JP6485446B2 - Active energy ray-curable coating agent composition - Google Patents

Description

The present invention relates to a coating agent composition that can be cured by irradiation with active energy rays. The composition of the present invention has low viscosity and fast curability, and the resulting cured film can achieve both excellent surface hardness and flexibility.
In the present specification, the acryloyl group and / or methacryloyl group is referred to as a (meth) acryloyl group, the acrylate and / or methacrylate is referred to as (meth) acrylate, and acrylic acid and / or methacrylic acid is referred to as (meth) acrylic acid.

As an active energy ray-curable coating composition, a composition mainly composed of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hereinafter referred to as “DPHA”) is known (Patent Document 1). The cured film obtained from the composition is widely used for hard coat applications because of its high surface hardness and resistance to scratching.
In addition, since the raw material DPHA itself has a high viscosity, the composition must be diluted with an organic solvent when used as a coating agent. In this case, there is a problem that the organic solvent contained in the composition erodes the substrate when applied to the plastic film, and it takes time and cost to dry the organic solvent.
In order to solve this problem, a composition in which a polyfunctional (meth) acrylate such as DPHA is diluted with a monofunctional (meth) acrylate or a bifunctional (meth) acrylate having a low viscosity is known (Patent Document 2). ).
As a method for improving the warp and breakability of a cured film, there is a coating agent composition mainly composed of urethane (meth) acrylate obtained by reacting a polyfunctional (meth) acrylate having a hydroxyl group with a polyvalent isocyanate. (Patent Document 3).

JP-A-6-248008 JP 2009-287017 A JP 2012-229412 A

However, the cured film of the composition described in Patent Document 1 has a problem that the warp at the time of curing is large and the film is likely to be deformed, and is easily broken, and cracking and peeling are caused when a hard-coated film substrate is bent. Has a problem that is likely to occur.
In addition, in the composition described in Patent Document 2, it is necessary to use 30 parts by weight or more of monofunctional (meth) acrylate or bifunctional (meth) acrylate in order to reduce the viscosity of the composition. There is a problem that the hardness of the formed cured film is too low.
Furthermore, since the composition as described in Patent Document 3 has a high viscosity, an organic solvent must be used as a diluent for the purpose of improving the handling during coating. is there.
The present inventors have low viscosity and excellent handling properties without using an organic solvent, and are excellent in curability. The resulting cured film has excellent surface hardness, flexibility and adhesion, and low curl. In order to find a certain active energy ray-curable coating agent composition, intensive studies were conducted.

In order to solve the above-mentioned problems, the inventors have prepared a compound having (meth) acrylate obtained from a polyol obtained by adding 3 to 24 mol of ethylene oxide to dipentaerythritol and three or more (meth) acryloyl groups. It was found that the combined composition had a sufficiently low viscosity without using an organic solvent, good curability, and excellent physical properties such as hardness and flexibility of the cured film, and the present invention was completed.
That is, the present invention provides the following (A), seeing containing (B) and component (C), a composition containing no organic solvent,
(A) component is 40 to 97 parts by weight, (B) component is 3 to 60 parts by weight, and (C) component is 0 with respect to 100 parts by weight of the total amount of components (A), (B) and (C). The present invention relates to an active energy ray-curable coating agent composition containing -30 parts by weight.
Component (A): Compound having two or more (meth) acryloyl groups obtained from polyol obtained by adding 3 to 18 moles of ethylene oxide to dipentaerythritol Component (B): Component having three or more (meth) acryloyl groups (A) Compound other than Component (C) Component: Compound having one ethylenically unsaturated group and / or Compound other than (A) component having two ethylenically unsaturated groups Hereinafter, the present invention will be described in detail. explain.

  According to the composition of the present invention, it is low viscosity and fast curable, and the resulting cured film has excellent surface hardness, flexibility and adhesion, and low curl.

The present invention is seen containing a (A), (B) and component (C), a composition containing no organic solvent, (A), (B) and (C) to the total amount 100 parts by weight of component On the other hand, it relates to an active energy ray-curable coating agent composition comprising 40 to 97 parts by weight of component (A), 3 to 60 parts by weight of component (B), and 0 to 30 parts by weight of component (C).
Hereinafter, components (A) to (C), other components, and methods of use will be described.

1. Component (A) Component (A) is a compound having two or more (meth) acryloyl groups obtained from a polyol obtained by adding 3 to 18 moles of ethylene oxide to dipentaerythritol (hereinafter simply referred to as “polyol”). .
The polyol which is a raw material compound in the component (A) is a compound having 6 hydroxyl groups in one molecule, a compound obtained by adding 3 to 18 mol of ethylene oxide to dipentaerythritol, and a compound obtained by adding 4 to 12 mol. preferable.
When the number of moles of ethylene oxide added is 2 or less, the performance and viscosity of the cured film are not different from those of DPHA, the viscosity is high and there is a problem in handling properties, and the flexibility of the cured film is problematic. On the other hand, when the number of added moles of ethylene oxide is 19 or more, the hardness of the cured film is lowered and the performance as a coating agent cannot be obtained.
In addition, with an alkylene oxide adduct other than ethylene oxide, the curing rate is slow, and thus tackiness tends to remain on the surface of the cured film.

