) component in a high yield; on the other hand, the one-stage reaction has a small number of steps, and the feature can be obtained at a low cost. It is appropriate. Further, in the two-stage reaction, since the reaction is easily controlled, it is preferred to react the polyol with a divalent carboxylic acid (anhydride) and then react the (meth)acrylic acid.

In the case of producing the component (B), the above conditions for the molar ratio and the equivalent ratio of each raw material used in the present invention may be satisfied, and the reaction temperature and the reaction time are not particularly limited.

The esterification reaction of the polyhydric alcohol with the divalent carboxylic acid (anhydride) is preferably carried out at a temperature of 50 to 300 ° C and preferably at a temperature of 70 to 250 ° C; when reacting the (meth)acrylic acid, in order to suppress ( The polymerization of methyl)acrylic acid is preferably carried out at a slightly lower temperature than the esterification reaction, and it is usually carried out at a temperature of about 50 to 130 ° C and at a temperature of about 65 to 110 ° C. The suitable reaction temperature for the one-stage reaction is the temperature at which the (meth)acrylic acid is reacted. The progress of the esterification reaction can be judged by the amount of water distilled from the reaction system, and if a predetermined amount of water is distilled off, the reaction can be terminated.

An acid catalyst can be used in the esterification reaction, and the same compounds as described above can be used.

Acid reminder relative to the acid component of divalent carboxylic acid (anhydride) and/or (meth)acrylic acid The ratio of the chemical agent is preferably from 0.1 to 20 mol%, and preferably from 1 to 7 mol%.

In the esterification reaction, it is preferred to carry out the reaction in the presence of a polymerization inhibitor, and the same compounds as mentioned above can be mentioned. Further, in the same manner as described above, it is possible to react in an atmosphere containing oxygen gas, or to introduce a gas containing oxygen into the reaction liquid.

Further, in the esterification reaction, an organic solvent is preferably used to azeotropically dehydrate the produced water, and the same compounds as described above may be mentioned.

5) Content ratio

The content of the component (B) is preferably 30 to 90% by weight, and preferably 40 to 85% by weight, based on 100% by weight of the total amount of the curable component.

When the content of the component (B) is less than 30% by weight, the surface hardness is reduced. When it exceeds 90% by weight, the cured film becomes brittle and the surface hardenability is reduced.

3. (C) ingredients

In the composition of the present invention, the components (A) and (B) are essential components, and the composition may be blended as needed for the purpose of lowering the viscosity of the composition or improving the adhesion of the cured product. The component C), that is, a compound having one ethylenically unsaturated group and/or a compound other than the component (A) and the component (B) having two or more ethylenically unsaturated groups.

The ethylenically unsaturated group may, for example, be a vinyl group or a (meth) acrylonitrile group.

Hereinafter, a compound having one ethylenically unsaturated group (hereinafter referred to as "monofunctional unsaturated compound") and having two or more ethylenic unsaturations will be described. The compound other than the component (A) and the component (B) (hereinafter referred to as "polyfunctional unsaturated compound") will be described.

1) Monofunctional unsaturated compounds

Examples of the monofunctional unsaturated compound include a (meth) acrylate group (meth) acrylate (hereinafter referred to as "monofunctional (meth) acrylate"), and one (meth) group. A (meth) acrylamide compound (hereinafter referred to as "monofunctional (meth) acrylamide)" which is an acrylonitrile group.

Specific examples of the monofunctional (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (methyl). Amyl acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, etc. Alkyl ester; cyclohexyl (meth)acrylate, isodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, bicyclo(meth)acrylate Monofunctional (meth) acrylate having an alicyclic group such as pentamoxyethyl ester or dicyclopentenyloxyethyl (meth)acrylate; glycidyl (meth)acrylate, (methyl) Tetrahydrofuran methyl acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclohexane spiro-2-(meth)acrylate a monofunctional (meth) acrylate having a cyclic ether group such as 1,3-dioxolan-4-yl)methyl ester or 3-ethyl-3-oxetanylmethyl (meth)acrylate; Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylate Aromatic monofunctional (meth) acrylate such as phenylphenoxy ester and (p-cumylphenol) vinyl ester; oxyethyl hexahydro imidate (meth) acrylate Monofunctional (meth) acrylate having a maleimine group; (meth) acrylonitrile group Alkoxyalkyl ester; (meth)acrylic acid ethyl carbitol ester, 2-ethylhexyl carbitol (meth) acrylate, etc. Monofunctional (meth) acrylate; 3-(meth) propylene methoxy propyl methyl dimethoxy decane, 3-(methyl) propylene methoxy propyl trimethoxy decane and 3- (a) An alkoxy group-containing monofunctional (meth) acrylate such as propylene methoxy propyl methyl diethoxy decane or 3-(methyl) propylene oxy propyl triethoxy decane.

Specific examples of the monofunctional (meth) acrylamide compound are N-methyl (meth) acrylamide, N-n-propyl (meth) acrylamide, and N-isopropyl (methyl). Acrylamide, N-n-butyl (meth) acrylamide, N-second butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-n-hexyl ( N-alkyl (meth) acrylamide such as methyl 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) decylamine, N , N-diethyl (meth) acrylamide, N,N-di-n-propyl (meth) acrylamide, N,N-diisopropyl (meth) acrylamide, N, N N-N-dialkyl (meth) acrylamide such as di-n-butyl (meth) acrylamide and N,N-dihexyl (meth) acrylamide.

In the case of the component (C), it is preferred that the compound having a hydrophilic group can further improve the adhesion to the substrate.

