JPH0443882B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a dental photopolymerizable resin containing an α-diketone and an amine as a photopolymerization initiator and a photopolymerizable monomer, and in particular to a photopolymerizable resin containing a benzyl sulfone compound as a photopolymerization catalyst. By doing so, the photopolymerization curability is improved and the strength of the cured product is increased.
This relates to a technology that significantly increases adhesive strength to teeth. [Prior Art] Because polymeric resin materials have excellent strength, aesthetics, and operability, their use has rapidly increased in the field of dental treatment as an alternative to conventional cement-based restorative materials. There is. These polymerizable resins are prepared in such a way that polymerization starts either by kneading with a polymerization initiator, by heating, or by irradiation with light, from the standpoint of storage stability and operability during use. Since the curing reaction starts immediately after bonding, the application to the adhesive surface, such as filling the tooth cavity, must be completed promptly within a predetermined time. Alternatively, the polymerization reaction can only be started by heating after filling or other operations are completed, but heating inside the oral cavity may cause pain to the patient. Compared to these methods, this method is further improved and has the characteristic that it causes less serious pain to the patient. However, polymerizable resin materials of the type in which polymerization is initiated by light irradiation have the following drawbacks. In other words, when performing intraoral tooth restoration treatment,
In order to allow the curing reaction to proceed sufficiently, the patient must be forced to remain in a certain position for a relatively long period of time, which is difficult in practice.Also, polymeric resin materials are generally translucent and the depth of light reaching them is limited. If it is shallow, it is unavoidable, and as a result, polymerization in the deep parts that are in direct contact with the tooth structure will be incomplete, and furthermore, polymerization will proceed faster and solidify in the superficial parts where the amount of light irradiation is large. Since the tooth is positioned first and then polymerization progresses on the deep side, a space is created in the deep part and the adhesion force to the tooth substance is likely to be insufficient. This has led to problems such as the filling falling off, or the lack of margin sealing properties allowing saliva to enter, inducing secondary caries in deep areas. [Problems to be Solved by the Invention] As mentioned above, when conventional photopolymerizable resin materials are applied to teeth, uniform polymerization and curing properties cannot always be obtained, and as a result, sufficient adhesion to the tooth structure is not achieved. I couldn't get it. The present invention was made as a result of repeated studies focusing on these circumstances, and aims to provide a dental photopolymerizable composition that has excellent photopolymerization curability and, as a result, excellent adhesiveness to teeth. It is something. [Means for Solving the Problems] The present invention provides a dental photopolymerizable resin containing an α-diketone and an amino as a photopolymerization initiator as well as a photopolymerizable monomer. The gist is that it is blended as a polymerization catalyst. [Function] The greatest feature of the present invention is that the photopolymerizable resin containing α-diketone and amine as a photopolymerization initiator is blended with a photopolymerizable monomer. By blending a benzyl sulfone compound, which is unique in nature, it is possible to improve the photopolymerizable curability of the photopolymerizable resin, increase the strength of the cured product, and increase the adhesion to teeth. The photopolymerizable monomer in the present invention includes any compound that initiates polymerization upon irradiation with light, and is not limited to its type.
Preferably has a (meth)acrylic group with two or more functionalities as a residue: 2,2'-bis(4-(3-(meth)acryloxy-2-hydroxypropoxy)
phenyl)propane and 2,2'-bis(4-(meth)
Acryloxyphenyl)propane, 2,2'-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2'-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2, 2'-bis(4-(meth)acryloxypropoxyphenyl)
Propane, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate
acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, penta Examples include erythritol tetraacrylate, and more preferably adhesive functional groups: -OH, -COOH,