  As a hydroxyl value of a polyol, 290-820 mgKOH / g is preferable, More preferably, it is 300-800 mgKOH / g.

The component (A) is preferably a compound having two or more (meth) acryloyl groups, more preferably a compound having 3 to 6 (meth) acryloyl groups.
In addition, the component (A) is a compound obtained by converting 2 to 6 of 6 hydroxyl groups of a polyol obtained by adding 3 to 18 moles of ethylene oxide to dipentaerythritol into a (meth) acryloyloxy group. A compound in which 4 to 6 are converted to a (meth) acryloyloxy group is more preferable.
The component (A) is usually obtained as a mixture of compounds having a plurality of (meth) acryloyl groups, and the (meth) acryloyl group equivalent is preferably 115 to 270 g / eq.
In the present invention, the (meth) acryloyl group equivalent means a value obtained by measuring the bromine number.
The component (A) is a mixture of tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate of a polyol obtained by adding 3 to 18 moles of ethylene oxide to dipentaerythritol. A mixture of tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate of a polyol obtained by adding 3 to 18 moles of ethylene oxide to dipentaerythritol is more preferable.

1) Manufacturing method (A) The component manufactured according to the conventional method can be used. Specifically, the manufacturing method of esterifying a polyol and (meth) acrylic acid, and the transesterification reaction of the polyol And the like.

  As the esterification reaction, a conventional method may be followed, and a method may be mentioned in which a polyol and (meth) acrylic acid are heated and stirred in the presence of an acid catalyst.

  The use ratio of (meth) acrylic acid is adjusted with respect to 1 mol of all hydroxyl groups of the polyol so as to be the intended (meth) acrylate, preferably 0.8 to 2.0 mol, more preferably 1.0 to 1.4 mol.

Examples of the acid catalyst include mineral acids such as sulfuric acid, and sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid.
The use ratio of the acid catalyst is preferably 0.05 mol% to 10 mol% with respect to the number of moles of the alcoholic hydroxyl group.

The esterification reaction may be carried out according to a conventional method.
The reaction temperature may be appropriately set according to the raw material to be used and the purpose, but is preferably 65 to 140 ° C, more preferably 75 to 120 ° C from the viewpoint of shortening the reaction time and preventing polymerization. By making reaction temperature 65 degreeC or more, esterification reaction can be performed rapidly and the fall of a yield can be prevented, On the other hand, (meth) acrylic acid or produced | generated by setting reaction temperature to 140 degrees C or less ( Thermal polymerization of (meth) acrylate can be prevented.

In the esterification reaction, it is preferable to promote dehydration while azeotroping water produced in the esterification reaction with an organic solvent.
Examples of preferable organic solvents include aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as hexane and heptane, and ketones such as methyl ethyl ketone.
The amount of the organic solvent used is preferably 10 to 75% by weight, more preferably 15 to 55% by weight, based on the total amount of polyol and (meth) acrylic acid.

  The degree of progress of the esterification reaction is monitored by monitoring the amount of water produced by the esterification reaction, that is, the amount of dehydration, analyzing the acid content concentration in the reaction solution, analyzing the composition of the product (meth) acrylate, Judgment is made by confirming whether the composition is the target.

In the esterification reaction, it is preferable to use a polymerization inhibitor in order to suppress polymerization of the raw material (meth) acrylic acid or the obtained (meth) acrylate.
As another effective method for suppressing polymerization, there are a method of reacting in an atmosphere of an oxygen-containing gas or a method of reacting while introducing an oxygen-containing gas into a reaction solution.

  The transesterification reaction may be performed according to a conventional method, and examples thereof include a method of heating and stirring a polyol and an alkyl (meth) acrylate in the presence of a catalyst.

As the alkyl (meth) acrylate, those having an alkyl group having 8 or less carbon atoms are preferred, and those having 4 or less are more preferably used.
Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) ) Acrylate and 2-ethylhexyl (meth) acrylate.

The catalyst is not particularly limited as long as it is usually used in transesterification, and examples thereof include a titanium-based catalyst, a tin-based catalyst, and sulfuric acid.
As a usage-amount of a catalyst, 0.05 mol%-20 mol% are preferable with respect to the number-of-moles of alcoholic hydroxyl group.

In the transesterification reaction, it is preferable to use a polymerization inhibitor in order to suppress the polymerization during the transesterification reaction, since alkyl (meth) acrylate having high radical polymerizability is used as a raw material.
As another effective method for suppressing polymerization, there are a method of reacting in an atmosphere of an oxygen-containing gas or a method of reacting while introducing an oxygen-containing gas into a reaction solution.

  The transesterification reaction can be performed without using a reaction solvent by using an excessive amount of alkyl (meth) acrylate as a raw material.