When a compound having a hydroxyl group as a hydrophilic group is used, it is preferably a monofunctional (meth) acrylate having a hydroxyl group and a (meth) acrylamide containing a hydroxyl group.

The monofunctional (meth) acrylate having a hydroxyl group may, for example, be a hydroxyl group of (meth)acrylic acid such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate or hydroxybutyl (meth)acrylate. Alkyl esters and the like.

The (meth) acrylamide containing a hydroxyl group may, for example, be N-hydroxyethyl(meth)acrylamide or the like.

In the case of using a compound having an acidic group as a hydrophilic group, (meth)acrylic acid; ω-carboxy-polycaprolactone mono(meth)acrylate; monohydroxyethyl citrate (methyl) A compound containing a carboxyl group or a (meth)acryl fluorenyl group such as an acrylate; a (meth) acrylate containing a phosphate group such as an esterified product of phosphoric acid and (meth)acrylic acid.

When the component (C) is a compound having an acidic group as a hydrophilic group, the ratio of the curable component is preferably 0.0001 to 20% by weight, and preferably 0.001 to 5% by weight.

2) Polyfunctional unsaturated compounds

Examples of the polyfunctional unsaturated compound include a compound having two or more (meth) acrylonitrile groups (hereinafter referred to as "polyfunctional (meth) acrylate)".

Among the polyfunctional (meth) acrylates, compounds having two (meth) acrylonitrile groups include ethylene di(meth)acrylate and 1,6-hexane di(meth)acrylate. a di(meth)acrylate of an aliphatic diol such as a diol ester and a decyl glycol di(meth)acrylate or a neopentyl glycol di(meth)acrylate; Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, di(methyl) a di(meth)acrylic acid polyalkylene glycol ester such as tripropylene glycol acrylate or polypropylene glycol di(meth)acrylate; glycerol di(meth)acrylate; trimethylolpropane di(meth)acrylate Di(meth)acrylic acid such as ester, neopentyl alcohol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, and dipentaerythritol di(meth)acrylate Polyol ester; bis(meth) acrylate of glycerol alkylene oxide adduct, di(meth) acrylate of neopentyl alcohol alkylene oxide adduct [except for (A) component], bishydroxyl Poly(alkylene oxide) such as di(meth)acrylate of a propane alkylene oxide adduct and di(meth)acrylate of an adgen adduct of dipentaerythritol (except for (A)) Di(meth)acrylate of the product; di(meth)acrylate of an isomeric cyanide alkylene oxide adduct; a pentaerythritol di(meth)acrylate and an amine group of an organic polyisocyanate Acid ester Di(meth) acrylate of an alicyclic diol such as tricyclodecane dihydroxymethyl (meth) acrylate; di(methyl) epoxide alkane adduct of bisphenol A A di(meth)acrylate such as an alkylene oxide adduct of a bisphenol compound such as a di(meth)acrylate of an acrylate or an alkylene oxide adduct of bisphenol F.

Further, examples of the alkylene oxide adducts include ethylene oxide adducts and propylene oxide adducts, and ethylene oxide and propylene oxide adducts.

Examples of the compound having three or more (meth)acryl fluorenyl groups include glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and tris or tetramethylpentaerythritol. Poly(meth)acrylic acid polyol esters such as acrylate, tris or tetramethyl (meth) acrylate of ditrimethylolpropane and tris, tetra, penta or hexa (meth) acrylate of dipentaerythritol Tris(meth)acrylate of glycerol alkylene oxide adduct, tris or tetra(meth)acrylate of neopentyl alcohol alkylene oxide adduct [except for (A) component), ditrimethylol Three, four, five or six (meth) acrylates of the propane alkylene oxide adducts of three or four (meth) acrylates and dipentaerythritol alkylene oxide additions (except for the (A) component) Poly(meth)acrylate of a polyol alkylene oxide adduct; tris(meth)acrylate of an isomeric cyanide alkylene oxide adduct; and pentaerythritol tris(meth)acrylate A urethane (meth) acrylate having a hydroxyl group and a reaction product of a compound having three or more (meth) acrylonitrile groups and an organic polyisocyanate.

In the above, examples of the alkylene oxide adducts include ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts.

Further, the organic polyisocyanate may be benzyl methylene diisocyanate, 1,6-hexane diisocyanate, 4,4'-diphenylmethane diisocyanate or polyisocyanate. Polyphenylene ester, 1,6-hexane diisocyanate 3, hydrogenated benzylidene diisocyanate, 4,4'-diphenylmethane diisocyanate, diisocyanate Terephthalic acid ester, hydrogenated terephthalate diisocyanate, p-phenylene diisocyanate, benzylimene diisocyanate 2, 1,5-naphthyl diisocyanate, Addition of hexamethylene isocyanate, 4,4'-dicyclohexylmethane diisocyanate, trimethylolpropane tris(phenylene diisocyanate) adduct and diisocyanate Acid isophorone Ester and the like.

An oligomer may also be used for the polyfunctional (meth) acrylate, and a diol, an organic polyisocyanate, and a reactant of a hydroxyl group-containing (meth) acrylate, that is, a urethane (meth) acrylate, may be used. And epoxy (meth) acrylate and the like.

