JPH11263804A - Photo-curing composition and method of curing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photo-curing composition capable of photo-curing a photo-curing composition containing a diaryliodonium salt as a photo-curing catalyst effectively and to provide a photo-curing composition which can cure in a short period of time even if it contains additives such as a pigment and which has excellent cured material properties. SOLUTION: A composition comprises a diaryliodonium salt derivative which acts as a photo cation polymerization catalyst, a polycyclic aromatic compound such as naphthalene derivative or phenanthrene derivative which has at least one of a hydroxyl group, an aralkyloxy group which may be substituted or an alkoxy group as a substituent, a thioxanthone derivative, a cation- polymerizable compound and a pigment such as titanium dioxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photocurable composition, and more particularly to a sensitized photocationically curable composition. The photocurable composition of the present invention is cured by irradiation with active energy rays such as light, electron beams, and X-rays, and has excellent characteristics particularly in long-wavelength photosensitivity, so that photocurable paints, adhesives, inks and the like can be obtained. It is suitably used for a photoresist, a photosensitive resin for stereolithography, and the like.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open Nos. 50-151997, 50-158680 and 50-15199
No. 6, the arylonium salt compound of the present invention includes:
It describes that it can be used as a catalyst for curing a cationically polymerizable compound such as an epoxy compound by radiation such as light, an electron beam, and X-ray. Since these arylonium salt compounds have little absorption at wavelengths longer than 360 nm, which is considered to be effective for ultraviolet curing, photocuring using additives such as photolithography using long-wavelength laser light and pigments is used. It is known that the curability of the composition is significantly reduced. In particular, the UV of arylonium salt compounds
A photocurable composition containing a large amount of a white pigment such as titanium oxide whose absorption region overlaps with the absorption region has many problems in use. As a solution to this, sensitizers have been studied. For example, various dye derivatives have been reported to be effective as sensitizers for diaryliodonium salts. It has been known. However, with these thioxanthone derivatives alone,
The photocurability of a photocurable composition using an additive such as a pigment is insufficient.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of these circumstances, and an object of the present invention is to effectively photo-cur a photocurable composition containing a diaryliodonium salt as a photocuring catalyst. While providing a photocurable composition capable of, it is possible to cure in a short time even a composition containing an additive such as a pigment, and a photocurable composition having excellent cured physical properties. To provide.

[0004]

Means for Solving the Problems The present inventors diligently studied to solve the above-mentioned problems, and found that a photocurable composition containing a diaryliodonium salt as a photocuring catalyst was added to a specific sensitizer as a sensitizer. They have found that a photocurable composition that overcomes the above-mentioned problems can be obtained by using a combination of a polycyclic aromatic compound and a thioxanthone derivative, and completed the present invention.

That is, the present invention provides a diaryliodonium salt derivative which acts as a photocationic polymerization catalyst, and a polycyclic aromatic compound having at least one hydroxyl group, an optionally substituted aralkyloxy group or an alkoxy group as a substituent. A photocurable composition comprising a thioxanthone derivative and a cationically polymerizable compound, preferably the photocurable composition wherein the polycyclic aromatic compound is a naphthalene derivative or a phenanthrene derivative; An alicyclic epoxy compound,
The present invention relates to the photocurable composition, which is one or more compounds selected from the group consisting of vinyl ether compounds and oxetane compounds.

Further, the present invention provides a diaryl iodonium salt derivative which acts as a photocationic polymerization catalyst, a polycyclic aromatic compound having at least one hydroxyl group, an optionally substituted aralkyloxy group or an alkoxy group as a substituent. And a thioxanthone derivative, a cationically polymerizable compound, and a pigment such as titanium dioxide.

Further, the present invention provides a diaryliodonium salt derivative which acts as a photocationic polymerization catalyst, a polycyclic aromatic compound having at least one hydroxyl group, an optionally substituted aralkyloxy group or an alkoxy group as a substituent. The present invention relates to a method for photocuring the above photocurable composition, which comprises irradiating a photocurable composition comprising a thioxanthone derivative, a cationically polymerizable compound, and a pigment with a gallium-containing lamp.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diaryl iodonium salt derivative which acts as a photocationic polymerization catalyst, a polycyclic aromatic compound having at least one hydroxyl group, an optionally substituted aralkyloxy group or an alkoxy group as a substituent. A photocurable composition comprising a compound, a thioxanthone derivative, a cationically polymerizable compound, and additives such as a pigment compounded as necessary.