  However, a solvent may be used for the purpose of efficiently removing the generated alcohol out of the system or for uniformly dissolving the raw materials and products. In this case, it is preferable to use a reaction solvent that can azeotrope with the generated alcohol and dissolve the polyfunctional (meth) acrylate as the product. Examples of reaction solvents 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 ethone and methyl isobutyl. Ketones such as ketones may be mentioned.

The transesterification reaction is preferably carried out while distilling the produced alcohol out of the system under reflux.
The reaction temperature depends on the produced alcohol, the raw material alkyl (meth) acrylate, the reaction solvent, etc., but it is preferable to adjust the reaction temperature to be higher than the boiling point of the produced alcohol. The reaction temperature can be adjusted to some extent by selecting the raw material alkyl (meth) acrylate and reaction solvent, and controlling the pressure (pressurization or decompression). A preferable reaction temperature is 60 to 160 ° C, and 80 to 150 ° C is more preferable. When the reaction temperature is less than 60 ° C, the reaction rate is slow, and when it exceeds 160 ° C, coloring and gelation are likely to occur.

2) Content ratio The content ratio of the component (A) is 40 to 97 parts by weight with respect to 100 parts by weight of the total amount of the components (A), (B) and (C) [hereinafter referred to as “curable component”]. Yes, preferably 60 to 95 parts by weight.
If the content ratio of the component (A) is less than 40 parts by weight, the hardness of the cured film will be insufficient, and if it exceeds 97 parts by weight, the adhesion to the substrate will be insufficient.

2. Component (B) The component (B) is a compound other than the component (A) having three or more (meth) acryloyl groups.
Specific examples of the component (B) include various compounds as long as the compound has three or more (meth) acryloyl groups. For example, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Polyol poly (meth) acrylates such as tri- or tetra (meth) acrylate of pentaerythritol, tri- or tetra (meth) acrylate of ditrimethylolpropane and tri-, tetra-, penta- or hexa (meth) acrylate of dipentaerythritol;
Tri (meth) acrylate of glycerol alkylene oxide adduct, tri or tetra (meth) acrylate of pentaerythritol alkylene oxide adduct, tri or tetra (meth) acrylate of ditrimethylolpropane alkylene oxide adduct, dipentaerythritol alkylene oxide adduct A poly (meth) acrylate of a polyol alkylene oxide adduct such as tri, tetra, penta or hexa (meth) acrylate [excluding (A) component];
Urethane which is a reaction product of an organic polyisocyanate and a tri (meth) acrylate of an isocyanuric acid alkylene oxide adduct; and a compound having a hydroxyl group such as pentaerythritol tri (meth) acrylate and having three or more (meth) acryloyl groups A (meth) acrylate etc. can be mentioned.
Examples of the alkylene oxide adduct include ethylene oxide adduct, propylene oxide adduct, ethylene oxide and propylene oxide adduct, and the like.
Examples of the organic polyisocyanate include tolylene diisocyanate, 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, 1,6-hexane diisocyanate trimer, hydrogenated tolylene diisocyanate, Hydrogenated 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, paraphenylene diisocyanate, tolylene diisocyanate dimer, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate mutual adduct, 4,4′- Dicyclohexylmethane diisocyanate, trimethylolpropane tris (tolylene diisocyanate) adduct, isophorone diisocyanate, etc. That.

  Among these compounds, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol Tri (meth) acrylate of propane alkylene oxide adduct and urethane (meth) acrylate which is a reaction product of pentaerythritol tri (meth) acrylate and organic polyisocyanate are preferable.

(B) The content rate of a component is 3-60 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component, Preferably it is 5-30 weight part.
When the content ratio of the component (B) is less than 3 parts by weight, the surface hardness decreases, and when it exceeds 60 parts by weight, the cured film becomes brittle.

3. Component (C) The composition of the present invention essentially comprises the components (A) and (B), but for the purpose of reducing the viscosity of the composition and improving the adhesion of the cured product. If necessary, a compound other than the compound (C) having one ethylenically unsaturated group and / or the component (A) having two ethylenically unsaturated groups as the component (C) may be blended.

Examples of the ethylenically unsaturated group include a vinyl group and a (meth) acryloyl group.
Hereinafter, compounds other than the component (A) having two ethylenically unsaturated groups (hereinafter referred to as “bifunctional unsaturated compounds”) and compounds having one ethylenically unsaturated group (hereinafter referred to as “monofunctional unsaturated compounds”). Will be described.

1) Monofunctional unsaturated compound Examples of the monofunctional unsaturated compound include (meth) acrylate having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”), and one ( And (meth) acrylamide compounds having a (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylamide”).