3) Suitable compounds

Among the compounds, the monofunctional (meth) acrylate is preferably tetramethylfuran methyl (meth) acrylate, phenoxyethyl (meth) acrylate and isodecyl (meth) acrylate; The acrylate is preferably hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate; trifunctional or higher (meth) acrylate It is preferably pentaerythritol penta(meth)acrylate, dineopentaerythritol hexa(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetrakis(meth)acrylate. Ester, trimethylolpropane tris(meth)acrylate, tris(meth)acrylate of trimethylolpropane alkylene oxide adduct, neopentyl glycol tri(meth)acrylate and organic polymerization The urethane (meth) acrylate of the isocyanate reactant.

4) Content ratio

In the total amount of the curable components, 100% by weight, the content of (C) is 0 to 30% by weight, and preferably 0.5 to 20% by weight.

When the content ratio of the component (C) exceeds 30% by weight, the hardness of the coating film may become insufficient.

4. Other ingredients

The composition of the present invention contains the components (A) and (B) as essential components and, if necessary, the component (C). However, depending on the purpose and use, it can be blended and used as a paint ‧ primer A wide variety of ingredients for the coating.

Suitable components include a photoradical polymerization initiator (hereinafter referred to as "(D) component"), an antioxidant, an ultraviolet absorber, a pigment ‧ dye, a leveling agent, and a decane coupling agent.

The components will be specifically described below.

Further, the specific compounds listed in the description of the other components may be used singly or in combination of two or more kinds.

1) (D) component

The component (D) is a photoradical polymerization initiator.

The component (D) is a compound which generates a radical by irradiation of an active energy ray and starts polymerization of a compound having an ethylenically unsaturated group. When the active energy ray is an electron beam, it is not necessary to blend the component (D).

Specific examples of the component (D) include benzyldimethylketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 1-hydroxyl group. Cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl -1-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone, 2-hydroxy-1-{4-[4- (2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)]phenyl ]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butane-1 -ketone, 3,6-bis(2-methyl-2- Anionic ketone compound such as -9-n-octylcarbazole, methyl phenylglyoxylate, ethyl hydrazine, and phenanthrenequinone; diphenyl ketone, 2-methyldiphenyl ketone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2,4,6-trimethyldiphenyl ketone, 4-phenyldiphenyl ketone, 4-(methylphenylthio) Phenylphenylmethane, methyl-2-diphenyl ketone, 1-[4-(4-benzylidenylphenylthio)phenyl]-2-methyl-2-(4-methyl Phenylsulfonyl)propan-1-one, 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone and 4- a diphenyl ketone compound such as methoxy-4 ' -dimethylaminodiphenyl ketone; bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 2,4,6 -trimethylbenzimidyldiphenylphosphine oxide, ethyl(2,4,6-trimethylbenzylidene)phenylphosphonate and bis(2,6-dimethoxybenzamide) Sulfhydryl phosphine compound such as -2,4,4-trimethylpentylphosphine oxide; oxygen sulfur 2-chlorooxosulfur 2,4-diethyloxysulfide Isopropyl oxysulfide 1-chloro-4-propyl oxysulfide , 3-[3,4-dimethyl-9-sideoxy-9H-oxygen sulfide -2-yloxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride and fluorosulfur Oxygen and sulfur A compound or the like.

Among these compounds, the α-hydroxyphenyl ketone is preferably coated on the film even under the atmosphere, and the surface hardenability is good, specifically 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl Phen-1-phenyl-propan-1-one is preferred.

In addition, when it is necessary to increase the thickness of the cured film, for example, if it is 50 μm or more, in order to improve the hardenability inside the cured film, or when a UV absorber or a pigment is used in combination, And bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, ethyl-(2,4,6 -Trimethylbenzhydryl)phenylphosphonate and fluorenylphosphine oxide compounds such as bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide , or 2-methyl-1-[4-(methylthio)]phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-dimethylamino-2-( 4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)butan-1-one and the like.

The content of the component (D) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, even more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total amount of the curable component. When the ratio of the component (D) is 0.01 parts by weight or more, the photocurability of the composition is good, and the adhesiveness is excellent, and when it is 20 parts by weight or less, the cured film can be hardened internally. Good in properties, and good adhesion to the substrate.

2) Antioxidants

The antioxidant is blended to improve the durability of the cured film such as heat resistance and weather resistance.

The antioxidant may, for example, be a phenol-based antioxidant, a phosphorus-based antioxidant, or a sulfur-based antioxidant.

The phenolic antioxidant may, for example, be a hindered phenol such as di-tert-butylhydroxytoluene. The marketer can AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, etc. made by ADEKA.

The phosphorus-based antioxidant may, for example, be a phosphine such as a trialkylphosphine or a triarylphosphine, or a trialkyl phosphite or a triaryl phosphite. Commercial products of such derivatives include, for example, ADEKA, ADEKA STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A. , 3010, etc.

The sulfur-based antioxidant may be a thioether-based compound, and the commercially available product may be AO-23, AO-412S or AO-503A manufactured by ADEKA.

These may be used in one type or in two or more types. A suitable combination of these antioxidants may be a combination of a phenolic antioxidant and a phosphorus-based antioxidant, and a phenolic antioxidant and a sulfur-based antioxidant.

The blending ratio of the antioxidant may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, and preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of the curable component.

When the blending ratio is 0.1 part by weight or more, the durability of the composition can be improved. On the other hand, when it is 5 parts by weight or less, the hardenability or the adhesion can be improved.

3) UV absorber

The ultraviolet absorber is used to blend the light resistance of the cured film.

UV absorbers can be made by BASF company TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN479, etc. UV absorption 剤, or benzotriazole UV absorbers such as TINUVIN900, TINUVIN928, TINUVIN1130.

