JPH10310674A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition that is radically polymerized by irradiation with visible to near-infrared light and can be stored without gelation, by making the composition include a monomer having an ethylenically unsaturated polymerizable functional group and/or an oligomer thereof, a colorant compound, an organoboron compound and storage stabilizer. SOLUTION: The colorant compounds is one represented by the formula: D<+> .M<-> (wherein D<+> is an organic cationic colorant; and M<-> is an organic or inorganic anion) and having absorptions in the visible or near-infrared region. The organoboron compound is represented by formula I [wherein B is a boride ion; R<1> to R<4> are each a group selected among alkyls, aralkyls, etc.; and Z<+> is an alkali metal ion, an alkaline earth metal ion or an ammonium ion of formula II (wherein R<5> to R<8> are each a group selected among H, alkyls, aryls, aralkyls, etc.)]. The storage stabilizer is desirably an amine compound or a phosphine compound. The monomer and/or the oligomer each has acryloyl or methacryloyl in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a photopolymerizable composition. More specifically, the present invention relates to a storage-stabilized photopolymerizable composition which is capable of undergoing a radical polymerization reaction with high sensitivity to light in the visible to near-infrared region.

[0002]

2. Description of the Related Art A photopolymerizable composition comprising a monomer and / or oligomer having one or more polymerizable functional groups having an ethylenically unsaturated bond, a dye compound, an organic boron compound, and other additives has been proposed. (Japanese
4-13142, JP-A-2-4804, JP-A-7-29
2014) However, the storage stability of the composition is affected by the free carboxylic acid present in the composition and the temperature even when stored under light shielding, and the stability is deteriorated.

[0003] Organic boron compounds generate radicals with high sensitivity when irradiated with light in the presence of a dye compound.
Alternatively, heating at about 80 ° C. causes a radical reaction.
For example, if the free carboxylic acid (in terms of acrylic acid) is about 0.05% by weight in the composition, the light-
It can be stored stably without gelling for more than 20 minutes.
Gel in 8 minutes. The composition was protected from light at 80 ° C.
The gelation takes 5 minutes even if the free carboxylic acid is 0.05% by weight, and 3 minutes if the free carboxylic acid is 0.5% by weight. Thus, the photopolymerizable composition had a problem in storage stability.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a method for radical polymerization with high sensitivity to light in the visible to near infrared region. An object of the present invention is to provide a photopolymerizable composition that does not gel even when the photopolymerizable composition that causes a reaction is stored for a long period of time or at a high temperature.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies and have found that by adding a storage stabilizer to a photopolymerizable composition, further stabilization can be achieved. . That is, the present invention relates to a monomer and / or oligomer having one or more polymerizable functional groups having an ethylenically unsaturated bond, and a compound represented by the following general formula (1): D ⁺ · M ⁻ (where D ⁺ is an organic cationic compound) a dye, M ^- is a dye compound having absorption in the visible light or near infrared light region represented by an anion of an organic or inorganic), the general formula (2): Wherein B ^- is a boron ion, R ¹ , R ² , R ³ , R ⁴
Is a group selected from an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alkynyl group, an alicyclic group, a heterocyclic group, and an allyl group, each of which may be the same or different And two or more of them may combine to form a cyclic structure, and Z ⁺ represents an alkali metal ion, an alkaline earth metal ion or

General formula (3): (Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen, an alkyl group,
A group selected from an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alkynyl group, an alicyclic group, a heterocyclic group, and an allyl group, which may be the same or different; Or more may be bonded to form a cyclic structure)], and a storage stabilizer. It is. In the above, the storage stabilizer is preferably an amine compound or a phosphine compound.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The composition of the present invention basically comprises a dye compound having absorption in the visible or near infrared region, an organic boron compound and one polymerizable functional group having an ethylenically unsaturated bond. It contains the monomer and / or oligomer having the above and a storage stabilizer as components. In addition, chlorinated polyolefin resins, polymer compounds such as rubber components, dyes, pigments, fillers (talc, silica gel, alumina, calcium carbonate, etc.) thixotropic agents, antioxidants, solvents, suspending agents, mats, etc. Agents, thickeners and the like may be included.

Hereinafter, the components constituting the composition of the present invention will be described in detail. The dye compound having an absorption in the visible or near infrared region that can be used in the composition of the present invention is a compound represented by the general formula (1). Typical examples thereof include polymethine dye compounds, diphenylmethane dye compounds, triphenylmethane dye compounds, and azo dye compounds. A composition appropriately selected from these groups can be used alone or in combination of two or more.