As a specific example of monofunctional (meth) acrylate,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, lauryl ( Alkyl (meth) acrylates such as (meth) acrylate and stearyl (meth) acrylate;
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc. A monofunctional (meth) acrylate having an alicyclic group of
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolane Monofunctional (meth) acrylates having cyclic ether groups such as -4-yl) methyl (meth) acrylate and 3-ethyl-3-oxetanylmethyl (meth) acrylate;
Aromatic monofunctional (meth) acrylates such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, o-phenylphenoxy (meth) acrylate and p-cumylphenolethylene (meth) acrylate;
A monofunctional (meth) acrylate having a maleimide group such as (meth) acryloyloxyethyl hexahydrophthalimide;
(Meth) acryloylmorpholine;
Monofunctional (meth) acrylates having alkoxyalkyl groups such as ethyl carbitol (meth) acrylate and alkyl carbitol (meth) acrylate such as 2-ethylhexyl carbitol (meth) acrylate;
Such as 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylmethyldiethoxysilane and 3- (meth) acryloxypropyltriethoxysilane Examples include alkoxyl group-containing monofunctional (meth) acrylates.

Specific examples of monofunctional (meth) acrylamide compounds include N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl (meth) acrylamide. N-alkyl (meth) acrylamides such as N-sec-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide; N-hydroxyethyl (meth) acrylamide and the like N-hydroxyalkyl (meth) acrylamide; and N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl ( (Meth) acrylamide, N, N-di-n- N, N-dialkyl (meth) acrylamide of propyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide and N, N-dihexyl (meth) acrylamide Is mentioned.

As the component (C), a compound having a hydrophilic group is preferable in order to further improve the adhesion to the substrate.
In the case of a compound having a hydroxyl group as a hydrophilic group, a hydroxyl group-containing monofunctional (meth) acrylate and a hydroxyl group-containing (meth) acrylamide are preferred.
Examples thereof include hydroxyalkyl (meth) acrylates such as a hydroxyl group-containing monofunctional (meth) acrylate 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
Examples of the hydroxyl group-containing (meth) acrylamide include N-hydroxyethyl (meth) acrylamide.
Examples of the compound having an acidic group as a hydrophilic group include carboxyl groups such as (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate and monohydroxyethyl (meth) acrylate phthalate and (meth ) Acryloyl group-containing compound, phosphoric acid group-containing (meth) acrylate such as esterified product of phosphoric acid and (meth) acrylic acid, and the like.
(C) As a ratio in case a component is a compound which has an acidic group as a hydrophilic group, 0.0001-20 weight% is preferable in a sclerosing | hardenable component total amount, More preferably, it is 0.001-5 weight%. It is.

2) Bifunctional unsaturated compound Examples of the bifunctional unsaturated compound include (meth) acrylate having two (meth) acryloyl groups (hereinafter referred to as “bifunctional (meth) acrylate”).

As bifunctional (meth) acrylates, aliphatic diols such as ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. Di (meth) acrylates of
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc. Of polyalkylene glycol di (meth) acrylates;
Polyol di (meth) such as glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, di (meth) acrylate of pentaerythritol, di (meth) acrylate of ditrimethylolpropane and di (meth) acrylate of dipentaerythritol ) Acrylate;
Di (meth) acrylate of glycerol alkylene oxide adduct, di (meth) acrylate of pentaerythritol alkylene oxide adduct, di (meth) acrylate of ditrimethylolpropane alkylene oxide adduct, di (meth) of dipentaerythritol alkylene oxide adduct ) Di (meth) acrylate of polyol alkylene oxide adduct such as acrylate [excluding (A) component];
Di (meth) acrylate of an isocyanuric acid alkylene oxide adduct;
Di (meth) acrylates of alicyclic diols such as urethane (meth) acrylate tricyclodecane dimethylol di (meth) acrylate of pentaerythritol di (meth) acrylate and organic polyisocyanate;
Examples include di (meth) acrylates of alkylene oxide adducts of bisphenol compounds such as di (meth) acrylates of alkylene oxide adducts of bisphenol A and di (meth) acrylates of alkylene oxide adducts of bisphenol F.
In addition, as an example of the above-mentioned alkylene oxide adduct, an ethylene oxide adduct, a propylene oxide adduct, ethylene oxide, a propylene oxide adduct, etc. are mentioned.

  As the bifunctional (meth) acrylate, an oligomer can also be used, which is a reaction product of diol, organic polyisocyanate and hydroxyl group-containing (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate and epoxy (meth). An acrylate etc. can be mentioned.

3) Preferred compounds Among these compounds, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate and isobornyl (meth) acrylate are preferred as monofunctional (meth) acrylate, and bifunctional (meth) acrylate is preferred. , Hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate are preferred.

4) Content ratio The content ratio of the component (C) is 0 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the total amount of the curable components.
When the content rate of (C) component exceeds 30 weight part, the hardness of a cured film will become inadequate.

4). Other components The composition of the present invention comprises the components (A) and (B) as essential components and, if necessary, a component (C). And it can mix | blend according to a use.
Preferable components include a radical photopolymerization initiator (hereinafter referred to as “component (D)”), an antioxidant, an ultraviolet absorber, a pigment / dye, a leveling agent, and a silane coupling agent.

