JP3409291B2 - Amine-based unsaturated compound and photocurable composition containing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel amine unsaturated compound useful as a polymerization accelerator at the time of photocuring and a photocurable composition containing the same and having less unpolymerized monomer and less elution after curing.

[0002]

2. Description of the Related Art Generally, a photocurable composition contains a polymerizable monomer and a photopolymerization initiator as essential components. As the photopolymerization initiator, a photosensitizer such as aromatic ketone or camphorquinone and a polymerization accelerator such as an amine compound are used in combination.

[0003]

Since the conventional photocurable composition is apt to be inhibited in polymerization activity by an acid group-containing monomer used for imparting adhesiveness and oxygen, an amine-based composition which is a polymerization accelerator is used. It is necessary to use a large amount of the compound, and as a result, the surface hardness after polymerization and curing becomes insufficient and the adhesive strength decreases when used as an adhesive due to an increase in the amount of unpolymerized monomer in the deep part. there were.

[0004]

Means for Solving the Problems As a result of various researches conducted by the present inventors to solve the above-mentioned defects as a photopolymerization initiator composed of a photosensitizer and an amine compound, a specific structure was obtained. It was found that a highly curable photocurable composition with less polymerization inhibition by an acid group-containing monomer or oxygen can be obtained by using a novel amine-based unsaturated compound having a Came to.

That is, the present invention has the following general formula:

[0006]

[Chemical 3]

(Wherein R ₁ and R ₂ are hydrogen atoms or alkyl groups, R ₃ is an alkyl group, i is an integer of 2 or 3,
j and k each represent an integer of 0 or 1), and a photocurable composition containing the amine unsaturated compound as a polymerization accelerator.

The amine-based unsaturated compound provided by the present invention is represented by the above general formula, R ₁ and R ₂ represent a hydrogen atom or an alkyl group such as a methyl group and an ethyl group, and R ₃ represents R ₁ and R _2.
And an alkyl group similar to Further, the integer of j is an integer of 0 or 1 depending on the value of i, k is an integer of 0 or 1, and i is an integer of 2 or 3.

Specific examples of suitable amine-based unsaturated compounds are given below.

[0010]

[Chemical 4]

These amine-based unsaturated compounds are light yellow transparent viscous liquids at room temperature and atmospheric pressure, and are soluble in common organic solvents such as benzene, ether, chloroform and alcohol, but insoluble in water. Also, its boiling point is very high.
Even under a reduced pressure of ˜3 mmHg, heating at 100 ° C. or higher is required.

The method for producing the amine-based unsaturated compound of the present invention is not particularly limited, but a typical production method will be described below.

The following general formula

[0014]

[Chemical 5]

(Wherein R ₁ and R ₂ are hydrogen atoms or alkyl groups, i is an integer of 2 or 3, and j and k are 0 or 1
And an alcoholic unsaturated compound represented by the following general formula

[0016]

[Chemical 6]

It can be obtained by reacting an amine compound represented by the formula (wherein R ₃ represents an alkyl group).

More specifically, first, the alcoholic unsaturated compound represented by the above general formula is mixed with the amine compound represented by the above general formula in an organic solvent such as benzene to prepare a catalyst such as p-toluenesulfonic acid. The esterification reaction is completed by dehydration under reflux for 2 days.
Next, an aqueous solution adjusted to be weakly alkaline with sodium hydrogen carbonate or the like is added in the same amount as the above organic solvent layer, and the unreacted amine compound is removed by washing with water, and then the organic solvent layer is taken out and the solvent is distilled off under reduced pressure. The desired compound can be obtained.

The structure of the amine-based unsaturated compound of the present invention can be confirmed by various analyzes (a) to (d) below.

(A) Infrared absorption spectrum (IR) Generally, in methacrylic acid ester (or acrylic acid ester), the absorption of carbonyl group is 1720 cm ^-1.
In addition, the absorption due to the double bond is observed at 1640 cm ^-1 . Meanwhile acids and esters thereof bonded to the benzene ring is observed 1670 cm ^-1 and 1690 cm ^-1.