Examples of the above-mentioned organic cationic dye compounds which can be used for the purpose of the present invention are described, for example, in "Dye Handbook" edited by Okawara, Kodansha, pp. 345-417. Examples of organic cationic dye compounds particularly suitable for the purpose of the present invention are listed in Table 1 together with their maximum absorption wavelengths (λmax).
I will give it. However, it goes without saying that the present invention is not limited to these dyes.

[0010]

[Table 1]

The organic boron compound that can be used in the present invention may be any compound having the structure of the general formula (2). Examples of the organic boron compound that can be suitably used in the present invention include tetramethylammonium n-butyltrianisylboron, tetramethylammonium n-butyltriphenylboron, tetramethylammonium n-octyltrianisylboron,
Tetramethyl ammonium n-octyl triphenyl boron, tetramethyl ammonium n-butyl tritolyl boron, tetramethyl ammonium n-butyl triphenyl silyl boron, tetraethyl ammonium
n-butyltrianisyl boron, tetraethyl ammonium n-butyl triphenyl boron, tetraethyl ammonium n-octyl trianisyl boron, tetraethyl ammonium n-octyl triphenyl boron, tetraethyl ammonium n-butyl triphenyl silyl boron, tetraethyl ammonium n-butyl tri Tolyl boron, tetraethyl ammonium tetra n-butyl boron, trimethyl ammonium hydrogen n
-Butyl trianisyl boron, trimethyl ammonium hydrogen n-butyl triphenyl boron, triethyl ammonium n-butyl trianisyl boron, triethyl ammonium n-butyl triphenyl boron, tetra hydrogen ammonium n-butyl trianisyl boron, tetra tetra ammonium n -Butyltriphenylboron, tetrahydrogenammonium tetraphenylboron, tetra-n-butylammonium n-butyltrianisylboron, tetra-n-butylammonium n
-Butyltriphenylboron, tetra-n-butylammonium n-butyltolylboron, tetra-n-butylammonium n-butyltriphenylsilylboron, sodium n-butyltriphenylboron, sodium n-butyltolylboron, sodium tetraphenyl Examples thereof include boron, potassium n-butyltriphenylboron, potassium n-butyltolylsylurium, and potassium tetraphenylboron.

As the monomers and / or oligomers having one or more polymerizable functional groups having an ethylenically unsaturated bond which can be used in the present invention, basically any compounds capable of radical polymerization can be used. Any compound can be used as long as it has at least one acryloyl group or methacryloyl group in the molecule. Examples of the monomer compound having at least one acryloyl group or methacryloyl group in a molecule that can be suitably used in the present invention include methyl acrylate, ethyl acrylate, isopropyl acrylate,
n-butyl acrylate, 2-ethylhexyl acrylate, isoamyl acrylate, isooctyl acrylate, lauryl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3-chloro-
2-hydroxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, acryloylmorpholine, N, N-dimethylacrylamide, N, N-diethylacrylamide, N,
N-dimethylaminopropylacrylamide, N, N-
Dimethylaminoethyl acrylate, phenoxyethyl acrylate, butoxyethyl acrylate, nonylphenoxyethyl acrylate, tetraethylene glycol-4-nonylphenyl ether acrylate, decaethylene glycol-4-nonylphenyl ether acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl Acrylate, tricyclo [5.
2.1.0 ^2.6 ] decanyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, isoamyl methacrylate, isooctyl methacrylate, isodecyl methacrylate,
Lauryl methacrylate, stearyl methacrylate,
Tetrahydrofurfuryl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 3-
Chloro-2-hydroxypropyl methacrylate, N,
N-dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminomethyl methacrylate, N, N-diethylaminoethyl methacrylate, phenoxyethyl methacrylate, nonylphenoxyethyl methacrylate, tetraethylene glycol-4-nonylphenyl ether Methacrylate, decaethylene glycol-4-nonylphenyl ether methacrylate, tricyclo [5.2.1.
0 ^2.6 ] decanyl methacrylate, glycidyl methacrylate, 2-methacryloylethyl isocyanate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, dimethylol tricyclodecane diacrylate , Tripropylene glycol diacrylate, hexapropylene glycol diacrylate, 2-hydroxy-1-
Acryloxy-3-methacryloxypropane, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butane Diol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6
-Hexanediol dimethacrylate, trimethylolpropane trimethacrylate and the like.