Hereinafter, these components will be specifically described.
In addition, the specific compound mentioned by description of the other component may use the said compound independently, and may be used in combination of 2 or more types.

1) Component (D) The component (D) is a radical photopolymerization initiator.
Component (D) is a compound that generates radicals by irradiation with active energy rays and initiates polymerization of a compound having an ethylenically unsaturated group. When an electron beam is used as the active energy ray, it is not always necessary to add the component (D).

Specific examples of the component (D) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1 -[4- (Methylthio)] phenyl] -2-morpholinopropan-1-one 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl- Aromatic ketone compounds such as phenyl) butan-1-one, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole, methyl phenylglyoxylate, ethyl anthraquinone 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) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis Benzophenone compounds such as (diethylamino) benzophenone and 4-methoxy-4′-dimethylaminobenzophenone;
Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6 -Acylphosphine oxide compounds such as -dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy] -2- Examples thereof include thioxanthone compounds such as hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone.

Among these compounds, α-hydroxyphenyl ketones are preferable because they have good surface curability even in the case of thin film coating in the atmosphere. Specifically, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one is more preferred.
Also, when it is necessary to increase the thickness of the cured film, for example, when it is necessary to make it 50 μm or more, the purpose of improving the curability inside the cured film, or when using a UV absorber or pigment together, (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6 -Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, an acylphosphine oxide compound, 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-ylphenyl) is preferably used in combination with butan-1-one and the like.

  As for the content rate of (D) component, 0.1-10 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.5-8 weight part. (D) By making the ratio of a component 0.1 weight part or more, it can make the photocurability of a composition favorable and can make it excellent in adhesiveness, and a cured film can be 20 weight part or less. The internal curability can be improved, and the adhesion to the substrate can be improved.

2) Antioxidant Antioxidant is mix | blended in order to improve durability, such as the heat resistance of a cured film, and a weather resistance.
Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
Examples of the phenolic antioxidant include hindered phenols such as di-t-butylhydroxytoluene. As what is marketed, Ade-20 Co., Ltd. AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80 etc. are mentioned.
Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphites and triaryl phosphites. Examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010 etc. are mentioned.
Examples of sulfur-based antioxidants include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.
These may be used alone or in combination of two or more. Preferred combinations of these antioxidants include the combined use of phenolic antioxidants and phosphorus antioxidants, and the combined use of phenolic antioxidants and sulfurous antioxidants.
What is necessary is just to set suitably as a mixture ratio of antioxidant according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1-1 weight part. It is.
When the blending ratio is 0.1 parts 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, curability and adhesion can be improved.

3) Ultraviolet absorber An ultraviolet absorber is mix | blended in order to improve the light resistance of a cured film.
Examples of the UV absorber include triazine UV absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole UV absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
What is necessary is just to set suitably as a compounding ratio of a ultraviolet absorber according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1-1 weight part. It is. When the blending ratio is 0.01% by weight or more, the light resistance of the cured film can be improved, and when it is 5% by weight or less, the curability of the composition is excellent. be able to.

4) Examples of the pigment / dye pigment include organic pigments and inorganic pigments.
Specific examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, benzidine yellow and pyrazolone red; soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet and Permanent Red 2B; Alizarin, Indantron And derivatives from vat dyes such as thioindigo maroon; phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone organic pigments such as quinacridone red and quinacridone magenta; perylene organic pigments such as perylene red and perylene scarlet; Isoindolinone organic pigments such as indolinone yellow and isoindolinone orange; pyranthrone organic pigments such as pyranthrone red and pyranthrone orange Thioindigo organic pigments; condensed azo organic pigments; benzimidazolone organic pigments; quinophthalone organic pigments such as quinophthalone yellow; isoindoline organic pigments such as isoindoline yellow; and other pigments such as flavanthrone yellow and acylamide Examples include yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, and dioxazine violet.
Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and oxidation. Examples include chrome green, cobalt green, amber, titanium black, and synthetic iron black. The carbon black exemplified as the filler can also be used as an inorganic pigment.
Various conventionally known compounds can be used as the dye.

5) Leveling agents Silicone leveling agents, fluorine leveling agents, and the like can be mentioned, and various leveling agents that are commercially available can be used.

6) Silane coupling agent A silane coupling agent is mix | blended in order to improve the interface adhesive strength of a cured film and a base material.
As the silane coupling agent, any known silane coupling agent can be used without particular limitation as long as it can contribute to the improvement of the adhesion to the substrate.

  Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 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, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3 -Aminopropyltrimethoxysilane, 3-mercaptopropylme Dimethoxysilane, 3-mercaptopropyl trimethoxy silane and the like.

The blending ratio of the silane coupling agent may be appropriately set according to the purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component. .
When the blending ratio is 0.1 parts by weight or more, the adhesive strength of the composition can be improved. On the other hand, when the blending ratio is 10 parts by weight or less, it is possible to prevent the adhesive force from changing over time.

