JPS6218403A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable composition which can give a noncoloring product which does not undergo any change in a hue with time and is excellent in mechanical properties, by mixing a vinyl monomer with a thiophosphoric acid derivative and a photopolymerization initiator comprising an alpha-diketone. CONSTITUTION:A photopolymerizable composition comprising a vinyl monomer and a photopolymerization initiator comprising a combination of a thiophosphoric acid derivative with an alpha-diketone. The thiophosphoric acid derivative used is preferably a monothiophosphoric acid compound of formula I (wherein A is S, B is H, an alkali metal or the like and X is a halogen), a dithiophosphoric acid ester of formula II (wherein C is H, an alkali metal or the like and R is a 1-20C alkyl) or a dithiophosphoric acid triester of formula III (wherein R1 is a 1-20C alkyl). The most suitable alpha-diketone is camphorquinone.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to thiophosphoric acid derivatives and α-diketones. The present invention relates to a photopolymerizable composition containing a vinyl compound as a primary polymerization initiator.

Photopolymerization is used in a wide variety of fields, including printing plate materials, photosensitive agents for copying, printed wiring, and image formation for fl' processing such as C1 shadow masks, as well as paints, printing inks, and adhesives.

Photopolymerization is also used in the dental field; for example, photopolymerizable substances are used in the production of tooth filling materials (composite resins, etc.), tooth sealants and dental adhesives, caries preventive filling base materials, dental crowns, etc. It is used for manufacturing dentures, etc.

[Conventional technology]

Conventionally, the J"L VX compositions used as described above include, for example, Japanese Patent Publication No. 54-10986, which has the following composition and can be cured by irradiation with dJ visual light or ultraviolet light. A photopolymerizable composition is described. That is, this photopolymerizable composition is prepared by combining a photosensitizer/reducing agent 1 with a photoinitiator, (a) the following general formula (%) (X here) is>0=D,>0RIR219 is>Ckara0R4-4, R, -R4 may be the same or 19 may be different, are hydrogen or a hydrocarbon group, n
is zero''1t is 1, the groups A are the same or different and are hydrocarbon groups or substituted hydrocarbon groups, and the two groups A are directly bonded or via a divalent hydrocarbon group. or the two radicals A may be taken together to form a combined aromatic ring system, when n is 1 and X is )OR,R2, and when n is zero (b) at least one photosensitizer represented by the following general formula (wherein the units R are the same or They may be different, such as hydrogen, hydrocarbon group, substituted hydrocarbon group, 1 is a group in which two units R form a ring system together with N, and three units R are substituted hydrocarbon groups at the same time. and a polymerizable ethylenically unsaturated substance. Specific examples of particularly preferred photosensitizers include biacetyl, benzyl, benzophenone, and camphorquinone, and examples of reducing agents include trimethylamine, tripropylamine, dimethylamine, propylamine, N, I
J'-dimethylaniline, N-methyldiphenylamine, ethylenediamine, hexamethylenediamine, dimethylaminoethyl methacrylate, piperidine, and the like are described. Although materials using these photopolymerization initiators are rapidly cured by light irradiation, the cured products are markedly colored (often yellow) and change greatly in color over time in sunlight and water, and their strength and physical properties deteriorate. It has the disadvantage of only being of a low standard.

[Problem that the invention seeks to solve]

An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a photopolymerizable composition that is free from coloration and color change over time and provides excellent mechanical properties.

[Means for solving problems]

The photopolymerizable composition of the present invention is a photopolymerizable composition comprising a vinyl hexamer and a photopolymerization initiator, in which a thiophosphoric acid visiting conductor and an α-diketone are used in all combinations as the photopolymerization initiator. Characteristic O The vinyl monomer forming the m-acid of the present invention may be a monofunctional vinyl compound or a primary polyfunctional vinyl compound.

Examples of monofunctional vinyl compounds include styrene, acrylonitrile, vinyl acetate, methyl acrylate and methacrylate, ethyl acrylate and methacrylate, butyl acrylate and methacrylate, hydroxyethyl acrylate and methacrylate, methoxyethyl acrylate and methacrylate, glycidyl acrylate and methacrylate, Examples include methacryloxyethyl trimellitic acid and its acid anhydride. Examples of polyfunctional vinyl compounds include ethylene glycol diacrylate represented by the following general formula (wherein R6 is a hydrogen atom, R6 is a methyl group, and p is an integer from 1 to 20). and methacrylate, diethylene glycol diacrylate and methacrylate, triethylene glycol diacrylate and methacrylate, polyethylene glycol diacrylate and methacrylates, 1,4-butanediol diacrylate and methacrylate), 1,3-butanediol diacrylate and methacrylate, 1 .6-hexanediol diacrylate and methacrylate, glycerin diacrylate and methacrylate, and the following general formula (wherein, R is a hydrogen atom or a methyl group, p is 1 to 20
is an integer. ), bisphenol A diglycidyl acrylate and methacrylates, urethane diacrylate and methacrylates, trimethylolpropane triacrylate and methacrylate, pentaerythritol tetraacrylate and methacrylate, bisphenol A diacrylate and methacrylate, etc. These acrylates and methacrylates may be used alone or in combination of two or more.

