JP2001181314A - Photo-polymerization initiator and photo-polymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photo-polymerization initiator which can initiate polymerization at a high sensitivity by irradiating visible light, and a photo-curable composition containing the photo-polymerization initiator. SOLUTION: There are provided a photo-polymerization initiator comprising combinedly 3-10 pts.wt. of a boron compound an 1 pt.wt. of an organic dye having no counter ions, and a photo-curable composition containing the photo-polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerization initiator capable of initiating polymerization of at least one ethylenically unsaturated monomer or oligomer with high sensitivity by visible light, and to a photopolymerization initiator. It relates to a photocurable composition.

[0002]

2. Description of the Related Art Photopolymerization is used in a variety of applications, such as curing of coating films, lithographic printing, resin letterpress, for making a printed circuit board, resist or photomask, and making a black and white or color transfer color forming sheet or color forming sheet. Have been. Photopolymerizable compositions are also used in the field of dental technology and the like. The photopolymerizable composition comprises an ethylenically unsaturated compound and a photopolymerization initiator (see, for example,
JP-A-138203 and JP-A-63-162769) and JP-A-63-162769 disclose an α-ketocarbonyl compound as a photopolymerization initiator and a vinyl compound in the presence of an amine such as N, N-dimethylaniline. Disclosed are photopolymerizable compositions that can be cured by ultraviolet irradiation, and they are also used in the manufacture of tooth fillings and sealants, crowns and denture bridges, and in the manufacture of synthetic dentures (for example, JP-A-63-99858, JP-A-6-99858
3-189144 and JP-A-63-203151). Further, ultraviolet curable inks have been actively developed as photopolymerizable compositions (for example, JP-A-1-229084, JP-A-1-271469 and JP-A-2-22370). However, photopolymerization using ultraviolet rays has problems in poor permeability of ultraviolet rays to monomers, ozone generation by ultraviolet rays, skin irritation, and the like.

[0003]

An object of the present invention is to provide a photopolymerization initiator capable of initiating polymerization with high sensitivity by irradiation with visible light, and a photocurable composition containing the photopolymerization initiator. And

[0004]

According to the present invention, in order to solve this problem, a photopolymerization initiator using an organic dye capable of absorbing visible light and a boron compound in combination and containing the photopolymerization initiator are provided. As a result of intensive studies on the photocurable composition, they have found that a photopolymerization initiator spectrally sensitized with visible light with high sensitivity and a photocurable composition containing the photopolymerization initiator can be obtained. That is, the present invention contains a photopolymerization initiator obtained by combining 3 to 10 parts by weight of the boron compound represented by the general formula (1) with 1 part by weight of an organic dye having no counter ion, and the photopolymerization initiator. It relates to a photocurable composition.

Formula (1):

Embedded image Wherein R ₁ , R ₂ , R ₃ and R ₄ are independently alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, silyl, alicyclic and saturated or unsaturated heterocyclic groups or Substituted alkyl, substituted aryl,
Substituted alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl and substituted silyl are shown. R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom,
Alkyl, aryl, allyl, alkaryl, aralkyl, alkenyl, alkynyl, alicyclic and saturated or unsaturated heterocyclic groups or substituted alkyl, substituted aryl, substituted alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl Show. )

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The organic dye having no counter ion used in the present invention is a dye in which the organic dye is not composed of a counter ion and which is formed by resonance within the same molecule.
And the types thereof include merocyanine-based, coumarin-based, indigo-based, aromatic amine-based, phthalocyanine-based, azo-based, quinone-based, and squarylium-based dyes that absorb in the visible light region. Typical examples include those shown in Table 1.

[0007]

[Table 1]

In Table 1, 1) Me represents a methyl group. 2) Et represents an ethyl group. 3) Bu represents an n-butyl group. 4) Pr represents an n-propyl group. 5) tBu represents a t-butyl group. 6) cHex represents a cyclohexyl group. 7) Oct represents an n-octyl group. 8) Ph represents a phenyl group. 9) MeO represents a methoxy group. 10) All represents an allyl group. 11) Bz represents a benzyl group. 12) Tol represents a p-methylphenyl group.