Examples of the oligomer include epoxy oligomers (trade names: UE8200 (manufactured by Dainippon Ink and Chemicals, Inc.), SP-1529X, SP-1509X (manufactured by Showa Polymer Co., Ltd.), YPB-40AM40 (manufactured by Toto Kasei Co.,
K ester A-BPE-4, NK ester BPE-20
0, NK ester BPE-500, NK ester BPE
-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester 30
02M, epoxy ester 3000A (manufactured by Kyoeisha Yushi Kagaku)], urethane oligomer [U-4HA, U-6H]
A, U-324A, U-200AX, U-340AX,
U-311 (manufactured by Shin-Nakamura Chemical Co., Ltd.), UN-9000PE
P, UN-5200, UN-9200A (manufactured by Negami Industry Co., Ltd.)].

The amine compound which can be used in the present invention has the following general formula (4): [Wherein, m = 1 to 6, R ⁹ and R ¹⁰ represent hydrogen, an alkyl group,
R ¹¹ is hydrogen, an alkyl group, a hydroxy group, an alkoxy group, an acryloyloxy group, a methacryloyloxy group, an aminoalkoxy group, an alkylaminoalkoxyl group, a dialkylaminoalkoxy group, R ¹² is a hydrogen, an alkyl group,
A hydroxy group, an alkoxy group, or a combination of R ⁹ and R ¹⁰ may form a cyclic structure. R ⁹ and R ¹¹ may be combined to form a cyclic structure), or

The following general formula (5) [Wherein, n = 1 to 6, y = 2 to 6, R ¹³ , R ¹⁴ , R ¹⁵ ,
R ¹⁶ is hydrogen, alkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, hydroxyalkyl, alkoxyalkyl, acryloyl, methacryloyl, R ¹⁷ and R ¹⁸ are hydrogen, alkyl, hydroxy, The alkoxy group, R ¹³ and R ¹⁵ may be bonded to form a cyclic structure. R ¹⁷ and R ¹⁸ may be combined to form a cyclic structure).

Examples of the compounds of the general formulas (4) and (5) include n-propylamine, isopropylamine, n
-Butylamine, diethylamine, butyltrimethylamine, triethylamine, 2-dimethylaminoethanol, triethanolamine, morpholine, piperidine,
N- (3-dimethylaminopropyl) methacrylamide, N- (3-dimethylaminopropyl) acrylamide, 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 3 -Dimethylaminopropyl acrylate,
3-diethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, 3-diethylaminopropyl methacrylate, bis (3-aminopropyl)
Ether, 2,2'-diaminodiethylether, ethylenediamine, diethylenetriamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,2-diaminopropane, 1,2-diamino-2 -Methylpropane, 1,3-diamino-2-propanol, 3,3′-diaminodipropylamine,
1,5-diamino-2-methylpentane, N, N-bis (3-aminopropyl) methylamine, 1,4-bis (3-aminopropyl) piperazine, N, N, N ′,
N ", N" -pentamethyldiethylenetriamine, N '
-Methyl-2,2'-diaminodiethylamine, isophoronediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane and the like Can be mentioned.

The phosphine compounds usable in the present invention include triphenylphosphine, tris (2-methylphenyl) phosphine, and tris (3-methylphenyl)
Phosphine, tris (4-methylphenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (4-
Methoxyphenyl) phosphine, tris (2,6-dimethoxyphenyl) phosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) Butane, 1,2-bis (dimethylphosphino) ethane, 1,3-bis (dimethylphosphino) propane,
1,4-bis (dimethylphosphino) butane and the like can be mentioned.

The above-mentioned storage stabilizer prevents the organoboron compound from radicalizing due to the carboxylic acid being contained in the composition or even under light shielding by heat, thereby preventing the composition from causing polymerization or the like. It acts to stably store things. Regarding the mechanism of action of the stabilizing agent, the amine compound is considered to be stabilized by reacting with the carboxylic acid in the composition and forming a structure coordinating with the organic boron compound. It is thought to be stabilized by creating a structure that coordinates directly with the organoboron compound independently.

