KR101549294B1 - Actinic-radiation curable composition - Google Patents

Abstract

The present invention is capable of obtaining a cured coating film having good active energy ray sensitivity and having the same hardness as that in the case of active energy ray irradiation under an atmosphere of nitrogen under active oxygen ray irradiation in the presence atmosphere of oxygen, (A) an isosorbide di (meth) acrylate, (b) a compound containing a polymerizable unsaturated group other than the component (a), and (c) an active energy ray-curable composition which is excellent in heat resistance and chemical resistance. Wherein the content of the component (a) is from 5 to 95 parts by mass based on 100 parts by mass of the total amount of the component (a) and the component (b), and the content of the component (b) 5 parts by mass to 95 parts by mass based on 100 parts by mass of the total amount of the components (a) and (b), and the content of the component (c) is 0.1 parts by mass To 20 parts by mass.

Description

[0001] ACTINIC-RADIATION CURABLE COMPOSITION [0002]

The present invention relates to an active energy ray-curable composition.

(Meth) acrylate esters are one of important monomer for copolymerization, and they are formulated into various kinds of purposes and uses. In general, however, the desired performance is not generally obtained by polymerization of a single monomer. For example, in order to obtain necessary properties, a plurality of other (meth) acrylic acid esters, oligomers, polymers, And this is polymerized to exhibit desired performance (Patent Document 1).

Particularly, in the dry film resist, the colored resist, and the black resist composition, in addition to the physical properties of the coating film after curing, particularly when the curing is carried out with active energy rays such as ultraviolet rays or electron beams, High sensitivity is required. Among them, a composition having a high light shielding property, such as a coloring resist and a black resist, which contains a high concentration of a pigment and a dye, is required to be cured even at a low exposure dose, but no satisfactory one has been obtained (Patent Document 2 , Patent Document 3).

Further, in the case of the conventional active energy ray-curable composition, when curing with active energy radiation in the presence atmosphere of oxygen (in air), curing inhibition by oxygen usually occurs. For this reason, there is a problem that the curability, particularly the hardness of the cured coating film, is lowered as compared with the case where irradiation with active energy rays is performed in a nitrogen atmosphere.

Japanese Patent Application Laid-Open No. 2003-261659 Japanese Patent Application Laid-Open No. 2001-089416 Japanese Patent Application Laid-Open No. 2008-046330

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a cured coating film (coating film) having an active energy ray sensitivity and a hardness equivalent to that of active energy ray irradiation under a nitrogen atmosphere, Which is excellent in moisture resistance, heat resistance and chemical resistance, and which has a cured coating film of high hardness.

(B) a polymerizable unsaturated group-containing compound other than the component (a), and (c) a polymerizable unsaturated group-containing compound other than the component (a) Wherein the content of the component (a) is 5 to 95 parts by mass based on 100 parts by mass of the total amount of the components (a) and (b), and the content of the component (b) Is 5 parts by mass to 95 parts by mass based on 100 parts by mass of the total amount of the components (a) and (b), and the content of the component (c) is 100 parts by mass based on the total amount of the components (a) 0.1 part by mass to 20 parts by mass.

The active energy ray curable composition of the present invention is a polymerizable resin composition comprising (meth) acrylate of a polyfunctional alcohol represented by conventional dipentaerythritol, pentaerythritol, ditrimethylol propane, trimethylol propane, pentaerythritol, etc. The active energy ray irradiation under the presence atmosphere of oxygen can obtain a cured coating film having the same hardness as that in the case of irradiation with active energy rays under a nitrogen atmosphere and the cured coating film has a high hardness Moisture resistance, heat resistance, chemical resistance, and the like.

Therefore, the active energy ray curable composition of the present invention is suitably used as a resist resin composition such as a dry film resist, a colored resist, a black resist, or a semiconductor resist. It is also suitably used as a composition for forming a clear paint or the like.

Further, since the composition of the present invention is obtained using plant-derived isosorbide as a main raw material, it is possible to provide a clean material which is less dependent on fossil resources.

Hereinafter, the present invention will be described in detail.

≪ Isosorbide di (meth) acrylate >

The isosorbide di (meth) acrylate used in the present invention is not particularly limited, but can be produced from isosorbide using the following (meth) acrylation reaction. That is, a method of esterifying a hydroxyl group with (meth) acrylic acid halide or (meth) acrylic acid anhydride, a transesterification reaction using an ester of a lower alcohol of (meth) acrylic acid such as MMA (methyl methacrylate) Dicyclohexylcarbodiimide), and WSCD (water-soluble carbodiimide), dehydration condensation with (meth) acrylic acid, and dehydration condensation using an acid catalyst. In addition, if necessary, a known polymerization inhibitor may be used to prevent polymerization from proceeding during production or storage of the product.