The diaryliodonium salt derivative of the present invention can be used without any limitation as long as it acts as a photocationic polymerization catalyst. For example, a diphenyliodonium salt represented by the following chemical formula (1) can be used. Compounds selected from the group consisting of derivatives, phenylnaphthyliodonium salt derivatives, and dinaphthyliodonium salt derivatives, such as those represented by Chemical Formula 1, can be used in combination of two or more. .
The counter anion of these derivatives is a non-nucleophilic anion such as SbF ₆ , As ₆ , PF ₆ , BF ₆ , (F ₅ C ₅ )
₄ B value, if it is not limited to the type and the like.

[0010]

Embedded image

Used as a sensitizer in the present invention;
Examples of the polycyclic aromatic compound having at least one hydroxyl group, an optionally substituted aralkyloxy group or an alkoxy group as a substituent include 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 1-stearyloxynaphthalene, 2-methoxynaphthalene, 2-dodecyloxynaphthalene, 4-methoxy-1-naphthol, glycidyl-1-naphthyl ether, 2- (2-naphthoxy) ethyl vinyl ether, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,7-dimethoxynaphthalene, 1,1′-thiobis (2-naphthol), 1,1′-bi-2-naphthol, 1,5-naphthyldi Glycidyl ether, 2,7-
Di (2-vinyloxyethyl) naphthyl ether, 4-
Methoxy-1-naphthol, ESN-175 (epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) or a series thereof, naphthalene derivatives such as condensates of naphthol derivatives and formalin, 9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-ethoxy Phenanthrene, 9-benzyloxyphenanthrene, 9,10-dimethoxyphenanthrene, 9,10-diethoxyphenanthrene, 9,
10-dipropoxyphenanthrene, 9,10-dibenzyloxyphenanthrene, 9,10-di-α-methylbenzyloxyphenanthrene, 9-hydroxy-10
Phenanthrene derivatives such as -methoxyphenanthrene and 9-hydroxy-10-ethoxyphenanthrene are used, and preferably phenanthrene derivatives such as 9,10-dimethoxyphenanthrene and 9,10-diethoxyphenanthrene can be exemplified.

In the present invention, the thioxanthone derivative used in combination with the above polycyclic aromatic compound as a sensitizer includes, for example, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone 2-chlorothioxanthone And the like.

The cationically polymerizable compound used in the present invention can be used without any limitation as long as it is a generally known monomer, oligomer or polymer having a cationically polymerizable group. Can be exemplified. (A) As the vinyl compound, styrene compounds such as styrene, α-methylstyrene, p-methoxystyrene, pt-butoxystyrene, methyl vinyl ether, n-
Butyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether,
Alkyl vinyl ether compounds such as 2-chloroethyl vinyl ether, 2-phenoxyethyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, and 2-acetoxyethyl vinyl ether; allyl vinyl ether; 2-methacryloyloxyethyl vinyl ether; Alkenyl vinyl ether compounds such as acryloyloxyethyl vinyl ether; aryl vinyl ether compounds such as phenyl vinyl ether and p-methoxyphenyl vinyl ether; N-vinyl carbazole;
-Polyfunctional such as cationically polymerizable nitrogen-containing compounds such as vinylpyrrolidone, butanediol divinyl ether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, 1,4-benzenedimethanol divinyl ether, hydroquinone divinyl ether, and sasolcinol divinyl ether. Vinyl compound, J
own of PolymerScience:
Part A: Polymer Chemistry,
Vol. 32, 2895 (1994), a Journal of Polym.
er Science: Part A: Polymer
Chemistry, Vol. 33, 2493 (19
95) the alkoxyallene compound described in Jo,
urnal of Polymer Science:
Part A: Polymer Chemistry,
Vol. 34, 1015 (1996), the Journal of Polymer.
Science: Part A: Polymer Ch
chemistry, Vol. 34, 2051 (1996)
And the like.