The thiophosphoric acid derivative used in conjunction with the photopolymerization initiator of the present invention preferably has the following general formula (where A represents a sulfur atom, and B represents hydrogen, an alkali metal atom, or a carbon number 1).
~20 alkyl groups, and X represents a halogen atom.

), a monothiophosphoric acid compound represented by the general formula (wherein,
O represents hydrogen, an alkali metal, and copper represents a zinc atom; R
represents an alkyl group having 1 to 20 carbon atoms. ) or a dithiophosphoric acid diester represented by the general formula (wherein, R1 represents an alkyl group having 1 to 2 carbon atoms).
It is a dithiophosphoric acid triester represented by n, and specific examples include the following.

Trioleyl thiophosphate, trisC2,3-dichloroglopyl) thiophosphate, O,O'-diethylthiophosphoryl chloride, o,o'-diisopropylthiol phosphate, monothiophosphoric acid compounds such as sodium cyamyl monothiophosphate, didithiophosphoric acid Dithiophosphoric acid diesters such as 0,0'-diethyl, sodium dipropyldithiophosphate, zinc diglopyldithiophosphate, o,o'-cy(2-ethylhexyl)copper dithiophosphate,
0-di-n-butyl-8-ethyldithiophosphate, 0.0-dimethyl-dithio-phosphate, 7-layer, 2 or more types
Used in combination with α-diketones.

α-diketones are not particularly limited and all can be used, but camphorquinone, benzyl, acetylbenzoyl, acenaphthenequinone α-naphthyl, dichlorobenzyl, biacetyl, β-naphthyl, benzoin, α-diketone, etc.
-naphthoin and β-naphthoin are preferred. Among them, camphorquinone is the most preferred.
An amount of 4 to 30% by weight in 0-5 weight, preferably 10"-"
Weight t%~15 weight-! 1%, particularly preferably from 10% to 10% by weight, preferably from 10% to 50% by weight
% by weight, particularly preferably in the range from 10% to 20% by weight. These blending amounts are suitable for obtaining a composition that does not cause coloration or change in color tone over time of the photopolymerized cured product and also has high mechanical strength.

In the composition of the present invention, a filler may be added to the above-mentioned components, if necessary. Such filler components include those listed in Periodic Law No. 1. Il, III.

■、■ group, transition metals and their oxides, hydroxides,
Chlorides, sulfates, sulfites, carbonates, phosphates, silicates, and mixtures and complex salts thereof, among others silicon disulfide, quartz powder, aluminum oxide, barium sulfate, +4 oxide, talc, glass powder, glass beads, glass fiber, barium salt, glass filler containing lead salt, silica gel, colloidal silica, carbon fiber,
Zirconium oxide, tin oxide, other ceramic powders, etc. are preferred.

The above-mentioned filler may be any of untreated fillers, surface-treated fillers using a silane coupling agent, etc., and organic composite fillers that are composited with a polymer and pulverized.

The amount of the filler blended may be changed as appropriate depending on the purpose of use of the photopolymerized cured product, but for example, when used as a filling material for dental materials,
It is blended in an amount of 1 to 10" mi %, preferably 10 to 9.5 x IQ 2% by weight, particularly preferably 20 to 9 x 1 ozg, and used as a paste composition.

Furthermore, the composition of the present invention may optionally contain a coloring agent, 1
Synthesis inhibitors (e.g., hydroquinone, methoxybenzophenone, methylphenol, hydroquinone monomethyl ether, etc.), oxidation stabilizers, ultraviolet absorbers (e.g.,
benzophenone, etc.), pigments (for example, iron oxide, titanium oxide, etc.), and dyes such as iron oxide and titanium oxide.

〔Example〕

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples.

Examples 1-5. Pour the 7-mer mixture consisting of Comparative Examples 1 and 2 into a Teflon tube (inner diameter 4 mm, height 20 mm) whose bottom surface is sealed until the upper liquid level matches the top surface of the Teflon tube.

Next, 3M's visible light irradiator (product name: 0PTILU)
It was arranged so that the distance between the light irradiation surface of X) and the above liquid level was one day, and the town light was irradiated for 50 seconds.

Then, remove the entire injected monomer mixture from the Teflon tube and
The "thickness" of the resulting photopolymerized cured product was measured, excluding the unpolymerized portion.