<Polymerizable unsaturated group-containing compound other than isosorbide di (meth) acrylate>

Examples of the polymerizable unsaturated group-containing compound other than isosorbide di (meth) acrylate include esters of a polyfunctional alcohol and (meth) acrylic acid. Specific examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) Acrylates such as di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di Pentaerythritol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- Acrylate, hydrogenated bisphenol F di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, tricyclodecane dimethanol di (Meth) acryloyloxy) hexahydrophthalic acid, 5-ethyl-2- (2-hydroxy-1,1-dimethylethyl) -5 (Meth) acrylate, methacryloxypropyl (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, (Meth) acrylate compounds such as 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene; (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (2-acryloyloxyethyl) isocyanurate, tris (2-acryloyloxypropyl) isocyanurate, caprolactone-modified tris (2-acryloyloxyethyl) isocyanurate Tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate; Tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, polyhydric alcohol and N-methylol Condensates with amides, or modified products thereof, and the like are suitably used. Further, an acrylic (meth) acrylate resin, a urethane (meth) acrylate resin, an epoxy (meth) acrylate resin and a polyester (meth) acrylate resin can also be used. These may be used alone or in combination of two or more. Of these, preferred are caprolactone-modified dipentaerythritol hexaacrylate, pentaerythritol triacrylate adduct of hexamethylene diisocyanate, tris (2-acryloyloxyethyl) isocyanurate, caprolactone modified tris (2- Acryloyloxyethyl) isocyanurate, and the like.

In addition to these, various general-purpose monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate, isobornyl (meth) acrylate, (meth) acryloylmorpholine, (meth) acrylamide, dicyclohexyl fumarate, dibenzyl fumarate, dibutyl fumarate, vinyl caprolactam, Vinyl pyrrolidone, vinyl acetate, styrene, or the like may be used.

&Lt; Polymerization initiator by active energy ray &gt;

The polymerization initiator by the active energy ray in the present invention includes both a photopolymerization initiator and a polymerization initiator by an active energy ray such as ultraviolet rays.

As the photopolymerization initiator, for example, aromatic ketones such as benzophenone, aromatic compounds such as anthracene and? -Chloromethylnaphthalene, and sulfur compounds such as diphenyl sulfide and thiocarbamate can be used.

Examples of the polymerization initiator by an active energy ray such as ultraviolet ray include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane- Examples of the organic solvent include at least one selected from the group consisting of xanthone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, Benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy- Methyl-1-phenylpropane-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2- (2-hydroxyethoxy) phenyl] -2-morpholino-propan-1-one, - (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) -2,4,4-trimethylpentylphosphine oxide, Propanone) and the like.

Examples of commercial products of the polymerization initiator by an active energy ray include those available under the trade names Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CI1850, CG24-61, DARACURE 1116, 1173, Lucifer TPO manufactured by BASF, UCB manufactured by UCB, and Ubecryl P36 manufactured by Pratelli Lamberty under the trade names Ejecure KIP150, KIP65LT, KIP100F, KT37, KT55, KIP75 / B and the like.

If necessary, a radical polymerization initiator may be used in combination with the photopolymerization initiator. Examples of the radical polymerization initiator include benzoyl peroxide, methylcyclohexanone peroxide, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butylperoxide, t-butylperoxybenzoate, diisopropylperoxy Organic peroxides such as carbonate and t-butylperoxyisopropyl monocarbonate, and azo compounds such as 2,2'-azobisisobutyronitrile (AIBN).

&Lt; Active energy ray curable composition &gt;

(B) a polymerizable unsaturated group-containing compound other than the component (a), and (c) a polymerizable unsaturated group-containing polymer (A) is contained in an amount of 5 to 95 parts by mass, preferably 10 to 90 parts by mass, per 100 parts by mass of the total amount of the components (a) and (b) More preferably 30 to 90 parts by mass, and the content of the component (b) is 5 parts by mass to 95 parts by mass, preferably 10 parts by mass (100 parts by mass) per 100 parts by mass of the total amount of the components (a) To 90 parts by mass, more preferably 10 parts by mass to 70 parts by mass. When the content of isosorbide di (meth) acrylate is less than 5 parts by mass, it is difficult to obtain a cured coating film having the same hardness by irradiation with active energy rays in the presence atmosphere of oxygen and active energy ray irradiation in a nitrogen atmosphere, The hardness of the cured coating film obtained by irradiation with active energy rays under the atmosphere is lower than the hardness of the cured coating film obtained by active energy ray irradiation under a nitrogen atmosphere. On the other hand, if it is more than 95 parts by mass, the shrinkage stress due to the curing is large, so that cracks are generated in the cured coating film.