The amine-based unsaturated compound represented by the above general formula of the present invention can be prepared by R. Analysis shows that the absorption of carbonyl groups of methacrylic acid ester or acrylic acid ester is 17
To 20 cm ^-1, the absorption of a carbonyl group adjacent to the benzene ring in 1690 cm ^-1, absorption based on C-H of an alkyl group in the vicinity of 2850 cm ^-1, absorption based on the double bond 1
Each appears at 640 cm ^-1 .

Therefore, I. R. By analysis, it is possible to confirm the presence or absence of a carbonyl group based on a methacrylic acid ester or an acrylic acid ester, a carbonyl group based on a carboxylic acid ester adjacent to a benzene ring, an alkyl group and a carbon-carbon double bond.

(B) Carbon 13 nuclear magnetic resonance spectrum In the ¹³ C nuclear magnetic resonance spectrum obtained by decoupling ¹ H, carbons having different environments each show one peak. The product can be identified by examining this chemical shift. Specific identification of the compound of the present invention will be described later in Examples, but the structure of the compound of the present invention can be almost completely confirmed by carbon 13 nuclear magnetic resonance spectrum.

(C) Elemental analysis Almost sure identification of the amine-based unsaturated compound can be confirmed by the carbon 13 nuclear magnetic resonance spectrum. The theoretically calculated values of H, C and N elements in the compound and the actually obtained values are obtained. A more definite identification is possible by comparing the results of each elemental analysis with the compound.

(D) Mass spectrum The molecular ion peak M ⁺ can be confirmed by measuring the (meth) acrylate represented by the above general formula using the field ion-mass spectroscopy.

The amine-based unsaturated compound of the present invention can be identified by the analytical means described above in (a) to (d).

The amine-based unsaturated compound of the present invention is a novel substance as described above, and can be widely used as a raw material for the photocurable composition described later.

One of the components of the photocurable composition of the present invention is a polymerizable monomer, and a (meth) acrylate monomer is usually used. As the (meth) acrylate-based monomer, a known one that is polymerized by a photopolymerization catalyst can be used without particular limitation.

Typical examples of the (meth) acrylate-based monomers that are generally preferably used include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n. -Butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Monofunctional (meth) acrylate monomers such as 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene Rikoruji (meth) acrylate, triethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-
Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, bisphenol A di (meth) acrylate, 2 , 2'-bis [(meth) acryloyloxypolyethoxyphenyl] propane, 2,
2'-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane, trimethylolpropane (meth) acrylate, trimethylolethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, etc. A functional (meth) acrylate-based monomer or the like is used.

When the photocurable composition of the present invention is used as an adhesive, an acidic group-containing monomer having an acidic group such as a carboxyl group or a phosphoric acid group in the molecule is used as the polymerizable monomer. It is preferably used by mixing with the (meth) acrylate-based monomer.

If the preferable examples of the acidic group-containing monomer are represented by the general formula,

[0032]

[Chemical 7]

{In the formula, R ₆ is an alkyl group or a hydrogen atom,
R ₇ is an organic residue having 2 to 20 carbon atoms, Y is a carboxyl group (when 1 = 2, Y may be present in the form of an acid anhydride group)
Or an —OPO (OH) R ₈ group (R ₈ is a hydroxyl group, an alkoxyl group or an aryloxyl group), p is an integer of 1 to 3, and 1
Is an integer of 1 or 2, m is an integer of 0 or 1, and p + 1 = 2
An acidic group-containing monomer represented by

In the above general formula, the group represented by R ₆ is a hydrogen atom or an alkyl group, and specific examples of the alkyl group include a methyl group and an ethyl group.

R ₇ is a divalent to tetravalent organic residue having 2 to 20 carbon atoms, the main chain of which may be interrupted by oxygen. When the carbon number is 1 or less, the adhesion durability under wet condition is low. When the carbon number is 21 or more, it is difficult to obtain the material, and the strength of the cured product cannot be obtained, and the adhesive force is low. The organic residue may be either an aliphatic or aromatic organic residue as long as it satisfies the above carbon number, and may be partially substituted with a substituent such as halogen, amino group and hydroxyl group.