The blending ratio of the ultraviolet absorber may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, and preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of the curable component. When the blending ratio is 0.01% by weight or more, the cured film can be made into a light-resistant property. On the other hand, when it is contained in an amount of 5% by weight or less, it is excellent in the curability of the composition.

4) Pigments ‧ Dyes

The pigments may, for example, be organic pigments and inorganic pigments.

Specific examples of the organic pigment include insoluble azo pigments such as toluidine red, toluidine chestnut, Hansa yellow, benzidine yellow, and pyrazole ruthenium; Lisuo red, Helio Bordeaux, pigment scarlet, and permanent red 2B. Isotropic azo pigments; derivatives derived from anthraquinone dyes such as alizarin, indanthrone and sulforaphane; anthocyanin-based organic pigments such as anthraquinone blue and anthraquinone green; quinacridone red and quinolin Quinacridone organic pigments such as acridone fuchsin; anthraquinone organic pigments such as ruthenium and anthraquinone; isoporphyrin organic pigments such as isoporphyrin yellow and isoindoline orange; Pipione orange and other skin ketone organic pigments; thioindole organic pigments; condensed azo organic pigments; benzimidazolone organic pigments; quinophthalone yellow and other quinophthalone organic pigments; isoporphyrin yellow Isoisoporphyrin-based organic pigments; and other pigments: flavanone yellow, mercaptophthalamide yellow, nickel azo yellow, copper azomethine yellow, perinone orange, onion ketone orange, Two blush and two Purple and so on.

Further, specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, indigo, and oxidation. Chrome green, cobalt green, amber, titanium black and synthetic iron black. Further, the carbon black exemplified by the aforementioned filler can also be used as an inorganic pigment.

As the dye, various compounds known from the past can be used.

5) Leveling agent

An anthrone-based leveling agent, a fluorine-based leveling agent, and the like can be used, and various commercially available leveling agents can be used.

6) decane coupling agent

The decane coupling agent is blended to improve the interfacial adhesion strength between the cured film and the substrate.

If the decane coupling agent helps to improve the adhesion to the substrate, there is no special limit. A well-known decane coupling agent can be used.

Specific examples of the decane coupling agent include 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, and 3-glycidoxypropylmethyl. Diethoxydecane, 3-glycidoxypropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2- (Aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxy Decane, 3-aminopropyltriethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyl Trimethoxy decane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like.

The blending ratio of the decane coupling agent may be appropriately set according to the purpose, and is preferably 0.1 to 10 parts by weight, and preferably 1 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable component.

By setting the blending ratio to 0.1 part by weight or more, the adhesion of the composition can be increased. On the other hand, by setting it to 10 parts by weight or less, the temporal change of the bonding force can be prevented.

7) Other ingredients than the foregoing

In addition to the foregoing, the composition of the present invention may be blended with various ingredients as a coating agent.

For example, the composition of the present invention is preferably used as a solventless type composition, and an organic solvent may be blended as needed.

Specific examples of suitable solvents include alcohols such as ethanol and isopropanol; alkyl glycol monoethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetols such as diacetone alcohol; and aromatic compounds such as toluene and xylene. Propylene glycol monomethyl ether acetate, An ester such as ethyl acetate or butyl acetate; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; an ether such as dibutyl ether; and N-methylpyrrolidone.

5. Active energy ray hardening composition

The present invention relates to an active energy ray-curable composition containing the components (A) and (B) as essential components and preferably containing the component (C).

The manufacturing method of the composition can be produced by mixing and mixing the components (A) and (B), and the components (C) and other components as needed, according to a usual method.

The viscosity of the composition may be appropriately set according to the purpose, and is preferably 500 to 50,000 mPa‧s.

Further, the viscosity in the present invention means a value measured at 25 ° C using an E-type viscometer.

The composition of the present invention can be used in various applications, and examples thereof include a coating agent, an ink, an adhesive, and a molding material.

As described above, the composition of the present invention can be used as a coating agent by utilizing the characteristics that the cured product is excellent in hardness, flexibility, and adhesion.

The coating agent can be used in various applications, such as paints for woodworking, paints for top coating such as mortars and slates, and waterproof coatings for printed substrates constituting electronic circuits. .

Specific examples of the coating agent can be applied to the back surface of a disc such as a CD or a DVD, the application of a mobile phone body, and the coating of an automobile headlight. Moreover, it is useful as a molding material, and a transparent acrylic plate, a material for liquid crystal, etc. are mentioned.

6. How to use

The method of using the composition of the present invention may be carried out according to a usual method.

For example, a method in which a composition is applied to a substrate and then irradiated with an active energy ray is used.

Further, a method in which a photopolymerization initiator and a thermal polymerization initiator are used in combination with a composition, and the active energy ray is irradiated to the active energy ray to heat and harden it, thereby improving the adhesion to the substrate.

The substrate to which the composition of the present invention is applicable can be applied to a wide variety of materials, such as plastic, wood, metal, inorganic materials, and paper.

Specific examples of the plastic include polymethyl methacrylate, polyethylene terephthalate, polyvinyl chloride, polycarbonate, epoxy resin, and polyurethane resin.

Wood can be used for natural wood and synthetic wood.

Inorganic materials can be used for plaster, cement, glass and stone.

Among the substrates, the composition of the present invention can be suitably used on a plastic substrate.

The coating method of the composition of the present invention on the substrate may be carried out according to a usual method.

For example, bar coating, roll coating, spin coating, dip coating, gravure coating, flow coating, and spray coating may be mentioned.

The active energy ray for curing the composition of the present invention may be ultraviolet rays, visible rays, electron beams or the like, and is preferably ultraviolet rays.