7) Other components other than the above In addition to the above, the composition of the present invention may contain various components used as a coating agent.
For example, the composition of the present invention is preferably used as a solvent-free composition, but an organic solvent can be blended as necessary.
Specific examples of preferred solvents include alcohols such as ethanol and isopropanol; alkylene glycol monoethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; aromatic compounds such as toluene and xylene; propylene glycol Examples thereof include esters such as monomethyl ether acetate, ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as dibutyl ether; and N-methylpyrrolidone.

5). The active energy ray-curable coating composition present invention, said components (A) and (B) as essential components, preferably to actinic radiation a coating composition comprising a component (C).
As a manufacturing method of a composition, what is necessary is just to follow a conventional method, for example, it can manufacture by stirring and mixing (A) and (B) component, and (C) component and another component as needed.

What is necessary is just to set the viscosity of a composition suitably according to the objective, and 200-3,000 mPa * s is preferable.
In the present invention, the viscosity means a value measured at 25 ° C. using an E-type viscometer.

6). Method of Use As a method of using the composition of the present invention, a conventional method may be followed.
For example, after apply | coating a composition to a base material, the method etc. of irradiating an active energy ray are mentioned.
Further, a method of improving the adhesion to the substrate by using a photopolymerization initiator and a thermal polymerization initiator in combination with the composition, irradiating the composition with active energy rays and then heat-curing it can be employed.

The substrate to which the composition of the present invention can be applied is applicable to various materials, and examples thereof include plastic, wood, metal, inorganic material, and paper.
Specific examples of the plastic include polymethyl methacrylate, a copolymer of methyl methacrylate and styrene, polyethylene terephthalate, polyvinyl chloride, polycarbonate, epoxy resin, and polyurethane resin.
Examples of the wood include natural wood and synthetic wood.
Examples of inorganic materials include mortar, concrete, glass, and stone.
Especially, the composition of this invention can be used suitably as a composition for plastic coating, and can be used more suitably as a composition for acrylic resin and / or polyester resin coating.

What is necessary is just to follow a usual method as a coating method to the base material of the composition of this invention.
Examples thereof include bar coat, roll coat, spin coat, dip coat, gravure coat, flow coat, and spray coat.

Examples of the active energy ray for curing the composition of the present invention include ultraviolet rays, visible rays, and electron beams, and ultraviolet rays are preferred.
Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED.
The irradiation energy should be appropriately set according to the type and composition of the active energy ray. As an example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 5,000 mJ / cm ² is preferable, and 200 to 1,000 mJ / cm ² is more preferable.

The composition of the present invention can be used for various applications, and includes paints for woodwork, topcoat paints such as mortar and slate, and waterproof paints for printed circuit boards constituting electronic circuits.
Specific usage forms of the coating agent include coating of the back surface of an optical disk such as CD and DVD, coating of a mobile phone body, and coating of a headlight for an automobile. It is also useful as a molding material, and examples thereof include a transparent acrylic plate and a liquid crystal material.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
In the following, “part” means part by weight, and “%” means percent by weight.
In the following, ethylene oxide is abbreviated as “EO” and propylene oxide is abbreviated as “PO”. Moreover, the acrylic group equivalent in a manufacture example is based on the value obtained by measuring the bromine number of the obtained acrylate.

1. Production example
1) Production Example 1 (Production of acrylate of dipentaerythritol EO 6 mol adduct)
In a 3 L side necked four-necked flask equipped with a reflux tube, 600 g of dipentaerythritol EO6 mol adduct (Aoki Yushi Kogyo Co., Ltd., Brownon DPE-E6R, hydroxyl value 643 mg KOH / g), acrylic acid 600 g (alcohol 1.21 mole ratio relative to 1 mole of all hydroxyl groups therein), 39 g of 70% methanesulfonic acid (hereinafter referred to as “MSA”), 3 g of cupric chloride and 540 g of toluene were added.
While oxygen-containing gas (oxygen 5 vol%, nitrogen 95 vol%) was blown into the flask, the mixture was heated and stirred at a reaction liquid temperature of 85 to 95 ° C. With the progress of the reaction, the dehydrated esterification reaction was carried out for 5 hours while taking out the generated water out of the system with a Dean-Stark tube.

After completion of the reaction, 900 g of toluene was added for dilution. Further, 240 g of distilled water was added and stirred and allowed to stand, and then the lower layer was removed. Next, 400 g of a 20% aqueous sodium hydroxide solution was added with stirring, and the mixture was sufficiently stirred and allowed to stand, and then the lower phase was removed. Subsequently, 240 g of distilled water was added to the organic phase under stirring, and the mixture was allowed to stand and then the lower layer was removed. The upper organic phase was heated under reduced pressure to distill off toluene.
The obtained acrylate was 930 g (yield 94%), the viscosity was 450 mPa · s (25 ° C.), and the acrylic group equivalent was 148 g / eq. Hereinafter, it is referred to as “acrylate 6EO”.

