JPS61197505A - Photosetting composition for dental purposes - Google Patents

Abstract

PURPOSE:A photosetting composition for dental purposes that contains, as a photopolymerization initiator, a polyvalent peroxy ester containing a benzophenone group, thus being polymerizable and curable with safe light close to visible light. CONSTITUTION:The objective composition contains, as a photopolymerization initiator, a polyvalent peroxyester containing benzophenone group of the formula (R1, R1' are tert.-alkyl of 4-8 carbon atoms, tert.-aralkyl of 9-12 carbon atoms; R2, R2' are H, tert.-alkoxy of 4-8 carbon atoms, tert.-aralkoxy of 9-12 carbon atoms) such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone and ethylenically unsaturated compounds such as methyl methacrylate, triethylene glycol dimethacrylate. The composition is readily curable with a safe light of 350-450nm in a short time with deeper curing and good clinical operation and economics.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a dental composition that can be polymerized and cured by light irradiation. In the present invention, the dental composition includes a dental crown restoration material, a caries prevention material, a denture base material, a dental adhesive restoration material, a dental impression material, etc., which contain an ethylenically unsaturated compound.

[Conventional technology]

Conventionally, methods for polymerizing and curing these dental compositions include:
A method of curing using a redox polymerization initiator based on K such as benzoyl peroxide and a tertiary amine, and a method of curing by irradiating a photosensitizer such as benzoin alkyl ether with ultraviolet rays have been used.

[Problem that the invention seeks to solve]

Room-temperature curing products using redox polymerization initiators are powder-curable.
Due to the liquid type or paste-paste type kneading method, air bubbles are likely to accumulate in the cured resin.
It also has the disadvantage of fast curing and short operating time.
In addition, the color tone changes due to the tertiary amine, resulting in poor aesthetics.On the other hand, when a normal UV photoinitiator such as benzoin alkyl ether is used, the UV light that is effective for polymerization curing does not penetrate the material. It is weak and cannot obtain sufficient curing depth, and in addition, among the ultraviolet rays used for this, 32
Ultraviolet rays with short wavelengths of 0 nm or less are harmful to the human body, so they must be protected with filters, and the mercury lamp used in the irradiation device deteriorates and has a short lifespan.

[Means to solve the problem]

As a result of repeated research in order to obtain a dental composition free of surface defects as described above, the present inventors have found that by using benzophenone group-containing polyvalent beroxy esters as a photopolymerization initiator, We have found an excellent dental composition that is polymerized and cured using safe light close to visible light of 450 nm, and is free from the problem of coloring.

That is, the present invention provides a photocurable dental composition comprising an ethylenically unsaturated compound and a photopolymerization initiator comprising a benzophenone group-containing polyvalent peroxyester represented by the following general formula (1). This is what we provide.

(However, R,, It, are respectively tertiary carbon atoms with 4 to 8 carbon atoms.
an alkyl group or a tertiary aralkyl group having 9 to 12 carbon atoms I R1+ R'2 is a hydrogen atom, a tertiary flukoxy group having 4 to 8 carbon atoms, or a tertiary aralkyl group having 9 to 12 carbon atoms, respectively;
Represents an aralkyloxy group. ) As the ethylenically unsaturated compound used in the present invention, all ethylenically unsaturated compounds conventionally used in dental compositions can be used; examples thereof include methacrylic acid derivatives such as methyl methacrylate, 2 -Hydroxyethyl methacrylate, neopentyl glycol dimethacrylate, l
, 4-butanediol dimethacrylate, 1,6-hexanethiol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dinotafrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, dibutylene glycol dimethacrylate, 11 Propylene gel 11 cold dimethacrylate, polypropylene glycol dimethacrylate,
Tetramethylolmethane trimethacrylate, tetramethylolmethanetetramethacrylate), 2,2-bis(
4-methacryloxyphel)propane, 2,2-bis(4-methacryloxyethoxyphenyl)furopane, 2
, 2-bis(4-methacryloxypolyethoxyphenyl)propane, 2.2-bis(4-(3-methacryloxy-2-hydroxypropoxy)phenyl)propane%
t.

2-bis(3-methacryloxy-2-hydroquinepropoxy)ethane, 2,2-bis(4-methacryloxyphenyl)propane, 2-hydroxy-1,3-dimethacryloxypropane, di-2-methacryloxyethyl- 2,
2,4-trimethylhexamethylene dicarbamate, 2
-Hydroxy-3-phenoxypropyl methacrylate, 2-hill methacrylate, methacryloxyethylphenyl phosphoric acid, 4-methacryoxyethyl trimellitate anhydride, and the like.

In addition, acrylic acid derivatives, styrene and its derivatives, etc. can also be used in the present invention. Furthermore, polymerizable oligomers such as maleate groups, rate oligomers, polyester acrylic oligomers, polyether acrylic oligomers, and polymerizable unsaturated polymers can also be used in the present invention.