The content of the component (c) is 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (a) and the component (b). If the content of the component (c) is less than 0.1, the active energy ray sensitivity becomes insufficient. On the other hand, if it is more than 20 parts by mass, the active energy ray does not sufficiently reach the deep portion of the coating film, and the hardening property of the coating film deep portion is lowered. If the amount is more than 20 parts by mass, the cured coating film is colored.

A light stabilizer, an ultraviolet absorber, a catalyst, a leveling agent, a defoaming agent, a polymerization promoter, an antioxidant, a flame retardant, an ultraviolet absorber and the like may be added to the active energy ray curable composition of the present invention.

The active energy ray curable composition of the present invention may be diluted with a solvent as desired. Examples of the solvent used for dilution include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Esters such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; Ethers such as tetrahydrofuran, dioxane and dimethoxyethane; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; Aromatic hydrocarbons, aliphatic hydrocarbons, and the like. These can be used in any combination.

The active energy ray curable composition of the present invention can be applied to the surface of a substrate (substrate). The method is not particularly limited, and examples thereof include a roller coating, a roll coating, a spin coating, a curtain coating, a slit coating, a bar coating, a spray coating, an electrostatic coating, Spin coating, and the like.

The substrate is not particularly limited, and examples thereof include various metal materials and plastic materials; Inorganic materials such as glass, cement, and concrete; wood; A fiber material (paper, cloth, etc.), and a coating layer such as a primer layer may be formed on these.

The film thickness of the coating film is appropriately set according to the purpose. For example, the film thickness is preferably 1 占 퐉 to 100 占 퐉, more preferably 1 占 퐉 to 50 占 퐉.

The energy source for curing the active energy ray-curable composition of the present invention is not particularly limited, and examples thereof include high-pressure mercury lamps, electron beams,? -Rays, carbon arc lamps, xenon lamps, metal halides (Light).

The irradiation amount is preferably in the range of 5 J / m 2 to 20,000 J / m 2, more preferably 100 J / m 2 to 10,000 J / m 2, for example.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples. In addition, "part (s)" and "%" refer to "part by mass" and "% by mass", respectively, unless otherwise specified.

1. Synthesis of isosorbide diacrylate

[Synthesis Example 1]

146 g (1 mol) of isosorbide, 144 g (2 mol) of acrylic acid, 0.15 g (0.0014 mol) of p-benzoquinone, 1.5 g (0.015 mol) of methanesulfonic acid and 700 g of toluene were placed in a 1 L four- , And the mixture was heated in an oil bath at 120 占 폚 while introducing air, and stirred for 10 hours. The reaction was carried out while distilling off water as the reaction progressed. After the completion of the reaction, the reaction mixture was cooled to room temperature and washed with 100 ml of distilled water to remove the catalyst. Thereafter, 0.025 g of hydroquinone was added, and the solvent was removed under reduced pressure to obtain a pale yellow viscous liquid.

This was analyzed by ¹ H-NMR, liquid chromatography (HPLC) and GC-mass spectroscopy to confirm that it was isosorbide diacrylate.

2. Preparation and evaluation of active energy ray-curable composition

[Example 1]

, 20 parts of isosorbide diacrylate, 0.75 part of caprolactone-modified dipentaerythritol hexaacrylate (5 parts of "Kayarad DPCA60" manufactured by Nippon Kayaku Co., Ltd., polymerization initiator (Ciba Specialty Chemicals, IRGACURE 184) Were mixed to obtain an active energy ray curable composition 1. The following evaluation tests were carried out on the obtained active energy ray curable composition 1. The evaluation results are shown in Table 1.

[Example 2]

, 20 parts of isosorbide diacrylate, 5 parts of pentaerythritol triacrylate adduct of hexamethylene diisocyanate, 0.75 part of polymerization initiator (Ciba Specialty Chemicals, IRGACURE 184) and 5 parts of butyl acetate were mixed to obtain an active energy Ray-curable composition 2 was obtained. The obtained active energy ray curable composition 2 was subjected to the following evaluation tests. The evaluation results are shown in Table 1.

[Example 3]

, 15 parts of isosorbide diacrylate, 10 parts of caprolactone modified tris (2-acryloyloxyethyl) isocyanurate (Aronix M-325 available from Toagosei Co., Ltd.), 10 parts of polymerization initiator (Ciba Specialty Chemicals Co., , IRGACURE 184, 0.75 part) and butyl acetate (5 parts) were mixed to obtain an active energy ray curable composition 3. The obtained active energy ray curable composition 3 was subjected to the following evaluation test. The evaluation results are shown in Table 1.

[Example 4]

10 parts of isosorbide diacrylate, 10 parts of caprolactone-modified tris (2-acryloyloxyethyl) isocyanurate (Aronix M-325 made by Toagosei Co., Ltd.), 5 parts of trimethylolpropane triacrylate, 0.75 part of a polymerization initiator (Ciba Specialty Chemicals, IRGACURE 184) and 5 parts of butyl acetate were mixed to obtain an active energy ray curable composition 4. The obtained active energy ray curable composition 4 was subjected to the following evaluation tests. The evaluation results are shown in Table 1.