(B) Epoxy compounds include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene Monooxide, 1,2-dodecylene oxide,
Monofunctional such as epichlorohydrin, 1,2-epoxydecane, ethylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide monomer,
1,1,3-tetradecadienedoxide, limonenedoxide, 3,4-epoxycyclohexylmethyl- (3,4-epoxycyclohexyl) carboxylate, di (3,4-epoxycyclohexyl) adipate, bisphenol A type epoxy Resin, bisphenol F type epoxy resin, o-, m-, p-cresol novolak type epoxy resin, phenol novolak type epoxy resin, polyglycidyl ether of polyhydric alcohol, K-62-722 manufactured by Shin-Etsu Silicone and Toshiba Silicone Epoxy silicone such as UV9300 manufactured by Journ
al of Polymer Science: Par
tA: Polymer Chemistry, Vo
l. And polyfunctional epoxy compounds such as the silicone-containing epoxy compounds described in U.S. Pat. No. 28,497 (1990).

(C) The bicycloorthoester compounds include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2] octane and 1-ethyl-4
And compounds such as -hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane.

(D) Spiro orthocarbonate compounds include 1,5,7,11-tetraoxaspiro [5,
5] undecane, 3,9-dibenzyl-1,5,7,1
1-tetraoxaspiro [5,5] undecane, 1,
4,6-trioxaspiro [4,4] nonane, 2-methyl-1,4,6-trioxaspiro [4,4] nonane,
Compounds such as 1,4,6-trioxaspiro [4,5] decane can be exemplified.

(E) Oxetane compounds include 3,3
-Dimethyloxetane, 3,3-bis (chloromethyl)
Oxetane, 2-hydroxymethyloxetane, 3-methyl-3-oxetanemethanol, 3-methyl-3-methoxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, resorcinol bis (3-methyl-
Examples thereof include compounds such as 3-oxetanylethyl) ether and m-xylylenebis (3-ethyl-3-oxetanylethylether). These may be used alone or in combination of two or more.

In the present invention, the compounding ratio of the diaryliodonium salt derivative and the cationically polymerizable compound is 0.01 to 20 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. 10 parts by weight. When the amount of the diaryliodonium salt derivative is small, the curability of the cationically polymerizable compound is reduced. When the amount is excessive, the properties of the cured product are reduced.

On the other hand, the mixing ratio of the polycyclic aromatic compound and the cation polymerizable compound is set to 10
The polycyclic aromatic compound is added in an amount of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 0 parts by weight. When the amount of the polycyclic aromatic compound is small, the photoreactivity of the diaryliodonium salt derivative decreases, and when the amount is excessive, the properties of the composition deteriorate. However, for example, the polycyclic aromatic compound having a cationically polymerizable group such as an epoxy group or a vinyl ether group is not limited thereto, and the mixing ratio can be arbitrarily changed. The thioxanthone derivative is used in an amount of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the cationically polymerizable compound.

The photocurable composition of the present invention can be easily cured by light. As the light source, a low-pressure mercury lamp,
Medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, carbon arc lamps, etc. are used, and semiconductor lasers, argon lasers, He-
Although laser light such as Cd laser can be used,
In the case of a photocurable composition containing titanium dioxide as a white pigment, 380 to 450 nm without absorption by titanium dioxide
The use of a lamp that emits light efficiently, particularly a gallium-containing lamp, enables effective photo-curing, and is preferable in terms of improving the curing speed, the properties of the cured product, and the thick film curability. Further, the photocurable composition of the present invention comprises α rays, β
It can be easily cured by ionizing radiation such as X-ray, γ-ray, neutron beam, X-ray and accelerating electron beam.

When the photocurable composition of the present invention contains a pigment, it can be used for inks and photoresists. As the pigment used in the present invention, carbon black, acetylene black, orchid black, black pigments such as aniline black, graphite, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navels yellow, Yellow pigments such as naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, tartrazine lake, red mouth lead, molybdenum orange, permanent orange GTR, pyrazolone orange , Vulcan orange, Indaslen brilliant orange RK, Benzidine orange G, Indaslen brilliant orange GK, etc., orange pigments, bengara, cadmium red, lead red, sulfuric acid Mercury cadmium, permanent red 4R, lithol red, pyrazolone red, watching red calcium salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, brilliant carmine 3B
Red pigment, manganese purple, fast violet B, etc.
Purple pigments such as methyl violet lake, navy blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, partially chlorinated phthalocyanine blue, fast sky blue, blue pigments such as indaslen blue BC,
Chrome green, chromium oxide, pigment green B,
Green pigments such as Malachite Green Lake and Fanal Yellow Green G; white pigments such as zinc white, titanium dioxide, antimony white and zinc sulfide; and barite powder, barium carbonate, clay, silica, silica, white carbon, talc, alumina white, etc. An extender can be exemplified.