2) Production Example 2 (Production of acrylate of dipentaerythritol EO 12 mol adduct)
In a 4-liter flask with a 3 L side tube provided with a reflux tube, 760 g of dipentaerythritol EO 12 mol adduct (Aoki Yushi Kogyo Co., Ltd., Brownon DPE-E12R, hydroxyl value 423 mg KOH / g), acrylic acid 480 g (alcohol The ratio of 1.16 moles per mole of all hydroxyl groups therein), 20 g of MSA, 2 g of cupric chloride and 540 g of toluene were added.
Heating and stirring at a reaction liquid temperature of 85 to 95 ° C. while blowing the same oxygen-containing gas as in Example 1 and removing the water produced by the same method as in Production Example 1 from the system for 6 hours of dehydration esterification reaction went.
After completion of the reaction, the organic phase was separated by the same treatment as in Example 1, and 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 acrylic group equivalent was 207 g / eq. Hereinafter, it is referred to as “acrylate 12EO”.

3) Comparative Production Example 1 (Production of acrylate of dipentaerythritol PO 6 mol adduct)
Into a 3 L side-tube four-necked flask equipped with a reflux tube, 660 g of PO6 mol adduct of dipentaerythritol (Aoki Yushi Kogyo Co., Ltd., BROWNON DPE-360R, hydroxyl value 565 mg KOH / g), acrylic acid 570 g (alcohol) The ratio of 1.19 moles per mole of all hydroxyl groups therein), 36 g of MSA, 3 g of cupric chloride and 540 g of toluene were charged.
The mixture was heated and stirred at a reaction liquid temperature of 85 to 95 ° C. while blowing the same oxygen-containing gas as in Example 1.
A dehydration esterification reaction was carried out for 8 hours while removing water produced by the same method as in Production Example 1 out of the system.
After completion of the reaction, the organic phase was separated by the same treatment as in Example 1, and heated under reduced pressure to distill off toluene.
The obtained acrylate was 970 g (yield 96%), the viscosity was 800 mPa · s (25 ° C.), and the acrylic group equivalent was 320 g / eq. Hereinafter, it is referred to as “acrylate 6PO”.

4) Comparative Production Example 2 (Production of acrylate of 24 mol adduct of dipentaerythritol EO)
In a 4-liter flask with a 3 L side tube equipped with a reflux tube, 895 g of EO24 mol adduct of dipentaerythritol (Aoki Yushi Kogyo Co., Ltd., Brownon DPE-E24R, hydroxyl value 260 mgKOH / g), 340 g of acrylic acid (alcohol The ratio of 1.14 mol to 1 mol of all hydroxyl groups therein, MSA (22 g), cupric chloride (1 g) and toluene (540 g) were added.
The mixture was heated and stirred at a reaction liquid temperature of 85 to 95 ° C. while blowing the same oxygen-containing gas as in Example 1.
A dehydration esterification reaction was carried out for 7 hours while removing water produced by the same method as in Production Example 1 out of the system.
After completion of the reaction, the organic phase was separated by the same treatment as in Example 1, and 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 acrylic group equivalent was 166 g / eq. Hereinafter, it is referred to as “acrylate 24EO”.

2. Examples and Comparative Examples
1) Production of active energy ray-curable coating agent composition The compounds shown in Table 1 below were stirred and mixed in the proportions shown in Table 1 to produce an active energy ray-curable coating agent composition.
The obtained composition was used and evaluated as described later. The results are shown in Table 2.

The brackets in Table 1 mean the number of copies.
Moreover, the symbol in Table 1 means the following.
M-305: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, Aronix M-305 manufactured by Toagosei Co., Ltd.
M-402: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Aronix M-402 manufactured by Toagosei Co., Ltd.
M-350: triacrylate of trimethylolpropane ethylene oxide modified product, Aronix M-350 manufactured by Toagosei Co., Ltd.
UA-510H: urethane acrylate composed of dipentaerythritol pentaacrylate and hexamethylene diisocyanate, light ester UA-510H manufactured by Kyoeisha Chemical Co., Ltd.
P-2M: 2-methacryloyloxyethyl acid phosphate, light ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.
M-240: polyethylene glycol (average number of moles of added ethylene oxide = 4) diacrylate, Aronix M-240 manufactured by Toagosei Co., Ltd.
HCPK: 1-hydroxycyclohexyl phenyl ketone, IRGACURE184 manufactured by BASF
TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, DAROCUR TPO manufactured by BASF
HMPP: 2-hydroxy-2-methyl-1-phenyl-propan-1-one BAPO: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, IRGACURE 819 manufactured by BASF

2) Evaluation method
(1) Viscosity The viscosity of the obtained composition was measured at 25 ° C. using an E-type viscometer.
A lower viscosity indicates better handling as a coating composition.