In the above general formula, Y is a carboxyl group or-
OPO (OH) R ₈ group having 1 or 2 to the above organic residue
Individually combined. Here, the group represented by R ₈ is any one of a hydroxyl group; an alkoxyl group such as a methoxy group, an ethoxy group and a butoxy group; and an aryloxyl group such as a phenoxy group and a benzyloxy group.

Specific examples of the acid group-containing monomer which are generally used are as follows:

[0038]

[Chemical 8]

Acidic group-containing monomer having one carboxyl group in the molecule such as;

[0040]

[Chemical 9]

Acidic group-containing monomer having two carboxyl groups in the molecule such as;

[0042]

[Chemical 10]

Acidic group-containing monomer having one phosphate group in the molecule such as;

[0044]

[Chemical 11]

Acid group-containing monomers having two phosphoric acid groups in the molecule such as

Specific examples of particularly preferable acidic group-containing monomers for exhibiting excellent adhesiveness include 7-methacryloxy-1,1-heptanedicarboxylic acid and 11-methacryloxy-1,1-undecanedicarboxylic acid. , 13
Examples thereof include dicarboxylic acids having two carboxyl groups in the molecule, such as methacryloxy-1,1-tridecanedicarboxylic acid.

Such an acidic group-containing monomer is usually used in an amount of 1 to 50 per 100 parts by weight of all the polymerizable monomers in the photocurable composition.
Includes parts by weight.

One of the other components of the photocurable composition of the present invention is a photosensitizer. As the photosensitizer, known ones used for ultraviolet rays or visible rays can be used without particular limitation.

Specific examples include diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3
-Octadione, 4,4'-dimethoxybenzyl, α-
Α-diketones such as naphthyl β-naphthyl, 4,4′-oxybenzyl, camphorquinone, 9,10-phenanthrenequinone and acenaphthenequinone; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether; 2,4-
Thioxanthone derivatives such as diethoxythioxanthone, 2-chlorothioxanthone and methylthioxanthone;
Benzophenone derivatives such as benzophenone, P, P'-dimethylaminobenzophenone and P, P'-methoxybenzophenone are preferably used.

The α-diketone is particularly preferable, and camphorquinone is particularly preferable.

The above-mentioned photosensitizers can be used not only individually but also in a combination of a plurality of types as required.

These photosensitizers are used in an amount of 0.05 to 10 with respect to 100 parts by weight of all the polymerizable monomers in the photocurable composition.
It is desirable to add parts by weight, preferably 0.1 to 5 parts by weight.

One of the other components of the photocurable composition of the present invention is the aforementioned amine-based unsaturated compound. Since the compound has two or more polymerizable functional groups and has a tertiary amine at the terminal, it not only acts as a polymerization accelerator, but also the compound itself is incorporated into the polymer in a crosslinked state after curing. . Further, discoloration of the cured product is considered to be a phenomenon caused by oxidation of amino groups,
Since the novel amine-based unsaturated compound of the present invention is cross-linked in the polymer, it is possible to obtain a cured product which is less likely to be oxidized by oxygen or the like and has little discoloration.

Such an amine-based unsaturated compound is usually added in an amount of 0.1% by weight per 100 parts by weight of all the polymerizable monomers in the photocurable composition.
It is desirable to add 05 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

If desired, a polymerization inhibitor, a coloring agent, a filler, an ultraviolet absorber and the like can be added to the photocurable composition of the present invention. In addition, when used for applications such as a filling material for repairing a caries cavity, it is general to add 100 to 500 parts by weight of the filler per 100 parts by weight of the total polymerizable monomer.

As the above-mentioned filler, there are an inorganic filler and an organic filler. Specific examples of the former include quartz powder, alumina powder, hydroxyapatite, calcium carbonate,
Fluoroalumina silicate glass, barium sulfate, titanium oxide, zirconia powder, ultrafine silica, spherical silica, spherical silica-titania, spherical silica-zirconia,
Amorphous silica-titania, amorphous silica-zirconia and the like can be mentioned, and examples of the latter include polymethylmethacrylate powder, polyethylenemethacrylate powder and the like.