The effect of the sensitizer in the photocurable composition of the present invention can be more effectively attained in a composition using a white pigment such as zinc white, titanium dioxide, antimony white, and zinc sulfide than when no pigment is used. It is more clearly exhibited, and is particularly effective when titanium dioxide is used.

In order to control the physical properties, curability and the like of the cured product of the photocurable composition according to the present invention, a radical polymerizable compound can be used. As the radical polymerizable compound used in the present invention, any monomers, oligomers and polymers having radical polymerizability can be used regardless of the kind thereof. As the radical polymerizable monomer, monofunctional or polyfunctional acrylate or methacrylate monomer, etc., as the radical polymerizable oligomer, epoxy acrylate, epoxy methacrylate, polyester acrylate, polyester methacrylate, polyether acrylate, polyether methacrylate, polyurethane acrylate, Polyurethane methacrylate, polybutadiene acrylate, polybutadiene methacrylate, and the like, and radical polymerizable polymers include polyester, polybutadiene, and polyether. , Urethane, each acrylates such as epoxy, the methacrylate compounds, can be exemplified unsaturated polyesters.

Examples of the radically polymerizable reactive diluent include acrylic acid ester monomers such as acrylic acid and ethyl acrylate, methacrylic acid ester monomers such as methacrylic acid and methyl methacrylate, and styrene.

[0025]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the present invention is not limited to these examples. (Preparation of photocurable composition) 100 parts by weight of UVR-6110 (alicyclic epoxy manufactured by UCC) and 100 parts by weight of titanium oxide (CR-58 manufactured by Ishihara Sangyo Co., Ltd.), 3 parts by weight of a diaryliodonium salt derivative as a pure component , Polycyclic aromatic compound 1
By weight, 1 part by weight of the thioxanthone derivative was mixed to prepare a formulation of the present invention. A comparative example did not contain 1 part by weight of the polycyclic aromatic compound or 1 part by weight of the thioxanthone derivative. Table 1 shows the composition.

(Photocurability test) The above composition was applied to a tin plate with a bar coater No. 4 and photocured under the following conditions. Table 1 shows the results. In this photocurability test, those that were cured to the inside of the formulation are indicated by a circle, those that were semi-cured are indicated by a triangle, and those that were not cured are indicated by a cross. UV irradiation equipment: belt conveyor type UV irradiation equipment (manufactured by Eye Graphics Co., Ltd.) Lamp: one condensing type 160W gallium-containing metaharatamp irradiation distance: 10cm (focal length) Belt conveyor speed: 40m / min

[0027]

[Table 1]

[0028]

The photocurable composition of the present invention can be cured by irradiating active energy rays such as light, electron beams and X-rays. Furthermore, since the diphenyliodonium salt derivative has no absorption region or can be cured even with light having a wavelength longer than 330 nm, which has extremely small absorption, it can be effectively photocured even in a composition containing an additive such as a pigment. can do. Therefore, it is suitably used for photocurable paints, adhesives, inks, photoresists, and photosensitive resins for stereolithography.

Claims (6)

[Claims] 1. A diaryliodonium salt derivative acting as a photocationic polymerization catalyst, a hydroxyl group as a substituent,
A polycyclic aromatic compound having at least one aralkyloxy group or an alkoxy group which may be substituted,
A photocurable composition comprising a thioxanthone derivative and a cationically polymerizable compound. 2. The photocurable composition according to claim 1, wherein the polycyclic aromatic compound is a naphthalene derivative or a phenanthrene derivative. 3. The method according to claim 1, wherein the cationically polymerizable compound is one or more compounds selected from the group consisting of an alicyclic epoxy compound, a vinyl ether compound and an oxetane compound. Photocurable composition. 4. The photocurable composition according to claim 1, wherein the photocatalyst composition further contains a pigment. 5. The photocurable composition according to claim 4, wherein the pigment is titanium dioxide. 6. A diaryliodonium salt derivative acting as a photocationic polymerization catalyst, a hydroxyl group as a substituent,
A polycyclic aromatic compound having at least one aralkyloxy group or an alkoxy group which may be substituted,
A photocuring method comprising irradiating a gallium-containing lamp to a photocurable composition comprising a thioxanthone derivative, a cationically polymerizable compound, and a pigment.