(2) Curability The obtained composition was applied to polyethylene terephthalate (PET) [manufactured by Toyobo Co., Ltd., Cosmo Shine A4300 (100 μm)] to a film thickness of 5 μm with a bar coater (# 3), 80 W / Irradiation of 200 mJ / cm ² per pass at a UV region (UV-A) intensity of 745 mW / cm ² centered at 365 nm using a cm high-pressure mercury lamp (UB032-5B manufactured by Eye Graphics Co., Ltd.) It was conveyed on a conveyor adjusted to be energy.
As a method for evaluating curability, the number of passes until the surface tack was eliminated was determined.

(3) Physical property of cured film In the following evaluation, a sample obtained by curing the composition by irradiating with ultraviolet rays in 4 passes (800 mJ / cm ² ) under the same conditions as in the curability test was used.

A) Pencil hardness In accordance with JIS K5600-5-4, evaluation was performed with a load of 750 g.

A) According to a flexible mandrel test (JIS K5600-5-1), a PET film having a cured film formed around a core rod having a diameter of 2 mm was wound and evaluated according to the following two levels.
○: No cracking or peeling of the cured film, ×: Cracking or peeling of the cured film was observed

C) A curled sample was cut into a size of 10 cm × 10 cm, and the heights at which the four corners were lifted were measured and evaluated by an average value. A smaller value indicates less deformation.

D) 100 squares having a size of 1 mm × 1 mm were formed on the adhesive cured film, and the cellophane tape was affixed and then peeled off strongly. The following three levels were evaluated based on the number of remaining films after peeling.
◎: Number of remaining film cells is 80 or more, ○: Number of remaining film cells is 60 to 79, ×: Number of remaining film cells is 59 or less

3) Evaluation results The evaluation results are shown in Table 2 below.

As is clear from the results of Examples 1 to 4, since the composition of the present invention has a low viscosity, excellent coating properties can be obtained without using an organic solvent as a diluent, and curability is also improved. It was excellent. Moreover, the cured film was excellent in all of hardness, flexibility, curling property, and adhesion, and had both flexibility while maintaining good surface hardness.
On the other hand, the composition of Comparative Example 1 containing as a main component a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate not added with EO provides high curability and surface hardness, but has high viscosity and handling. In addition to poor properties, the flexibility and adhesion were insufficient and the base film was greatly deformed. Further, the composition of Comparative Example 2 containing no component (B) had a low viscosity, and although the cured film was excellent in hardness and flexibility, the adhesion to the substrate was insufficient. The composition of Comparative Example 3 using acrylate 6PO (acrylate added with PO instead of EO) in place of component (A) has poor curability and the surface hardness and adhesion of the cured film cannot be obtained. It was. In place of the component (A), the composition of Comparative Example 3 using acrylate 24EO (an acrylate having an EO addition mole number of 24) has large curability and hardness and a decrease in a cured film, and obtains performance as a coating agent. I could not.

  The composition of the present invention is useful as a coating agent for various substrate surfaces.

Claims (9)

Following (A), seeing containing (B) and component (C), a composition containing no organic solvent,
(A) component is 40 to 97 parts by weight, (B) component is 3 to 60 parts by weight, and (C) component is 0 with respect to 100 parts by weight of the total amount of components (A), (B) and (C). Active energy ray-curable coating agent composition comprising -30 parts by weight.
Component (A): Compound having two or more (meth) acryloyl groups obtained from polyol obtained by adding 3 to 18 moles of ethylene oxide to dipentaerythritol (B) Component: Having three or more (meth) acryloyl groups (A) Compound other than component (C) Component: Compound having one ethylenically unsaturated group and / or Compound other than (A) component having two ethylenically unsaturated groups   2. The active energy ray-curable coating composition according to claim 1, wherein in the component (A), a polyol obtained by adding 3 to 18 moles of ethylene oxide to dipentaerythritol is a compound having a hydroxyl value of 290 to 820 mgKOH / g.   The active energy ray-curable coating composition according to claim 1 or 2, wherein in the component (A), the polyol is a polyol obtained by adding 4 to 12 moles of ethylene oxide to dipentaerythritol.   The active energy ray according to any one of claims 1 to 3, wherein the component (A) is a reaction product of a polyol obtained by adding 3 to 18 moles of ethylene oxide to dipentaerythritol and (meth) acrylic acid. A curable coating agent composition.   The active energy ray-curable coating agent composition according to any one of claims 1 to 4, wherein the component (A) is a compound having a (meth) acryloyl group equivalent of 115 to 270 g / eq.   Furthermore, the radical photoinitiator is contained as 0.01 to 20 weight part with respect to 100 weight part of total amounts of (A), (B), and (C) component as (D) component. The active energy ray hardening-type coating agent composition of any one of these. The active energy ray-curable coating agent composition according to any one of claims 1 to 6 , which is used for plastic coating. Laminate comprising a cured product of the substrate and the active energy ray-curable coating composition according to any one of claims 1 to 7 formed on the substrate. The laminate according to claim 8 , wherein the base material is plastic.