The photocurable composition of the present invention is finally mixed with all the components, but in order to prevent deterioration during storage, it may be packaged in two stable packages if necessary.
For example, a package (A) consisting of an acidic group-containing monomer, a part of a (meth) acrylate-based monomer and a photosensitizer, and a polymerization accelerator and a part of a (meth) acrylate-based monomer. A combination of packaging (B) is common.

[0058]

The amine-based unsaturated compound of the present invention can be polymerized by itself, but when it is used as a polymerization accelerator in a photocurable composition, it is a highly sensitive cured product with less polymerization inhibition. Therefore, it is particularly useful as a filling material for restoration or an adhesive in the field of dentistry.

[0059]

EXAMPLES Examples will be shown below to more specifically describe the present invention, but the present invention is not limited to these examples. The (meth) acrylate-based monomer, the acid group-containing monomer, the photosensitizer, the amine-based unsaturated compound and the polymerization inhibitor used in the examples are abbreviated as follows.

11-methacryloxy-1,1-undecanedicarboxylic acid; 11-MUDCA 2-methacryloxyethyl succinic acid; 2-MEC 6-methacryloxyhexyl phosphate; 6-MHP bisphenol A diglycidyl methacrylate; Bis
GMA Triethylene glycol dimethacrylate; TEGDM
A 2-hydroxyethyl methacrylate; HEMA neopentyl glycol dimethacrylate; NPG camphorquinone; CQ hydroquinone monomethyl ether; HQME

[0061]

[Chemical 12]

Example 1 A 300 ml eggplant-shaped flask was charged with 22.8 g of 1,3-dimethacryloxyglycerin, 17.1 g of N, N-dimethylaminobenzoic acid, 1.0 g of p-toluenesulfonic acid and 180 ml of benzene. The mixture was heated with sufficient stirring to carry out an azeotropic dehydration reaction. When the amount of water generated by the dehydration reaction became close to the theoretical value, the reaction was stopped and the temperature was returned to room temperature, and then an aqueous sodium hydrogen carbonate solution was added to remove unreacted substances in the aqueous layer. Target 2 by removing the solvent in the benzene layer under reduced pressure
9.3 g was obtained. The yield was 78%. According to the infrared absorption spectrum of the obtained reaction product, 1670 cm ^-1
The absorption due to the carboxylic acid adjacent to the benzene ring in the vicinity disappeared, and the absorption by the ester of the carboxylic acid bonded to the benzene ring appeared at 1690 cm ^-1 . Also, absorption of the carbonyl group of the methacrylic acid ester was observed at 1720 cm ^-1 .

Next, the product was identified using the ¹³ C nuclear magnetic resonance spectrum. The results are as follows.

[0064]

[Chemical 13]

Further, the results of elemental analysis of the product are shown below.

[0066] Furthermore, from the mass spectrum of the product, m / e = 3
75 molecular ion peaks were observed. From these results, it was confirmed that the reaction product was the compound having the above structure.

Example 2 Add the following compounds to a 300 ml eggplant-shaped flask.

[0068]

[Chemical 14]

20.0 g of N, N-dimethylaminobenzoic acid (17.2 g), p-toluenesulfonic acid (1.0 g) and benzene (180 ml) were added, and the mixture was heated under reflux to carry out an esterification reaction by azeotropic dehydration. After completion of the reaction, separation and purification were carried out in the same manner as in Example 1 to obtain 24.3 g of viscous liquid.
According to infrared absorption spectrum (70% yield) the product obtained, the carboxylic acid absorption attributed to the carboxylic acid adjacent to the benzene ring of 1670 cm ^-1 is bonded to lost benzene ring 1690 cm ^-1 Absorption by the ester appeared. Also, absorption of the carbonyl group of the methacrylic acid ester was observed at 1720 cm ^-1 .

Next, the product was identified using the ¹³ C nuclear magnetic resonance spectrum. The results are as follows.

[0071]

[Chemical 15]

Example 3 Add the following compounds to a 300 ml eggplant-shaped flask.