The ultraviolet irradiation device may be a high pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, or an LED.

The irradiation energy is appropriately set according to the type of the active energy ray or the blending composition. If a high-pressure mercury lamp is used as an example, the irradiation energy in the UV-A range is preferably 100 to 5,000 mJ/cm ² and 200 to 1,000. mJ/cm ^{2 is} preferred.

Example

The examples and comparative examples are shown below to more specifically illustrate the present invention.

In addition, the following "parts" means parts by weight, and "%" means % by weight.

Further, the following ethylene oxide is abbreviated as "EO" and propylene oxide is abbreviated as "PO". Further, the acryl oxime equivalent in the production example is based on the value obtained by measuring the bromine valence of the obtained acrylate.

Manufacturing example

1) Production Example 1 (Production of acrylate of dipentaerythritol EO6 molar addition product)

In a four-necked flask equipped with a 3 L side tube of a reflux tube, 600 g of dipentaerythritol EO6 molar addition product (made by Aoki Oil & Fats Co., Ltd., BLAUNON DPE-E6R, hydroxyl group 643 mgKOH/g) was charged. 600 g of acrylic acid (ratio to 1.21 moles relative to total hydroxyl 1 mol in alcohol), 39 g of 70% methanesulfonic acid (hereinafter referred to as "MSA"), 3 g of copper (II) chloride, and 540 g of toluene.

An oxygen-containing gas (oxygen 5% by volume, nitrogen 95% by volume) was blown into the flask while heating and stirring at a temperature of the reaction solution of 85 to 95 °C. While the reaction was being carried out, the resulting water was taken out of the system by a Dean Stark tube, and a dehydration esterification reaction was carried out for 5 hours.

After the reaction was completed, 900 g of toluene was added to dilute. Further, 240 g of distilled water was added and stirred, and the lower layer was removed after standing. Next, 400 g of a 20% aqueous sodium hydroxide solution was added under stirring and stirred well, and the lower layer was removed after standing. Next, add 240g of distillation to the organic phase with stirring. The water was stirred and the lower layer was removed on standing. The upper organic phase was heated under reduced pressure to distill off toluene.

The obtained acrylate was 930 g (yield 93%), the viscosity was 450 mPa s (25 ° C), and the propylene oxime equivalent was 148 g/eq. Hereinafter referred to as "DPET6EO".

2) Production Example 2 (Production of acrylate of dipentaerythritol EO5 molar addition product)

In a four-necked flask equipped with a 3 L side tube of a reflux tube, 600 g of dipentaerythritol EO5 molar addition product (made by Aoki Oil & Fats Co., Ltd., BLAUNON DPE-E5, hydroxyl group 716 mgKOH/g) was charged. 640 g of acrylic acid, 20 g of MSA, 2 g of copper (II) chloride and 530 g of toluene.

The same oxygen-containing gas as in Example 1 was blown while being heated and stirred at a temperature of the reaction solution of 85 to 95 ° C, and the generated water was removed to the outside of the system for 6 hours in the same manner as in Production Example 1. Dehydration esterification reaction.

After completion of the reaction, the same treatment as in Example 1 was carried out to separate the organic phase, and the mixture was heated under reduced pressure to distill off toluene.

The obtained acrylate was 964 g (yield 95%), the viscosity was 550 mPa s (25 ° C), and the propylene oxime equivalent was 138 g/eq. Hereinafter referred to as "DPET5EO".

3) Production Example 3 (Production of acrylate of dipentaerythritol EO4 molar addition)

In a four-necked flask equipped with a 3 L side tube of a reflux tube, 600 g of dipentaerythritol EO4 molar addition product (made by Aoki Oil & Fats Co., Ltd., BLAUNON DPE-E4, hydroxyl group 782 mgKOH/g) was charged. 698 g of acrylic acid, 20 g of MSA, 2 g of copper (II) chloride and 560 g of toluene.

While blowing the same oxygen-containing gas as in Example 1, while at the temperature of the reaction solution The mixture was heated and stirred at 85 to 95 ° C, and the resulting water was removed to the outside of the system in the same manner as in Production Example 1, and subjected to a dehydration esterification reaction for 6 hours.

After completion of the reaction, the same treatment as in Example 1 was carried out to separate the organic phase, and the mixture was heated under reduced pressure to distill off toluene.

The obtained acrylate was 989 g (yield 94%), the viscosity was 650 mPa s (25 ° C), and the propylene oxime equivalent was 130 g/eq. Hereinafter referred to as "DPET4EO".

4) Production Example 4 (Production of acrylate of dipentaerythritol EO12 molar addition)

In a four-necked flask equipped with a 3 L side tube of a reflux tube, 760 g of dipentaerythritol EO12 molar addition product (made by Aoki Oil & Fats Co., Ltd., BLAUNON DPE-E12R, hydroxyl group 423 mgKOH/g) was charged. 480 g of acrylic acid (relative to the total hydroxyl 1 mol in the alcohol, in a ratio of 1.16 mol), 20 g of MSA, 2 g of copper (II) chloride and 540 g of toluene.

The same oxygen-containing gas as in Example 1 was blown while being heated and stirred at a temperature of the reaction solution of 85 to 95 ° C, and the generated water was removed to the outside of the system for 6 hours in the same manner as in Production Example 1. Dehydration esterification reaction.

After completion of the reaction, the same treatment as in Example 1 was carried out to separate the organic phase, and the mixture was heated under reduced pressure to distill off toluene.