Specific examples of the boron compound used in the present invention include tetramethylammonium n-butyltriphenylboron, tetramethylammonium n-butyltrianisylboron, tetramethylammonium n
-Octyl triphenyl boron, tetramethyl ammonium n-octyl trianisyl boron, tetraethyl ammonium n-butyl triphenyl boron, tetraethyl ammonium n-butyl trianisyl boron, trimethyl hydrogen ammonium n-butyl triphenyl boron, triethyl hydrogen ammonium n-butyl Triphenyl boron, tetrahydrogen ammonium n-butyl triphenyl boron, tetramethyl ammonium tetraphenyl boron, tetraethyl ammonium tetraphenyl boron, tetrabutyl ammonium tetraphenyl boron, tetramethyl ammonium tetraanisyl boron, tetraethyl ammonium tetraanisyl boron, tetra Butyl ammonium tetraanisyl boron, tetrame Le ammonium triphenyl naphthyl boron, tetraethylammonium triphenyl naphthyl boron, tetrabutylammonium triphenyl naphthyl boron, tetramethylammonium tetrabutyl borate, tetraethylammonium tetrabutyl borate,

[0010] Tetramethylammonium tri-n-butyl (
(Triphenylsilyl) boron, tetraethylammonium tri-n-butyl (triphenylsilyl) boron, tetrabutylammonium tri-n-butyl (triphenylsilyl) boron, tetramethylammonium tri-n-butyl (
Dimethylphenylsilyl) boron, tetraethylammonium tri-n-butyl (dimethylphenylsilyl) boron, tetrabutylammonium tri-n-butyl (dimethylphenylsilyl) boron, tetramethylammonium n-
Octyl diphenyl (di-n-butylphenylsilyl) boron, tetraethyl ammonium n-octyl diphenyl (
Di-n-butylphenylsilyl) boron, tetrabutylammonium n-octyldiphenyl (di-n-butylphenylsilyl) boron, tetramethylammonium dimethylphenyl (trimethylsilyl) boron, tetraethylammonium dimethylphenyl (trimethylsilyl) boron,
And tetrabutylammonium dimethylphenyl (trimethylsilyl) boron.

In the present invention, the boron compound is added in an amount of 3 to 10 parts by weight, more preferably 3 to 5 parts by weight, based on 1 part by weight of the organic dye of the present invention.
A photopolymerization initiator capable of initiating polymerization with high sensitivity by irradiation with visible light of 00 to 700 nm is obtained. By adding the photopolymerization initiator according to the present invention to a free-radical addition-polymerizable or crosslinkable compound, or a mixture of the compound and an organic or inorganic filler or a composite thereof, visible light irradiation is performed. Thus, the photopolymerizable composition of the present invention that can be polymerized can be obtained. Further, if necessary, general coloring dyes and pigments or other dyes absorbing light having a wavelength longer than visible light can be added.

The photopolymerization initiator of the present invention is preferably used in combination with an oxygen removing agent capable of absorbing oxygen in a free radical chain process and a chain transfer agent of an active hydrogen donor. Examples of oxygen scavengers include phosphine, phosphite, phosphonate, stannous salts, and other compounds that are easily oxidized by oxygen. Chain transfer agents include N-substituted N-phenylglycine such as N-phenylglycine, methacryloxy-β-hydropropyl-N-phenylglycine, trimethylbarbituric acid, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, N, N -Dialkylaniline and the like. Examples of N, N-dialkylaniline include one or more of an ortho, meta or para position having an alkyl group, a phenyl group, an acetyl group, an ethoxycarbonyl group,
It is substituted by a carbonyl group, a carboxylate group, a silyl group, an alkoxy group, a phenoxy group, an acetyloxy group, a hydroxy group, a halogen group, or the like.

A particularly preferred example is one in which the ortho position is substituted with an alkyl group, and 2,6-diisopropyl-
N, N-dimethylaniline, 2,6-diethyl-N, N-dimethylaniline, N, N, 2,4,6-pentamethylaniline and pt
-Butyl-N, N-dimethylaniline and the like. Furthermore, the photopolymerization initiator used in the present invention can further increase the sensitivity when used in combination with an organic peroxide. Examples of organic peroxides used are all conventional organic peroxides, specifically diacetyl peroxides such as dibenzoyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide, 3,
3 ', 4,4'-tetra- (t-butylperoxycarbonyl)
Examples include peroxycarbonates such as benzophenone.

Furthermore, the free-radical addition-polymerizable or crosslinkable compounds for which the photoinitiators according to the invention can be used are all customary ethylenically unsaturated compounds,
In particular, acrylic acid esters or methacrylic acid esters of monohydric alcohols or polyhydric alcohols or aromatic polycarboxylic acids containing 4- (meth) acryloyloxyl group and their acid anhydrides, and these esters include so-called urethane acrylates or methacrylates And the reactants known from U.S. Pat. No. 3,066,112, such as 2,2-bis (4- (3-methacryloxy-2-hydroxypropoxy) -phenyl) propane and di (methacryloxyethyl) trimethylhexamethylenediamine. Urethane, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, tetramethylolmethanetrimethacrylate, tetramethylolmethanetetramethacrylate,
Also included are dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 4- (meth) acryloyloxymethoxycarbonylphthalic acid and its anhydride, 4- (meth) acryloyloxyethoxycarbonylphthalic acid and its anhydride, and the like.