[0073]

[Chemical 16]

34.0 g of N, N-dimethylaminobenzoic acid (17.5 g), p-toluenesulfonic acid (1.0 g) and benzene were added and the mixture was heated under reflux to carry out an esterification reaction by azeotropic dehydration. After completion of the reaction, separation and purification were carried out in the same manner as in Example 1 to obtain 36.5 g of viscous liquid. (Yield 75
%) According to the infrared absorption spectrum of the product obtained, 1
The absorption due to the carboxylic acid adjacent to the benzene ring at 670 cm ^-1 disappeared, and the absorption by the ester of the carboxylic acid bonded to the benzene ring appeared at 1690 cm ^-1 . Also, the absorption of the carbonyl group of methacrylate ester is 1720c.
Observed at m ^-1 .

Next, the product was identified by using the ¹³ C nuclear magnetic resonance spectrum. The results are as follows.

[0076]

[Chemical 17]

Further, the results of elemental analysis of the product are shown below.

[0078] Furthermore, the mass spectrum of the product shows m / e = 4
87 molecular ion peaks were observed. From these results, it was confirmed that the reaction product was the compound having the above structure.

Example 4 Add the following compounds to a 300 ml eggplant-shaped flask.

[0080]

[Chemical 18]

34.0 g of N, N-dimethylaminobenzoic acid (21.0 g), p-toluenesulfonic acid (1 g) and benzene were added, and the mixture was heated under reflux to carry out an esterification reaction by azeotropic dehydration. After completion of the reaction, separation and purification were carried out in the same manner as in Example 1 to obtain 35.4 g of viscous liquid. (Yield 72%)
According to the infrared absorption spectrum of the obtained product, 167
The absorption due to the carboxylic acid adjacent to the benzene ring at 0 cm ^-1 disappeared, and the absorption by the ester of the carboxylic acid bonded to the benzene ring appeared at 1690 cm ^-1 . Also, the absorption of carbonyl group of methacrylate ester is 1720 cm ^-1
Was observed.

Next, the product was identified using the ¹³ C nuclear magnetic resonance spectrum. The results are as follows.

[0083]

[Chemical 19]

Further, the results of elemental analysis of the product are shown below.

[0085] Furthermore, from the mass spectrum of the product, m / e = 5
Fifteen molecular ion peaks were observed. From these results, it was confirmed that the reaction product was the compound having the above structure.

Examples 5 to 8 and Comparative Example 1 The following compositions were divided into predetermined amounts in a mortar and then kneaded to prepare paste-like photocurable compositions. Examples,
The types and amounts of the photosensitizer and the polymerization accelerator used in Comparative Examples are as shown in Table 1.

Composition: Bisphenol A diglycidyl methacrylate 15 parts by weight Trithylene glycol dimethacrylate 10 parts by weight Photosensitizer x parts by weight Polymerization accelerator y parts by weight Hydroquinone monomethyl ether 0.05 parts by weight Spherical silica zirconia (average particle size 0. 75 parts by weight) The various physical properties of these photocurable compositions were measured according to the methods described below.

(1) The surface hardness paste was filled in a stainless split mold having a hole having a diameter of 6 mm and a depth of 3 mm, and pressed with a polypropylene film. Next, the tip of the quartz rod of a visible light irradiator White Light (trade name, manufactured by Takara Belmont Co., Ltd.) was fixed to the pressing surface and light irradiation was performed for 60 seconds. After irradiation, the cured polymer was removed from the split mold and immersed in distilled water at 37 ° C. for 24 hours for storage. After storage, the surface hardness of the irradiated surface was measured using a Micro Brinell hardness tester manufactured by Mori Tester. Compressive strength: The paste was filled in a stainless split mold having a hole with a diameter of 4 mm and a depth of 3 mm, and pressed with a polypropylene film. Next, fix the tip of the quartz rod of white light on the pressure contact surface and
Light irradiation was performed for 0 seconds. After the irradiation, the cured polymer was removed from the split mold, and the bottom surface of the cured product was further irradiated with light for 30 seconds.
Next, the cured product was immersed and stored in distilled water at 37 ° C. for 24 hours, and then the pressure contact strength was measured using Shimadzu Autograph AG5000D. The crosshead speed is 10m
It was set to m / min.