The obtained acrylate was 1003 g (yield 93%), the viscosity was 380 mPa s (25 ° C), and the acryl oxime equivalent was 207 g/eq. Hereinafter referred to as "acrylate 12EO".

5) Production Example 5 (Synthetic acrylic pentaerythritol 2EO addition ester)

In a four-necked flask equipped with a 2 L side tube of a reflux tube, 430 g of a neopentyl alcohol 2EO adduct (hydroxyl 992 mg KOH/g) and 660 g of acrylic acid were charged. (70% of methanesulfonic acid (hereinafter referred to as MSA), 2 g of hydroquinone monomethyl ether (hereinafter referred to as MEHQ), and 480 g of toluene (1.20 moles relative to the total hydroxyl group of the alcohol). An oxygen-containing gas (oxygen 5% by volume, nitrogen 95% by volume) was blown into the flask while heating and stirring at a temperature of the reaction solution of 82 to 97 °C. While the reaction was being carried out, the resulting water was taken out of the system by a Dean-Stark tube, and a dehydration esterification reaction was carried out for 5 hours.

After the reaction was completed, 1000 g of toluene was added to dilute. 600 g of a 20% aqueous sodium hydroxide solution was added under stirring and stirred well, and the lower layer was removed after standing. Next, 250 g of distilled water was added to the organic phase with stirring and stirred, and the lower layer was removed after standing. The upper organic phase was heated under reduced pressure to distill off toluene.

The obtained acrylate was 840 g (yield 84%), the viscosity was 166 mPa s (25 ° C), and the acryl oxime equivalent was 132 g/eq. Hereinafter referred to as "PET2EO".

6) Production Example 6 (Synthetic acrylic pentaerythritol 4EO addition ester)

In a four-necked flask equipped with a 1 L side tube of a reflux tube, 520 g of a neopentyl alcohol 4EO adduct (hydroxyl price: 717 mgKOH/g) and 570 g of acrylic acid (relative to the total hydroxyl group of the alcohol in the alcohol, 1.20) were charged. Moire ratio), 25 g of MSA, 2 g of copper (II) chloride, 0.2 g of MEHQ, 480 g of toluene.

While blowing the same oxygen-containing gas as in Example 1, the mixture was heated and stirred at a temperature of the reaction solution of 82 to 97 °C.

The resulting water was removed from the Dean-Stark tube to the outside of the system for 6 hours of dehydration esterification.

After the reaction was completed, 1050 g of toluene was added to dilute. Further, 250 g of distilled water was added and stirred, and the lower layer was removed after standing. Then, add it under stirring 360 g of 20% aqueous sodium hydroxide solution was added and stirred well, and the lower layer was removed after standing. Next, 250 g of distilled water was added to the organic phase with stirring and stirred, and the lower layer was removed after standing. The upper organic phase was heated under reduced pressure to distill off toluene.

The obtained acrylate was 830 g (yield 95%), the viscosity was 145 mPa s (25 ° C), and the acryl oxime equivalent was 158 g/eq. Hereinafter referred to as "PET4EO".

7) Comparative Production Example 1 (Production of acrylate of dipentaerythritol PO6 molar addition product)

Into a four-necked flask equipped with a 3 L side tube of a reflux tube, 660 g of p-rhinotetraol was added to a PO6 molar addition product (available from Aoki Oil & Fats Co., Ltd., BLAUNON DPE-360R, and a hydroxyl group of 565 mgKOH/g). 570 g of acrylic acid (relative to the total hydroxyl 1 mol in the alcohol, a ratio of 1.19 moles), 36 g of MSA, 3 g of copper (II) chloride and 540 g of toluene.

While blowing the same oxygen-containing gas as in Example 1, the mixture was heated and stirred at a temperature of the reaction solution of 85 to 95 °C.

The dehydrated esterification reaction was carried out for 8 hours while removing the generated water to the outside of the system in the same manner as in Production Example 1.

After completion of the reaction, the same treatment as in Example 1 was carried out to separate the organic phase, and the mixture was heated under reduced pressure to distill off toluene.

The obtained acrylate was 970 g (yield 96%), viscosity was 800 mPa ‧ (25 ° C), and propylene oxime equivalent was 320 g/eq. Hereinafter referred to as "DPET6PO"

7) Comparative Production Example 2 (Production of acrylate of dipentaerythritol EO24 molar addition product)

In a four-necked flask equipped with a 3L side tube with a return tube, 895g was charged. Dipentaerythritol EO24 Moer Additive (Aoki Oil Industry Co., Ltd., BLAUNON DPE-E24R, hydroxyl price 260 mgKOH/g), 340 g of acrylic acid (relative to the total hydroxyl 1 molar in the alcohol, 1.14 Mo The ratio of ears), 22 g of MSA, 1 g of copper (II) chloride and 540 g of toluene.

While blowing the same oxygen-containing gas as in Example 1, the mixture was heated and stirred at a temperature of the reaction solution of 85 to 95 °C.

The resulting water was removed to the outside of the system in the same manner as in Production Example 1, and a dehydration esterification reaction was carried out for 7 hours.

After completion of the reaction, the same treatment as in Example 1 was carried out to separate the organic phase, and the mixture was heated under reduced pressure to distill off toluene.

The obtained acrylate was 1005 g (yield 90%), the viscosity was 400 mPa s (25 ° C), and the propylene oxime equivalent was 166 g/eq. Hereinafter referred to as "DPET24EO".