In the composition of the present invention, a mixture of a monomer and / or oligomer having at least one polymerizable functional group having an ethylenically unsaturated bond, a dye compound, an organic boron compound, an amine compound and / or a phosphine compound. The ratio is not particularly limited, and the monomer and the oligomer can be mixed at an arbitrary ratio depending on the viscosity and the polymer properties. However, in general, the dye compound is in the range of 0.005 to 5 parts by weight, more preferably 0.1 to 100 parts by weight per 100 parts by weight of the monomer and / or oligomer.
In the range of from 0.5 to 2 parts by weight, from 0.01 to 2 parts by weight of the organic boron compound.
It is in the range of 10 parts by weight, more preferably in the range of 0.2 to 5 parts by weight. The compounding amount of the amine compound is in the range of 0.3 to 10 equivalents, more preferably in the range of 0.5 to 5 equivalents, based on the total of the carboxylic acid (in terms of acrylic acid) and the organic boron compound of the composition. The amount of the phosphine compound is in the range of 0.3 to 10 equivalents, more preferably in the range of 0.5 to 5 equivalents, based on the organic boron compound.

[0020]

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples. The names and contents of the components used in the following examples are shown below. Oligomer: UN-9200A (0.76% by weight of carboxylic acid) UE-8200 (0.72% by weight of carboxylic acid) SP-1509 (0.68% by weight of carboxylic acid) Monomer: Trimethylolpropane triacrylate (Carboxyl) Acid content: 0.01% by weight or less) Tetrahydrofurfuryl acrylate (carboxylic acid content)
Acryloyl morpholine (Carboxylic acid content: 0.01% by weight or less) Isobornyl acrylate (Carboxylic acid content: 0.12% by weight or less) (The above carboxylic acid content is in terms of acrylic acid.) Agent: Acrylic-modified chlorinated polypropylene (Supercron 2
24H Nippon Paper Industries Co., Ltd. Talc (300 mesh manufactured by Kishida Chemical Co., Ltd.) Silica gel (200-425 mesh manufactured by Kishida Chemical Co., Ltd.) The above components were mixed to produce the photopolymerizable composition of the example. A storage stability test (80 ° C.) was performed using the obtained composition.
Middle). Further, the effect of the free carboxylic acid concentration on the temperature of the photopolymerizable composition was measured. Detection was performed by tracking changes in polymerization temperature. Tables 2 and 3 show the results.
Shown in

(Example 1) Ingredient Addition amount UE-8200 70 g Isobornyl acrylate 30 g Acryloylmorpholine 5 g Tetra n-butylammonium 0.4 g N-butyltriphenylboron 1,1,5,5-tetrakis- (4 -Diethylamino 0.1 g Phenyl) pentadienylium p-toluenesulfonic acid (D11 in Table 1) Diethylenetriamine 0.8 g Carboxylic acid in the composition (in terms of acrylic acid) 0.57 g About 5 g of the prepared composition was placed in a glass test tube. HO
80 with T DRY BATH (Pasolina)
The sample was set on an aluminum block heated to ° C., and a thermocouple was inserted into the composition to observe a change in temperature. The time when the thermocouple was inserted was set as the start time, and the time until polymerization was measured.

(Example 2) Ingredient Addition amount UE-8200 70 g Isobornyl acrylate 30 g Acryloylmorpholine 5 g Tetra n-butylammonium 0.4 g N-butyltriphenylboron 1,1,5,5-tetrakis- (4 -Diethylamino 0.1 g Phenyl) pentadienylium p-toluenesulfonic acid 1,3-diaminopropane 0.6 g Carboxylic acid content (in terms of acrylic acid) in the composition 0.57 g Measured in the same manner as in Example 1.

(Example 3) Ingredient Addition amount UE-8200 70 g Isobornyl acrylate 30 g Acryloyl morpholine 5 g Tetra n-butylammonium 0.4 g N-butyltriphenylboron 1,1,5,5-tetrakis- (4 -Diethylamino 0.1 g Phenyl) pentadienylium p-toluenesulfonic acid 1,3-diamino-2-propanol 0.7 g Carboxylic acid content in the composition (in terms of acrylic acid) 0.57 g Measured in the same manner as in Example 1. .

(Example 4) Ingredient Addition amount UE-8200 70 g Isobornyl acrylate 30 g Acryloylmorpholine 5 g Tetra n-butylammonium 0.4 g N-butyltriphenylboron 1,1,5,5-tetrakis- (4 -Diethylamino 0.1 g Phenyl) pentadienylium p-toluenesulfonic acid 1,5-diamino-2-methylpentane 1.0 g Carboxylic acid content in the composition (in terms of acrylic acid) 0.57 g Measured in the same manner as in Example 1. did.