[Comparative Example 1]

20 parts of tricyclodecane dimethanol diacrylate, 5 parts of caprolactone-modified dipentaerythritol hexaacrylate, 0.75 part of polymerization initiator (Ciba Specialty Chemicals, IRGACURE 184) and 5 parts of butyl acetate were mixed to prepare an active energy ray Curable composition 5 was obtained. The obtained active energy ray curable composition 5 was subjected to the following evaluation test. The evaluation results are shown in Table 1.

[Comparative Example 2]

20 parts of tricyclodecane dimethanol diacrylate, 5 parts of pentaerythritol triacrylate adduct of hexamethylene diisocyanate, 0.75 part of polymerization initiator (Ciba Specialty Chemicals, IRGACURE 184) and 5 parts of butyl acetate were mixed, An active energy ray curable composition 6 was obtained. The obtained active energy ray curable composition 6 was subjected to the following evaluation test. The evaluation results are shown in Table 1.

&Lt; Evaluation test &gt;

(Trial version)

Each active energy ray-curable composition was applied on a glass substrate by bar coater so that the dry film thickness became 10 mu m. Subsequently, the substrate was dried at 60 DEG C for 4 minutes to remove the solvent. Subsequently, the coating film was irradiated with ultraviolet rays of 600 mJ / cm 2 under an air atmosphere and a nitrogen atmosphere using an ultra-high pressure mercury lamp to cure the coating film to obtain a test plate.

(Hardenability)

The curability of the resultant cured coating film was evaluated with the hardness of the coating film (universal hardness value (HUk), load at maximum indentation: 2 mN at (hour)) using an ultrahigh hardness tester (Fisher Scope H-100 manufactured by Fisher Instruments) did.

(Moisture resistance)

The test plate was allowed to stand for 240 hours in an internal humidity tester (cab temperature 49 ± 1 ° C, relative humidity 95% or higher) to conduct the test. The coated film surface after the test was visually observed and evaluated according to the following criteria.

O: No change is recognized on the coating film surface.

DELTA: Insufficient gloss.

X: A blister is generated.

(Heat resistance)

The test plate was allowed to stand at 85 캜 for 96 hours. The coated film surface after the test was visually observed to examine changes in appearance.

(Chemical resistance)

0.1N-HCl and 0.1N-NaOH were spotted on the cured coating film of the test plate, the surface was covered with a watch glass (dish), preserved at 25 ° C for 24 hours, and then the surface was wiped And evaluated according to the following criteria.

O: No change is recognized on the coated film surface.

?: Some whitening or blister was recognized on the coating film surface.

X: White patches or air bubbles are remarkably recognized on the surface of the coated film.

As shown in Table 1, the active energy ray curable composition of the present invention exhibited equivalent curability under a nitrogen atmosphere even in an air atmosphere. In addition, the active energy ray curable composition of the present invention exhibited excellent moisture resistance, heat resistance and chemical resistance even when cured in an atmosphere of air or under a nitrogen atmosphere. On the other hand, the active energy ray-curable composition of the comparative example was inferior in curability under an air atmosphere compared to a nitrogen atmosphere. In addition, the active energy ray-curable composition of the comparative example was inferior in moisture resistance when cured in an air atmosphere, as compared with the case of curing under nitrogen atmosphere.

The active energy ray curable composition of the present invention has a high active energy ray sensitivity and can obtain a cured coating film having the same hardness as that in the case of active energy ray irradiation under an atmosphere of nitrogen under active oxygen ray irradiation in the presence atmosphere of oxygen, Resistant property, heat resistance and chemical resistance, it can be suitably used as a coating material for forming a resist resin composition such as a dry film resist, a colored resist, a black resist, and a clear paint.

Claims (2)

(a) isosorbide di (meth) acrylate,
(meth) acrylate, (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) Two or more, and
(c) a polymerization initiator by an active energy ray,
Wherein the content of the component (a) is 30 parts by mass to 90 parts by mass in 100 parts by mass of the total amount of the component (a) and the component (b)
The content of the component (b) is 10 parts by mass to 70 parts by mass in 100 parts by mass of the total amount of the component (a) and the component (b)
Wherein the content of the component (c) is 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (a) and the component (b). The method according to claim 1,
Wherein the component (b) is selected from the group consisting of caprolactone-modified dipentaerythritol hexaacrylate, pentaerythritol triacrylate adduct of hexamethylene diisocyanate, caprolactone modified tris (2-acryloyloxyethyl) isocyanurate, Propane triacrylate, and the like. The active energy ray-curable composition according to claim 1,