(2) The tensile strength paste was filled in a stainless steel split mold having a hole having a diameter of 6 mm and a depth of 3 mm, and pressed with a polypropylene film. Next, the tip of the quartz rod of white light was fixed to the pressure contact surface, and light irradiation was performed for 30 seconds. After the irradiation, the cured polymer was removed from the split mold, and the bottom surface of the cured product was further irradiated with light for 30 seconds. Next, the cured product was immersed and stored in distilled water at 37 ° C. for 24 hours, and then the tensile strength was measured using Shimadzu Autograph AG5000D. The crosshead speed was 10 mm / min.

(3) Toothbrush wear depth The paste was filled in a Teflon mold having holes of 10 mm in length, 10 mm in width and 1.5 mm in depth, and pressed with a polypropylene film. Next, the tip of the quartz rod of the white light irradiator, a visible light irradiator, was fixed to the pressing surface and light irradiation was performed for 60 seconds. After irradiation, the cured polymer was removed from the mold and immersed in distilled water at 37 ° C for 7 days for storage. The polymerized cured product was abraded 1500 mm by a load of 400 g.
The wear depth was obtained by dividing the wear weight by the density of the polymerized and cured product.

(4) The color-changing paste by the dye was filled in a stainless steel split mold having a hole with a diameter of 6 mm and a depth of 3 mm and pressed with a polypropylene film. Next, the tip of the quartz rod of white light was fixed to the pressure contact surface, and light irradiation was performed for 30 seconds.

Then, the cured product was placed in distilled water at 37 ° C. for 24 hours.
After soaking and storing for a period of time, the irradiated surface is softened (product name:
3H) and the cured product is immersed in an aqueous coffee solution containing 8% of instant coffee powder (Nescaf Nestle Japan), and the change in color tone after 24 hours is measured. The color tone change amount is represented by a difference ΔE between the color tone before the immersion in the coffee aqueous solution and the color tone after the immersion in the coffee aqueous solution for 24 hours. Here, ΔE is ΔE (Lab) proposed by Hunter.

A colorimetric color difference meter TC-1800MKII type manufactured by Tokyo Denshoku Co., Ltd. was used for the measurement of the cured product.

The obtained results are also shown in Table 1.

[0095]

[Table 1]

Examples 9 to 11 and Comparative Example 2 Photocurable compositions having various compositions shown in Table 2 were prepared according to Examples 5 to 8 and the adhesive strength to dentin was measured using these. . The results are also shown in Table 2. The measuring method is as follows.

The bovine anterior teeth were removed within 24 hours after slaughter, and the dentin was carved under water with an # 800 emery paper so as to be horizontal to the labial surface. Next, compressed air is blown to the surface for about 10 seconds to dry it, and paraffin wax with a hole of 4 mmφ in diameter is fixed to the surface of this dentin with double-sided tape to form a simulated cavity with the surface as the bottom surface. did. Compressed air is blown to the surface to dry, and then the pasty curable composition obtained by mixing the components shown in Table 1 by a conventional method is applied, and then a commercially available visible light irradiator "White Light" is used. (Manufactured by Takara Belmont) was used for light irradiation for 10 seconds. Further, a commercially available curable composite resin “Palfique Esterite” (manufactured by Tokuyama Soda Co., Ltd.) was filled on the above, pressure-contacted, and then again irradiated with light for 30 seconds to be cured.

After the composite resin was cured, the paraffin wax was removed, and the composite resin was left standing in water at 37 ° C. for 24 hours. Next, metal attachments were attached to the bovine anterior teeth and the cured composite resin, and the adhesion strength between the dentin and the photocurable composition was measured by a tensile tester (crosshead speed: 10 mm / min).

[0099]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07C 229/60 C08F 2/50 CAPLUS (STN)

Claims (2)

(57) [Claims] 1. A general formula: (Wherein, the R _1, R ₂ is a hydrogen atom or an alkyl group, R ₃
Is an alkyl group, i is an integer of 2 or 3, and j and k are integers of 0 or 1, respectively). 2. A polymerizable monomer (a), a photosensitizer (b),
And (c) a polymerization accelerator, and (c) the polymerization accelerator is represented by the following general formula: (Wherein, the R _1, R ₂ is a hydrogen atom or an alkyl group, R ₃
Is an amine group, i is an integer of 2 or 3, and j and k are integers of 0 or 1, respectively) are photo-curable compositions.