(Example 5) Ingredient Addition amount UE-8200 70 g Isobornyl acrylate 30 g Tetrahydrofurfuryl acrylate 10 g Tetra n-butylammonium 0.4 g N-butyltriphenylboron 1,1,5,5-tetrakis- (4-diethylamino 0.1 g phenyl) pentadienylium n-butyltriphenylboron (D12 in Table 1) N′-methyl-2,2′-diaminodiethylamine 1.1 g Carboxylic acid (acrylic acid) in the composition (Converted) 0.56 g silica gel 100 g Measured in the same manner as in Example 1.

(Example 6) Ingredient Addition amount UN-9200A 70 g Isobornyl acrylate 20 g Acryloylmorpholine 5 g Trimethylolpropane triacrylate 5 g Tetra n-butylammonium 0.4 g N-butyltriphenylboron 1,1,5 5-tetrakis- (4-diethylamino 0.1 g phenyl) pentadienylium n-butyltriphenylboron N- (3-dimethylaminopropane) acrylamide 1.5 g Carboxylic acid content (in terms of acrylic acid) in the composition 51 g It was measured in the same manner as in Example 1.

(Example 7) Ingredient Addition amount UN-9200A 70 g Isobornyl acrylate 20 g Tetrahydrofurfuryl acrylate 10 g Trimethylolpropane triacrylate 5 g Tetra n-butylammonium 0.4 g n-butyltriphenylboron Crystal violet (Table 1 of D14 of _{X = N (CH 3) 2} ) 0.1g n- butylamine 0.6g carboxylic acid content of the composition (as measured in the same manner as acrylic acid conversion) 0.54 g example 1.

(Example 8) Ingredient Addition amount UN-9200A 70 g Isobornyl acrylate 20 g Tetrahydrofurfuryl acrylate 10 g Trimethylolpropane triacrylate 5 g Tetra n-butylammonium 0.4 g n-butyltrianisyl boron crystal violet 0. 1 g Isophorone diamine 1.2 g Carboxylic acid content (in terms of acrylic acid) in the composition 0.54 g Measured in the same manner as in Example 1.

(Example 9) Component Addition amount SP-1509 60 g Isobornyl acrylate 40 g Acryloylmorpholine 10 g Tetra n-ethylammonium 0.4 g N-butyltriphenylboron 1,1,5,5-tetrakis- (4 -Diethylamino 0.1 g phenyl) pentadienylium n-butyltriphenylboron 1,2-diaminopropane 0.9 g carboxylic acid content (in terms of acrylic acid) 0.67 g talc 100 g Measured in the same manner as in Example 1 did.

(Example 10) Ingredient Addition amount UE-8200 70 g Isobornyl acrylate 30 g Acryloylmorpholine 5 g Tetra n-butylammonium 0.4 g N-butyltriphenylboron 1,1,5,5-tetrakis- (4 -Diethylamino 0.1 g Phenyl) pentadienylium p-toluenesulfonic acid 1,2-bis (diphenylphosphino) ethane 3.5 g Carboxylic acid content in the composition (in terms of acrylic acid) 0.57 g Same as in Example 1. It was measured.

(Example 11) Ingredient Addition amount UE-8200 70 g Isobornyl acrylate 30 g Acryloylmorpholine 5 g Tetra n-butylammonium 0.4 g N-butyltriphenylboron 1,1,5,5-tetrakis- (4 -Diethylamino 0.1 g Phenyl) pentadienylium p-toluenesulfonic acid 1,3-bis (diphenylphosphino) propane 3.5 g Carboxylic acid content in the composition (in terms of acrylic acid) 0.57 g Same as in Example 1. It was measured.

Example 12 Ingredient Addition Amount UE-8200 70 g Isobornyl acrylate 10 g Acryloylmorpholine 15 g Tetra n-butylammonium 0.4 g N-butyltriphenylboron 1,1,5,5-tetrakis- (4 -Diethylamino 0.1 g phenyl) pentadienylium p-toluenesulfonic acid 1,3-diamino-2-propanol 0.7 g carboxylic acid in the composition (in terms of acrylic acid) 0.50 g chlorinated polyolefin (Supercron 224H) 40 g Toluene 60 g Measured in the same manner as in Example 1.

Comparative Example 1 Composition (1) UE-8200 70 g isobornyl acrylate 30 g acryloylmorpholine 5 g tetra-n-butylammonium 0.4 g n-butyltriphenylboron 1,1,5,5-tetrakis- ( 4-Diethylamino 0.1 g Phenyl) pentadienylium p-toluenesulfonic acid Carboxylic acid content in the composition (in terms of acrylic acid) 0.57 g Measured in the same manner as in Example 1.