Table 1 shows the type and amount of the photopolymerization initiator and the results of the above-mentioned "thickness" measurement.

Table 1 As is clear from Table 1, the composition according to the present invention has superior f'LZt original curing performance compared to the known composition of the comparative example. However, the appearance of the photocurable polymer according to the present invention was significantly cleaner than that of the comparative example, with almost no coloration.

Examples 11-20. Comparative Examples 3 to 4 A Teflon tube (inner diameter 4 ms) whose lower surface was sealed with a seven-layer filler mixture (paste).

The paste was packed to a height of 20 cm until the upper paste surface was aligned with the top surface of the Teflon cylinder. Next, 3M's IG viewing illuminator (
Place the paste so that the distance between the light irradiation surface of the product (product name: 0PTILUX) and the above paste surface is 1 m, and apply for 30 seconds.
Irradiated with visible light.

Thereafter, the injection paste was removed from the Teflon tube, the unpolymerized portion was removed, and the thickness of the obtained f'L nine-polymerized cured product was measured.

Table 2 shows the type and amount of the photopolymerization initiator and the results of the above-mentioned "thickness" measurement.

Table 2 [ As is clear from Tables 1 and 2, even when a filler is added, the composition according to the present invention has excellent photocuring performance compared to the known composition of the comparative example. I understand. Moreover, the appearance of the photocurable polymer according to the present invention had almost no coloration, and was significantly worse than that of the comparative example.

Comparative Example 5 After injecting the mixtures corresponding to Examples 1 and 11 into the Teflon tube, the top surface of the Teflon tube was covered with aluminum foil to prevent visible light from reaching the injected mixture.
Place the injection mixture so that the distance between the top surface and the light irradiation surface is 1 inch, and apply the visual light for 3 minutes! Comparative Example 6 Mixture corresponding to Examples 1 and 11?No polymerization occurred after complete irradiation? After each injection into the thiamin cylinder, the top surface of the Teflon cylinder was covered with aluminum foil to prevent visible light from reaching the injection mixture.
Heat the skin to 60℃ for 3 minutes, but no polymerization occurs.

Examples 21-30. A monomer/filler mixture (paste) consisting of Comparative Examples 7 to 9 was operated in the same manner as in Example 11 and irradiated with dJ visual rays for 60 seconds, and the resulting cured light 1 mixture was cut into 4×6 A cylindrical specimen of - was made from F'F-, and its compressive strength, color change after a one-week exposure test to sunlight, and color change after a one-week immersion test in 60°C water were measured.〇Table 3 The composition and amount of the photopolymerization initiator and the above-mentioned measurement results are shown in FIG.

As is clear from Table 3, the compositions according to the present invention have superior mechanical properties and extremely high color stability compared to the known compositions of comparative examples.

〔Effect of the invention〕

Since the photopolymerizable composition of the present invention uses a photopolymerization initiator that can be cured in the visible light range, it is not harmful to the human body and has poor curing performance, which is a disadvantage of conventional photopolymerization using ultraviolet rays. This method solves all the problems such as poor depth (depth) and high equipment investment, and the cured product obtained by photocuring has excellent A, which was not possible with conventional methods.
7j Has good color stability and appearance performance and high mechanical properties.

Claims (1)

[Claims] 1. A photopolymerizable composition comprising a vinyl monomer and a photopolymerization initiator, characterized in that the photopolymerization initiator is a combination of a thiophosphoric acid derivative and an α-diketone. sexual composition. 2. The photopolymerizable composition according to claim 1, further comprising a filler in addition to the vinyl monomer and the photopolymerization initiator. 3. Thiophosphoric acid derivatives have the general formula ▲ mathematical formula, chemical formula, table, etc. represents a halogen atom), there are general formulas, mathematical formulas, chemical formulas, tables, etc. (where C represents hydrogen, alkali metal, copper or zinc atom, and R represents a carbon number of 1 to 1). Dithiophosphoric acid diester represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents an alkyl group having 1 to 20 carbon atoms.) The photopolymerizable composition according to claim 1 or 2, which is an acid triester. 4. The photopolymerizable composition according to claim 1 or 2, wherein the α-diketone is camphorquinone. 5, the monothiophosphoric acid compound is triol thiophosphate,
Tris(2,3-dichloropropyl)thiophosphoric acid ester, O,O'-diethylthiophosphoryl chloride, O,
O'-diisopropylthiol phosphate or sodium diamyl monothiophosphate, and the diester dithiophosphate is O,O'-diethyl dithiophosphate, sodium dipropyldithiophosphate, zinc dipropyldithiophosphate or O,O'-di(2- ethylhexyl) dithiophosphate, and the dithiophosphate triester is O,O-
Di-n-butyl-S-ethyldithiophosphate or O
, O-dimethyl-dithio-phosphorylacetic acid.