Further, a filler can be added to the photopolymerizable composition containing the photopolymerization initiator and the ethylenically unsaturated compound of the present invention. Examples of the filler include organic or inorganic, or a composite thereof.Examples of the organic filler include those obtained by finely pulverizing the polymer of the above-mentioned ethylenically unsaturated compound, and examples of the inorganic filler. ,
Silica, silica-alumina, alumina, quartz, glass,
Calcium carbonate, kaolin, talc, mica, aluminum sulfate, barium sulfate, calcium sulfate, titanium oxide,
Powders such as calcium phosphate and the like can be mentioned. Organic-inorganic composites obtained by coating the surface of these inorganic powders with a polyfunctional (meth) acrylate monomer or a silane coupling agent, and these inorganic fillers Examples thereof include those mixed with the above-mentioned ethylenically unsaturated compound, polymerized and cured, and then finely pulverized.

The organic dye constituting the photopolymerization initiator of the present invention having an absorption in the visible light region is from 0.01 to 20% by weight, preferably from 0.1 to 10% by weight, based on the ethylenically unsaturated compound. Further, the oxygen scavenger and the chain transfer agent can be added in the same amount as the organic dye. In addition, a composition that can be polymerized by both visible light and near-infrared light can be obtained in combination with an initiator that can start polymerization by near-infrared light.

The photopolymerization initiator of the present invention is sensitive to visible light of 400 to 700 nm and initiates polymerization, but polymerization is not initiated by near-infrared light and infrared light of 700 nm or more, When using the polymerization initiator, it is desirable to handle it under light such as an infrared lamp. Applicable examples of the photopolymerization initiator according to the present invention include a photopolymerization is used, screen printing, sheet-fed printing, lithographic printing, letterpress printing,
Metal surface processing, ink, printing board creation, resist or photomask, black and white or color transfer coloring sheet or coloring sheet creation, copier toner, copier capsule toner, paint, adhesive, and curing of unsaturated polyester , Rubber cross-linking, polyolefin modification and cross-linking.

The composition comprising the photopolymerization initiator, an ethylenically unsaturated compound and a leuco dye or a coloring dye or pigment can be used for producing a black or color transfer color forming sheet or a color forming sheet. Yes, and
These compositions can be used by being encapsulated in microcapsules. In addition, it can be applied as a photopolymerizable composition for dental treatment, such as a denture with a denture, a dental prosthetic material and a tooth filling composition, and a coating and adhesive composition for dental purposes. However, the photopolymerization initiator according to the present invention is not limited to these application examples.

A specific example of application to a printing ink is a photocurable ink obtained by kneading a monomer and a prepolymer containing an ethylenically unsaturated group, which is generally used as an active vehicle, with a photopolymerization initiator and a pigment. 5μm on aluminum foil paper used for cosmetics and food packaging
It can be dried and fixed on aluminum foil paper without permeation and drying properties by printing with a thickness of 10 mm and irradiating with a visible light irradiating device.

[0020]

EXAMPLES The present invention will be further described below with reference to examples. Examples 1, 2 Trimethylolpropane trimethacrylate 10 parts by weight Organic dye As shown in Table 2 Boron-based compound As shown in Table 2, a mixture composed of an infrared lamp (manufactured by PHILIPS, IR150
The sample was prepared under the light of R), filled in a stainless steel-steel mold (inner diameter 6 mm, height 8 mm), and the surface was covered with polyester foil to prepare a sample.

Examples 3,4 Tetramethylolpropane trimethacrylate 10 parts by weight Organic dyes Shown in Table 2 Boron compounds Shown in Table 2 N, N, 2,4,6-pentamethylaniline 0.04 parts by weight of a mixture comprising To an infrared lamp (PHILIPS, IR150
The sample was prepared under the light of R), filled in a stainless steel-steel mold (inner diameter 6 mm, height 8 mm), and the surface was covered with polyester foil to prepare a sample.

Example 5 Tetramethylolpropane trimethacrylate 6 parts by weight Triethylene glycol dimethacrylate 4 parts by weight Organic dyes Shown in Table 2 Boron compounds Shown in Table 2 N, N, 2,4,6-pentamethylaniline 04 parts by weight of a mixture consisting of an infrared lamp (manufactured by PHILIPS, IR150
The sample was prepared under the light of R), filled in a stainless steel-steel mold (inner diameter 6 mm, height 8 mm), and the surface was covered with polyester foil to prepare a sample.