Comparative Example 2 Composition (2) UN-9200A 60 g Isobornyl acrylate 40 g Acryloylmorpholine 5 g Tetra n-butylammonium 0.6 g N-butyltriphenylboron 1,1,5,5-tetrakis- ( 4-diethylamino 0.2 g phenyl) pentadienylium p-toluenesulfonic acid Carboxylic acid content in the composition (in terms of acrylic acid) 0.54 g It was measured in the same manner as in Example 1.

[0035]

[Table 2]

[0036]

[Table 3]

In Examples 1 to 9, the photopolymerizable composition was prepared by adding 0.3 to 10 equivalents of an amine compound to the total amount of the free acid (in terms of acrylic acid) and the organic boron compound present in the composition. Examples 10 and 11 are photopolymerizable compositions obtained by adding 0.3 to 10 equivalents of a phosphine compound to an organic boron compound. In Examples 5 and 9, a filler was added, and in Example 12, a polymerizable compound and a solvent were added to the photopolymerizable composition. The results in Table 1 show that the storage stability at 80 ° C was significantly improved in each case. It also shows that stabilization can be achieved even when additives are contained. From the results in Table 2, when the amount of free acid present in the composition is small, there is storage stability near room temperature, but at high temperatures, the storage stability is lost, so it is not sufficient to simply remove the free acid. You can see that.

[0038]

The photopolymerizable composition of the present invention is a monomer having at least one polymerizable functional group having an ethylenically unsaturated bond and a dye compound having absorption in the visible or near-infrared region, an organic boron compound. And / or an oligomer and an amine compound or a phosphine compound, and can be stably stored even at a high temperature (80 ° C.) even when a carboxylic acid is contained in the composition. Therefore, the storage management of the photopolymerizable composition becomes easy.

[Table 1]

[Table 1]

[Table 1]

Claims (5)

[Claims] 1. A monomer and / or oligomer having at least one polymerizable functional group having an ethylenically unsaturated bond, and a compound represented by the following general formula (1): D ⁺ · M ⁻ (where D ⁺ is an organic cationic compound) a dye, M ^- is a dye compound having absorption in the visible light or near infrared light region represented by an anion of an organic or inorganic), the general formula (2): Wherein B ^- is a boron ion, R ¹ , R ² , R ³ , R ⁴
Is a group selected from an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alkynyl group, an alicyclic group, a heterocyclic group, and an allyl group, each of which may be the same or different Or two or more of them may combine to form a cyclic structure, and Z ⁺ represents an alkali metal ion, an alkaline earth metal ion or a general formula (3): (Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen, an alkyl group,
A group selected from an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alkynyl group, an alicyclic group, a heterocyclic group, and an allyl group, which may be the same or different; Or more may be bonded to form a cyclic structure)], and a storage stabilizer. . 2. The photopolymerizable composition according to claim 1, wherein the storage stabilizer is an amine compound. 3. The amine compound represented by the general formula (4): (Wherein, m = 1 to 6, R ⁹ and R ¹⁰ are hydrogen, an alkyl group,
R ¹¹ is hydrogen, an alkyl group, a hydroxy group, an alkoxy group, an acryloyloxy group, a methacryloyloxy group, an aminoalkoxy group, an alkylaminoalkoxyl group, a dialkylaminoalkoxy group, R ¹² is a hydrogen, an alkyl group,
A hydroxy group, an alkoxy group, or a combination of R ⁹ and R ¹⁰ may form a cyclic structure. The photopolymerizable composition according to claim 2, wherein R ⁹ and R ¹¹ may be combined to form a cyclic structure. 4. The amine compound represented by the general formula (5): (Where n = 1 to 6, y = 2 to 6, R ¹³ , R ¹⁴ , R ¹⁵ ,
R ¹⁶ is hydrogen, an alkyl group, an aminoalkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an acryloyl group, a methacryloyl group, and R ¹⁷ and R ¹⁸ are a hydrogen, an alkyl group, a hydroxy group , An alkoxy group, and R ¹³ and R ¹⁵ may be bonded to form a cyclic structure. R ¹⁷ and R ¹⁸ may be combined to form a cyclic structure. The photopolymerizable composition according to claim 2, which is represented by the formula: 5. The photopolymerizable composition according to claim 1, wherein the storage stabilizer is a phosphine compound.