8) Production Example 7 [Production of (B) component]

In a four-necked flask equipped with a 3 L side tube with a reflux tube, 164 parts of hexahydrohydrous citric acid, 235 parts of trimethylolpropane, 250 parts of acrylic acid, 20 parts of p-toluenesulfonic acid, and 0.2 parts of 4-methoxyl were mixed. Phenol and 780 g of toluene were heated and stirred at a reaction liquid temperature of 82 to 97 ° C while blowing an oxygen-containing gas (oxygen 5 vol%, nitrogen 95 vol%) into the flask. While the reaction was being carried out, the resulting water was taken out of the system by a Dean-Stark tube, and a dehydration esterification reaction was carried out for 5 hours.

After the reaction was completed, 1000 g of toluene was added to dilute. 600 g of a 20% aqueous sodium hydroxide solution was added under stirring and stirred well, and the lower layer was removed after standing. Next, 250 g of distilled water was added to the organic phase with stirring and stirred, and the lower layer was removed after standing. The upper organic phase was heated under reduced pressure to distill off toluene.

The obtained acrylate was 630 g (yield 96%) and had a viscosity of 35,000 mPa s (50 ° C). Hereinafter referred to as "PEA1".

The respective elution times of the peaks showing the molecular weight distribution were measured by PEA1, and each of the above elution times was obtained by using GPC (column: Styragel HR 4ETHF and Styragel HR 1THF, and a solution of THF: THF).

The molecular weight corresponding to each elution time converted from the standard curve is distributed according to the molecular weight of the constituent components of trimethylolpropane, hexahydroanhydroxamic acid, and the acrylic acid added to the terminal, thereby calculating the number of repetitions. The result is a mixture containing repeats of 1 to 48.

9) Production Example 8 [Production of (B) component]

In a four-necked flask equipped with a 3 L side tube of a reflux tube, 152 parts of tetrahydroanhydrous citric acid, 201 parts of trimethylolpropane, and 130.5 g of tris(2-hydroxyethyl) isocyanurate were mixed. 288 parts of acrylic acid, 15 parts of p-toluenesulfonic acid, 0.2 parts of 4-methoxyphenol, 780 g of toluene, and an oxygen-containing gas (oxygen 5 vol%, nitrogen 95 vol%) was blown into the flask while the reaction liquid temperature was 82. Heat and stir at ~97 °C. While the reaction was being carried out, the generated water was taken out of the system by a Dean-Stark tube, and a dehydration esterification reaction was carried out for 5 hours.

After the reaction was completed, 1000 g of toluene was added to dilute. 600 g of a 20% aqueous sodium hydroxide solution was added under stirring and stirred well, and the lower layer was removed after standing. Next, 250 g of distilled water was added to the organic phase with stirring and stirred, and the lower layer was removed after standing. The upper organic phase was heated under reduced pressure to distill off toluene.

The obtained acrylate was 620 g (yield 80%) and the viscosity was 39,000 mPa. s (50 ° C). Hereinafter referred to as "PEA2".

The respective elution times of the peaks of the molecular weight distribution were measured by using PEA2, and each of the above elution times was obtained by using GPC (column: Styragel HR 4ETHF and Styragel HR 1THF, lysate: THF).

The molecular weight corresponding to each dissolution time converted from the standard curve, according to the constituent components of tris(2-hydroxyethyl) isocyanate, trimethylolpropane, tetrahydroanhydrous decanoic acid and addition thereto The molecular weight of the terminal acrylic acid was assigned to calculate the number of repetitions, and as a result, a mixture containing 1 to 40 repeats was contained.

2. Examples and comparative examples

1) Production of active energy ray hardening composition

The compound shown in the following Table 1 was stirred and mixed at a ratio shown in Table 1 to prepare an active energy ray-curable composition.

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

In addition, the brackets in Table 1 mean the number of copies.

Also, the abbreviations in Table 1 are as follows.

‧M-305: a mixture of neopentyl glycol triacrylate and neopentyl glycol tetraacrylate, Aronix M-305 manufactured by East Asia Synthetic Co., Ltd.

‧THF-MA: tetrahydrofurfuryl methacrylate

‧M-309: Trimethylolpropane triacrylate, Aronix M-309 manufactured by East Asia Synthetic Co., Ltd.

‧M-402: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Aronix M-402 manufactured by East Asia Synthetic Co., Ltd.

‧UA-510H: urethane acrylate composed of dipentaerythritol pentaacrylate and hexamethylene diisocyanate, Light Ester UA-510H manufactured by Kyoeisha Chemical Co., Ltd.

‧HCPK: 1-hydroxy-cyclohexyl-phenyl-ketone, IRGACURE 184 manufactured by BASF

‧TPO: 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide, DAROCUR TPO manufactured by BASF

2) Evaluation method

Curability, adhesion, hardness and flexibility were evaluated according to the methods described below.

(1) Hardenability

The obtained composition was applied to a polyethylene terephthalate (PET) film (Toyobo Co., Ltd.) PET film Cosmo Shine A4300 (film thickness 100 μm) by a bar coater so as to have a film thickness of 20 μm. )), and use a high-pressure mercury lamp (Eyegraphics, UB032-5B) of 80W/cm, and use the 365nm-centered ultraviolet range (UV-A) intensity of 280mW/cm ² , and adjust it to 1 The conveyor was conveyed by a conveyor that irradiated energy at 500 mJ/cm ² .

The evaluation method of the hardenability is to determine the number of times until the surface becomes non-sticky.

(2) hardened film properties

In the following evaluation, a sample obtained by curing the composition was subjected to ultraviolet irradiation under the same conditions as the hardenability test until it became non-tacky.