Specific examples of the benzophenone group-containing polyvalent peroxyesters represented by the general formula (1) used in the present invention include 3.3', 414'-tetra-(t-phthylberoxycarbonyl)penzophenone. , 3.3', 4
．． 4″-tetra-(t-amylberoxycarbonyl)
Benzophenone, 3.3', 4゜4'-tetra (
t-hexylperoxycarbonyl)benzophenone,
3.3', 4. 4'-tetra(1-octylberoxycarbonyl)benzophenone, 3, 3', 4
．． 4'-tetra(cumylperoxycarbonyl)benzophenone, 3.3', 4. Examples include 4'-tetra(p-isopropylcumylberoxycarbonyl)benzophenone and carbonyl di(t-butyto).

The dental composition of the present invention comprises 1 flJ or more of the above-mentioned ethylenically unsaturated compounds, one or more benzophenone group-containing polyberoxy esters as a photopolymerization initiator, and all active ingredients. It is more preferable that the concentration of benphenone group-containing polyperoxy esters as a photopolymerization initiator is 0.01 to 10% by weight based on the ethylenically unsaturated compound. 0.05 to 5 [i]. The concentration of photopolymerization initiator is 0.01J1. The composition does not harden under dusty conditions, and
If the weight ratio exceeds 0, the physical properties of the cured product will deteriorate, which is not preferable.

The dental composition of the present invention may be used with appropriate addition of a filling material commonly used in dentistry, if necessary.

Examples of the filler include apatite, glass, quartz,
Silica gel, borosilicate glass, synthetic sapphire (alumina), and radioactive opaque filling materials, such as haflparicum and zirconium glass, are available in spherical, fine powder,
They may be platelets, fibers, whiskers, or have irregular shapes. - If necessary, in addition to the above-mentioned components, binder resins, polymerization inhibitors, antioxidants, stabilizers, pigments, dyes, thickeners, etc. may be added in appropriate amounts depending on the amount of water required.

The dental composition of the present invention uses benzophenone group-containing polyvalent peroxyesters as a photopolymerization initiator, and is easily cured by a light source containing light in the wavelength range of 350 nm to 450 nm.

The light irradiator used in the present invention emits light having a wavelength within the above-mentioned range, and any light source can be used. Examples of such light sources include xenon lamps, xenon lamps, tungsten lamps, fluorescent lamps, and metal halide lamps. lamp,
There are lasers, etc.

The dental composition of the present invention is mixed in advance into a single liquid by a supplier, filled into a light-shielded container, and supplied to doctors and dental technicians. After applying, filling or molding the dental composition of the present invention, a doctor or a dental technician can polymerize and harden it with light emitted from an irradiator. [Effects of the Invention] The dental composition of the present invention Since the composition uses a specific photopolymerization initiator, it is easily cured in a short time by non-toxic light in the range of 350 mm to 450 nm, and the curing depth is comparable to that of conventional ultraviolet light photopolymerization initiators. It is superior to those using agents. Further, according to the photopolymerization initiator of the present invention, a cured product with excellent aesthetics without coloring can be obtained, and furthermore, it is excellent in terms of clinical operability and economic efficiency.

[Examples] The present invention will be explained in more detail below using Examples and Comparative Examples.

A dental composition was prepared by uniformly dissolving a photopolymerization initiator in the compound. This composition was filled in a polyethylene cylinder with an inner diameter of 10-1 and a depth of 10 cm, and a 10-gen lamp (15V-150
Polymerization and curing were carried out by irradiating light with Wl from a distance of 3 cm from the top of the cylinder. Further, the curing depth at this time was measured using a micrometer after taking out the polymerized cured product from the gold cylinder and removing unreacted substances. The results are shown in Table 1.

Examples 11 to 12 A photopolymerization initiator was uniformly dissolved in an ethylenically unsaturated compound at the composition ratio shown in Table 1 to obtain parabolic silica gel. The hardening depth was measured in the same manner as in Examples 1-10.

The results are shown in Table IK.

As is clear from the results in Table 1, the dental composition of the present invention can be cured to a sufficient depth by removing light of 350 nm or less and irradiating it with a halogen lamp for a short period of about 30 to 60 seconds. It is excellent as an I material for dental crown restoration, a caries prevention material, a denture base material, a tooth, M-adhesive repair plate material, and a dental impression material. It can be seen that the coloring book has good aesthetics and clinical operation.

Comparative Example - I Using triethylene glycol dimethacrylate (Q) as an ethylenically unsaturated compound, and adding the polymerization initiator shown in Table 2, a test similar to that of Example was conducted.The results are shown in Table 2. However, it can be seen that the composition is not cured with light excluding light of 350 nm or less even if a conventional ultraviolet photopolymerization initiator is used.

Procedural amendment i (voluntary) May 22, 1985

Claims (2)

[Claims] (1) Ethylenically unsaturated compound and the following general formula (I)
A photocurable dental composition comprising a photopolymerization initiator consisting of a benzophenone group-containing polyvalent peroxyester represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (However, R_1 and R'_1 are each a tertiary alkyl group having 4 to 8 carbon atoms, or a tertiary aralkyl group having 9 to 12 carbon atoms, R_2 , R'_2 each represent a hydrogen atom, a tertiary alkoxy group having 4 to 8 carbon atoms, or a tertiary aralkyloxy group having 9 to 12 carbon atoms.) (2) The photocurable dental composition according to claim 1, wherein the ethylenically unsaturated compound is a methacrylic acid ester.