Example 6 2,2-bis (4- (3-methacryloxy-2-hydroxypropoxy) -phenyl) propane 4 parts by weight Tetramethylolpropane trimethacrylate 4 parts by weight Triethylene glycol dimethacrylate 2 parts by weight Organic dye Indicated in Table 2 Boron-based compound Indicated in Table 2 N, N, 2,4,6-pentamethylaniline 0.04 parts by weight Fine silica (particle diameter 10 μm or less, average particle diameter 5 μm) 30 parts by weight of a mixture comprising Lamp (PHILIPS, IR150
The sample was prepared under the light of R), filled in a stainless steel-steel mold (inner diameter 6 mm, height 8 mm), and the surface was covered with polyester foil to prepare a sample.

Examples 7,8 Tetramethylolpropane trimethacrylate 6 parts by weight Diethylene glycol dimethacrylate 4 parts by weight Organic dyes Shown in Table 2 Boron-based compounds Shown in Table 2 N, N, 2,4,6-pentamethylaniline 04 parts by weight Coloring dye A mixture consisting of the components shown in Table 2 was mixed with an infrared lamp (manufactured by PHILIPS, IR150
The sample was prepared under the light of R), filled in a stainless steel-steel mold (inner diameter 6 mm, height 8 mm), and the surface was covered with polyester foil to prepare a sample.

Examples 9,10 Tetramethylolpropane trimethacrylate 6 parts by weight Diethylene glycol dimethacrylate 4 parts by weight Organic dyes Shown in Table 2 Boron compounds Shown in Table 2 N-phenylglycine 0.03 parts by weight Coloring dyes Shown in Table 2 The mixture consisting of the mark is transferred to an infrared lamp (PHILIPS, IR150
The sample was prepared under the light of R), filled in a stainless steel-steel mold (inner diameter 6 mm, height 8 mm), and the surface was covered with polyester foil to prepare a sample.

Examples 11 and 12 Tetramethylolpropane trimethacrylate 6 parts by weight Diethylene glycol dimethacrylate 4 parts by weight Organic dyes Shown in Table 2 Boron-based compounds Shown in Table 2 Organic peroxides Shown in Table 2 PH150, IR150
The sample was prepared under the light of R), filled in a stainless steel-steel mold (inner diameter 6 mm, height 8 mm), and the surface was covered with polyester foil to prepare a sample.

Comparative Example 1 A sample was prepared in the same manner as in Example 1 except that the boron compound was not used. The samples obtained in the above Examples 1 to 12 and Comparative Example 1 were irradiated with light from a dichroic coat type halogen lamp (2 W / cm ² ) using an infrared cut filter, and irradiated with only visible light for 1 second to polymerize. The sex was evaluated. Table 3 shows the evaluation results.
Shown in

[0028]

[Table 2]

In Table 2, TMAPB: tetramethylammonium n-butyltriphenylboron TBAPB: tetrabutylammonium n-butyltriphenylboron TMHPB: triethylhydrogenammonium n-
Butyltriphenylboron TBABB: Tetrabutylammonium tetra-n-butylboron TBATS: Tetrabutylammonium tri-n-butyl (dimethylphenylsilyl) boron TBBPB: 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) Benzophenone TEKP: Methyl ethyl ketone peroxide

[0030]

[Table 3]

[0031]

According to the present invention, a photopolymerization initiator comprising 3 to 10 parts by weight of a boron compound and 1 part by weight of an organic dye having no counter ion, which can initiate polymerization with high sensitivity by irradiation with visible light. And a photopolymerizable composition containing the photopolymerization initiator.

Claims (4)

[Claims] 1 to 3 parts by weight of a boron compound represented by the general formula (1) and 1 part by weight of an organic dye having no counter ion and having an absorption in the visible light region represented by the general formula (2). A photopolymerization initiator comprising General formula (1); (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently an alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, silyl, A cyclic or saturated or unsaturated heterocyclic group or substituted alkyl, substituted aryl, substituted alkaryl, substituted allyl, substituted aralkyl, substituted alkenyl, substituted alkynyl, substituted silyl, and R ₅ , R ₆ , R ₇ and R
₈ is independently hydrogen atom, alkyl, aryl, allyl, alkaryl, aralkyl, alkenyl, alkynyl, alicyclic and saturated or unsaturated heterocyclic group or substituted alkyl, substituted aryl, substituted alkaryl, substituted allyl, It represents substituted aralkyl, substituted alkenyl, and substituted alkynyl. ) 2. An organic dye having absorption in the visible light region and having no counter ion is a merocyanine-based, coumarin-based, indigo-based, aromatic amine-based, phthalocyanine-based, azo-based, quinone-based, or squarylium-based organic dye. The photopolymerization initiator according to claim 1, which is: 3. A photopolymerizable composition comprising the photopolymerization initiator according to claim 1 and an ethylenically unsaturated compound. 4. The photopolymerizable composition according to claim 3, wherein the composition comprises at least one of an inorganic filler, an organic filler and an organic-inorganic composite.