A) Adhesion

100 lattices of 1 mm × 1 mm size were formed on the cured film, and were strongly peeled off after adhering the transparent tape. According to the number of residual films after peeling, it was evaluated according to the following three levels.

A: The number of residual film grids is 80 or more, B: The number of residual film grids is 60 to 79, and C: The number of residual film grids is 59 or less.

B) pencil hardness

The evaluation was carried out in accordance with JIS K 5600-5-4 at a load of 750 g.

C) softness

According to the mandrel test (JIS K5600-5-1), the PET film on which the coating film has been formed is taken up on a mandrel having a diameter of 3 mm to 10 mm, and no crack is observed. Or the core diameter of the smallest diameter stripped. Any crack that is visible on the coating film even if it is a 10 mm core rod or peeled off is marked as ">10". Further, the smaller the core rod diameter, the higher the flexibility of the coating film.

3) Evaluation results

The evaluation results are shown in Table 2 below.

As is clear from the results of Examples 1 to 8, the composition of the present invention has less hardening resistance by oxygen in the air, even if it is a composition containing the polyester acrylate as the main component of the component (B). And the hardenability is good. Moreover, while maintaining good surface hardness, it is also possible to have both flexibility.

On the other hand, in the case of the composition of Comparative Example 1 containing the trimethylolpropane triacrylate without addition of EO in place of the component (A), the flexibility of the cured film is insufficient except that the hardenability is greatly reduced. of. Substituting (A) with a mixture containing di pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate In the case of the composition of Comparative Example 2 of the composition, although good curability and surface hardness were obtained, the cured film did not have flexibility in addition to high viscosity and poor handleability. In the case of the composition of Comparative Example 3 containing the urethane acrylate-substituted (B) component, both the curability and the hardness may be obtained, but the cured film does not have flexibility. The composition of Comparative Example 4 in which the EO acrylate was replaced by the addition of EO to the component (A) had poor curability and the surface hardness of the cured film was insufficient. In the composition of Comparative Example 5 in which (A) was replaced with an EO addition molar number of 24, the hardenability was insufficient, and the hardness of the cured film was greatly reduced. The ratio of the component (A) to the component (B) is a composition of Comparative Example 6 which falls outside the suitable range of the present invention, and the adhesion is not good, and even if the flexibility is to be evaluated, the coating film is easily peeled off from the substrate. . Further, the composition of Comparative Example 7 containing no component (A) had a large influence on the hardening resistance by oxygen, and therefore the surface hardenability was not good, and the flexibility of the cured film was also insufficient.

Industrial availability

The composition of the present invention can improve the hardenability and impart flexibility without impairing the excellent substrate adhesion or hardness peculiar to the polyester (meth) acrylate, and is useful as a coating agent for various substrate surfaces. of.

Claims (13)

An active energy ray-curable composition containing the following components (A), (B), and (C), and containing 10% by weight of the total of the components (A), (B), and (C) ~70% by weight of the component (A), 30 to 90% by weight of the component (B) and 0 to 30% by weight of the component (C), wherein the component (A) is added from the dipentaerythritol. a compound (A1) having two or more (meth) acrylonitrile groups obtained by using a polyol of ~18 mole ethylene oxide, and/or having 2 to 6 moles of ethylene oxide added from neopentyl alcohol a compound (A2) having two or more (meth) acrylonitrile groups obtained by a polyol; (B) component: a polyol, a divalent carboxylic acid or an anhydride thereof, and a reaction with (meth)acrylic acid; Component C: A compound having one ethylenically unsaturated group and/or a compound other than the component (A) and the component (B) having two or more ethylenically unsaturated groups. The active energy ray-curable composition of claim 1, wherein among the components (A1), the polyol having 3 to 18 moles of ethylene oxide added to the dipentaerythritol is a hydroxyl group of 290 to 820 mg KOH. /g compound. The active energy ray-curable composition of claim 1, wherein among the components (A2), a polyol having 2 to 6 moles of ethylene oxide added to neopentyl alcohol is a valence of 500 to 1,000 mg KOH. /g compound. An active energy ray-curable composition according to any one of claims 1 to 3, In the above (A1) component, a reactant of a polyol having 3 to 18 moles of ethylene oxide and (meth)acrylic acid added to diheptaerythritol is used. The active energy ray-curable composition according to any one of claims 1 to 4, wherein the component (A1) is a compound having a (meth) acrylonitrile equivalent of 115 to 270 g/eq. The active energy ray-curable composition according to any one of claims 1 to 5, wherein the component (A2) is a compound having a (meth)acryl oxime equivalent of from 108 to 180 g/eq. The active energy ray-curable composition according to any one of claims 1 to 6, wherein among the components (B), the polyol is an alkylene glycol, a dialkyl alkyl glycol, or a trimethylolpropane. , neopentyl alcohol or tris(2-hydroxyalkyl) isocyanurate; the divalent carboxylic anhydride is phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride. The active energy ray-curable composition according to any one of claims 1 to 7, wherein the number of repeating units of the polyol of the component (B) and the divalent carboxylic acid or its anhydride is from 1 to 50. The active energy ray-curable composition according to any one of claims 1 to 8, wherein the optical component is further contained in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C). The base polymerization initiator is used as the component (D). An active energy ray-curable coating composition comprising the composition of any one of claims 1 to 9. An active energy ray-curable coating composition according to claim 10 which is for plastic coating. a laminate body comprising a substrate and a request item formed on the substrate 10 or a cured product of the active energy ray-curable coating composition of claim 11. The laminate of claim 12, wherein the substrate is a plastic.