【formula】 【formula】

【formula】

Examples include (meth)acrylate derivatives having the formula: In addition, α-diketones include cankuarquinone, benzyl, biacetyl, 9,10
-phenanthrenequinone, naphthoquinone, etc. are exemplified, and various organic amines are mentioned as the amine, and more preferably N,N-dimethylaminoethyl methacrylate, N,N-dimethyl-P-ethyl benzoate, N,N- Examples include tertiary amines such as dimethyl-P-benzaldehyde. By the way, the combination of these α-diketones and amines is 420
By irradiating blue light in the range of ~450 mm, the α-diketone first creates an excited triplet state, which interacts with the amine to generate ion radicals, which in turn act on the photopolymerizable monomer. Polymerization proceeds. At this time, in the case of conventional materials, polymerization and curing in the deep part is delayed compared to the surface part due to the depth of light reach as described above, and sometimes is incomplete. However, the photopolymerizable dental composition of the present invention
In particular, by newly blending a benzyl sulfone compound as a photopolymerization catalyst, the above-mentioned poor curing can be eliminated, the strength of the cured product can be increased, and the adhesive strength to teeth can be significantly increased. Examples of benzyl sulfone compounds having such effects include the general formula: [However, R is an alkyl group, an aryl group, a benzyl group, or a -CH ₂ SO ₂ R ¹ group, R' is an alkyl group or an aryl group, and X is H, an alkyl group, or an aryl group, respectively] More specifically, benzyl monosulfinate derivatives include methyl benzylsulfinate, ethyl benzylsulfinate, propyl benzylsulfinate, ethyl benzylsulfinate chloride, phenethyl benzylsulfinate, and benzylsulfinate. Phenyl sulfinate, ethyl benzylmethylsulfinate,
Compounds such as propyl benzylmethylsulfinate are exemplified, and benzyldisulfone derivatives include: benzylsulfonylphenylsulfonylmethane, benzylsulfonylmethylsulfonylmethane, 1-benzylsulfonyl-1-methylsulfonylethane, 2-benzylsulfonyl-2 -methylsulfonyl-ethylbenzene, methyl 3-benzylsulfonyl-3-methylsulfonylpropionate, and the like. These benzyl sulfone compounds generate benzyl radicals and sulfinyl radicals when irradiated with light, and the former initiates polymerization of the photopolymerizable monomer with α-diketone and amine, which are essential components of the present invention. The growth reaction is further promoted, and the latter becomes sulfinic acid and then acts as an anaerobic polymerization catalyst, thereby increasing α
- It is thought that radical polymerization by diketone is further promoted. This increases the degree of polymerization in the deep part of the restored tooth, increases the strength of the polymer, and strengthens its adhesion to the tooth. In the dental photopolymerizable composition of the present invention, the photopolymerization initiator consisting of a combination of an amine and an α-diketone usually has an amine ratio of 0.5 to 10% relative to the polymerizable monomer.
% by weight, α-diketone: is added in the range of 0.05 to 5% by weight, but the type and blending ratio of the benzyl sulfone compound according to the present invention depends on the characteristics of these photoinitiators and photopolymerizable monomers. It is desirable to select and determine the appropriate amount depending on the amount to be added or the convenience of dental treatment. It is recommended that the blending ratio is preferably in the range of 0.5 to 5% by weight based on the photopolymerizable monomer; if the blending ratio is lower than this, the sufficient effect cannot be exerted, and if it is too high, the polymerization reaction will occur. The excess benzyl sulfone compound that does not participate in the above causes a decrease in the scientific and technological properties (especially adhesive strength) of the polymer. [Example] Tri(2-methacryloxyethyl) pyrophosphate (65 parts by weight), 2-hydroxyethyl methacrylate (5 parts by weight), acetone (30 parts by weight), camphorquinone (0.28 parts by weight), benzyl ( 0.12 parts by weight), N,N-dimethylaminoethyl methacrylate (1.2 parts by weight), hydroquinone monomethyl ether (0.053 parts by weight), and a sulfone compound selected in the present invention (5 parts by weight) as shown in Table 1 below. Stir and mix thoroughly to dissolve and use as a bonding agent. The adhesive strength of each bonding agent obtained was measured according to the sample preparation and tensile strength measurement methods described below. The results are shown in Table 1. Note that the comparative examples in Table 1 are the results in the case where no benzyl sulfone compound was added. (Sample preparation and tensile strength measurement method) () The surface of a fresh bovine tooth was ground flat and finished with emery paper, and then the sample was immersed and stored in water at 37±1°C. () In a measurement room adjusted to an air temperature of 23°C and a humidity of 50±10%, take out the sample and coat its surface with an etching agent [Clear Film F manufactured by Kuraray Co., Ltd.].
] After treatment, it was washed with water and dried with air. () Add one drop of the universal liquid and catalyst liquid and mix them on a plate to obtain an adhesive. Apply this thinly to the surface of the sample 1 with a piece of sponge or cotton ball as shown in Figure 1, and immediately Volatile components were evaporated by blowing air (2.2 Kg/cm ² ) for 10 seconds. () Stainless steel tube 4 was filled with photopolymerized composite resin (Aurafil, manufactured by Johnson & Johnson, USA) to a thickness of 2 mm, and irradiated for 30 seconds with a visible light irradiator (Opteirax, manufactured by Demetron, USA). After that, the photopolymerized composite resin was additionally filled and the handle 3 was placed. Thereafter, light was irradiated for 30 seconds to completely cure the microwave oven, thereby completing adhesion of the composite resin to the adhesive-coated surface. () After being immersed in water at 37°C±1°C for 24 hours, the adhesive strength was measured using an auto club. Autograph...full scale: 50Kg or 100Kg, tensile speed: 1mm/min, adhesive area...diameter 6mm. The test is conducted on 5 points each, of which 2
If the scores differed by 15% or more from the average value, a retest was conducted. If one of the five points had a variation of 15% or more from the average value, the average value of the remaining four points was used.

[Table] As is clear from Table 1, when the bonding agent of the present invention is used, the adhesive strength to bovine dentin is approximately
It shows a significantly high value of 1.3 to 2.3 times. In addition, the adhesion strength to bovine tooth enamel was compared with the comparative example for Example 5 (phenethyl benzyl sulfinate), Example 6 (phenyl benzyl sulfinate), and Example 9 (propyl benzyl metasulfinate). Although almost the same adhesive strength was obtained, other examples (Example 1)
-4, 7-8, 10-14) significantly increased by approximately 1.2 to 1.6 times. [Effects of the Invention] The present invention is configured as described above, and a suitably selected benzyl sulfone compound is added to a photopolymerizable resin containing a photopolymerizable monomer and an α-diketone and an amine as a photopolymerization initiator. By blending, it has become possible to provide an excellent dental photopolymerizable composition that improves photopolymerization curability and increases the strength of the cured product, and has high adhesive strength to teeth.

[Brief explanation of drawings]

FIG. 1 is a perspective explanatory view showing an adhesive strength testing method. 1...Sample, 2...Resin, 3...Handle, 4
...Stainless steel pipe, 5...Adhesive.

Claims (1)

[Claims] 1. A dental photopolymerizable composition comprising a dental photopolymerizable resin containing an α-diketone and an amine as a photopolymerization initiator and a photopolymerizable monomer, and a benzyl sulfone compound blended therein. thing.