JPS63286484A - Photocuring adhesive - Google Patents

Abstract

PURPOSE:To obtain the titled adhesive consisting of an unsaturated monomer, compound having a specific structure, alpha-ketocarbonyl compound and amine, having excellent photocuring properties in low temperature area near ordinary temperature under humid state as well as good water-resisting adhesion of cured product and useful as a dental material. CONSTITUTION:The aimed adhesive obtained by blending (A) a radical polymerizable unsaturated monomer with (B) phosphoric acid hydrogen acryloyl(or methacryloyl)oxyalkylalkoxyphenyl compound expressed by the formula (R1 is H or methyl; R2 is 2-3C alkylene; R3 is 1-2C alkyl), (C) alpha-ketocarbonyl compound and (D) amine. The component B is preferably phosphoric acid hydrogen 2-methacryloyloxyethyl 4-methoxyphenyl.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a photocurable adhesive that has excellent photocurability in a low temperature region around room temperature and under humid conditions, and has excellent water-resistant adhesive performance of the cured product, and further relates to Specifically, it can be used as an adhesive dental filling material, adhesive resin cement, or orthodontic adhesive, or as a dental filling material such as ordinary composite resin, or as a dental material that enhances the adhesion to teeth. Related to photocurable adhesives.

[Prior Art] Conventionally, many curable compositions comprising radically polymerizable monomers such as (meth)acrylic acid ester-based vinyl nitrates and curing agents have been proposed as adhesives for teeth.

The performance required of tooth adhesives is that in addition to a high curing speed in a low temperature region around room temperature, the cured product must have excellent water-resistant adhesive strength to teeth. In addition, with recent remarkable progress in tooth restoration treatment technology, requirements for adhesive performance have become stricter.

Among conventional tooth curable compositions consisting of a radically polymerizable monomer such as (meth)acrylic acid ester vinyl monomer and a polymerization initiator, a photopolymerization initiator is used as a polymerization initiator, and photocuring is performed. Several methods have been proposed that attempt to achieve the above-mentioned performance improvement by adopting a method of increasing the performance. For example, Japanese Patent Publication No. 54-10986 and Japanese Patent Publication No. 53-33687 propose a method of carrying out polymerization in the presence of a photopolymerization initiator consisting of a carbonyl compound such as α-diketone and amines. .

Further, JP-A-56-120610 proposes a photopolymerizable dental material containing an acidic group in the molecule and comprising a nyl monomer, an α-diketone, and an aromatic sulfinate salt.

[Problems to be Solved by the Invention] However, all of these photocurable compositions have drawbacks such as insufficient curing speed and low water-resistant adhesive strength. was not obtained.

In this way, there is still no dental photocurable material that exhibits adhesive strength to both dentin and enamel, and that exhibits strong adhesive strength for a long period of time even in humid conditions such as the oral cavity and in environments with many temperature changes. Not discovered.

[Means for Solving the Problems] In view of the above-mentioned problems in the prior art, the present inventors have developed scientific and engineering properties necessary for dental adhesives, such as hardness, compressive strength, and water absorption. The present invention was achieved as a result of extensive research in order to obtain a dental photocurable adhesive having the above characteristics and excellent adhesion to dentin and enamel.

That is, according to the present invention, (a) a radically polymerizable unsaturated monomer, (b) general formula (1) [where RI is a hydrogen atom or a methyl group, and R2 is an alkylene group having 2 or 3 carbon atoms] and R3 represents an alkyl group having 1 or 2 carbon atoms].

(C) α-ketocarbonyl compound, and (d) amine A photocurable adhesive is provided.

The radical polymerizable monomer (a) blended into the photocurable adhesive of the present invention is an unsaturated compound having radical polymerizability. Specifically, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, etc.
meth) Alkyl acrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, methacrylic acid
2-Hydroxyethyl, ethylene glycol di(meth)
Acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polybrobylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, 2,2-bis [4-(meth)acryloyloxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxycyclohexylcopropane, 2,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxyphenyl ] Propane, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri(trimethylsiloxy)silane, γ-methacryloxypropylpentamethyldisiloxane, isopropyl dimethacrylylisostearoyl titanate, styrene, α-methylstyrene, vinyltoluene, divinyltoluene, divinylbenzene,
Examples include vinyl compounds such as vinyl acetate,
A mixture of two or more of these components can also be used.

The compound (b) represented by the general formula (1) is usually synthesized from an alkoxyphenol. For example, in the case of 2-methacryloyloxyethyl 4-methoxyphenyl hydrogen phosphate, it is usually synthesized as follows.

! H・CH2=C-C00CHaCH20H Examples of compounds represented by the formula (1) include 1, 2-methacryloyloxyethyl hydrogen phosphate, 4-methoxyphenyl, 2-methacryloyloxyethyl hydrogen phosphate, 3
,4-dimethoxyphenyl.

2-Acroyloxyethyl hydrogen phosphate 4-methoxyphenyl, 3-methacryloyloxypropyl hydrogen phosphate 4-methoxyphenyl, 2-methacryloyloxyethyl hydrogen phosphate 4-ethoxyphenyl, 2-acryloyloxyethyl hydrogen phosphate 2 -methoxyphenyl,
Examples include 2-methacryloyloxyethyl hydrogen phosphate, 3-methoxyphenyl, etc., and compounds having different numbers of substituents or different substituent positions on the alkoxy group can also be used as a mixture.

The compound represented by formula (1) is usually used in a proportion of 0.5 to 20% by weight based on the radically polymerizable monomer (a). This compound is less than 0.5% by weight, or 2
If it exceeds 0% by weight, sufficient adhesive strength cannot be obtained.

The α-ketocarbonyl compound (C) and amine (d) that are blended into the curable composition of the present invention are used as photopolymerization initiators.

Examples of the α-ketocarbonyl compound (C) include α-diketones, α-ketoaldehydes, α-ketocarboxylic acids, α-ketocarboxylic acid esters, and the like. More specifically, diacetyl, 2,3-pentadione, 2
．． 3-hexadione, benzyl, 4,4'-dimethoxybenzyl, 4゜4'-jethoxybenzyl, 4,4'-
α-diketones such as oxybenzyl, 4,4′-dichlorobenzyl, 4-nitrobenzyl, α-naphthyl, β-naphthyl, camphorquinone, and 1,2-cyclohexanedione; α-keto such as methylglyoxal and phenylglyoxal; Examples include aldehydes, pyruvic acid, benzoylformic acid, phenylpyruvic acid, methylpyruvate, ethyl benzoylformate, methyl phenylpyruvate, and butyl phenylpyruvate. Among these α-ketocarbonyl compounds, α-diketones are preferably used from the viewpoint of stability.

Among the α-diketones, diacetyl, benzyl, and camphorquinone are preferred.

As the amine (d), N,N-dimethyl-p-toluidine, N,N-getanol-p-toluidine, N,N
-dimethylaminoethyl methacrylate, etc. are used.

The α-ketocarbonyl compound (c) is usually used in an amount of 0.1 to 5% by weight based on the radically polymerizable monomer (a), and the amine (d) is It is usually used in a proportion of 0.1 to 5% by weight based on a). α-ketocarbonyl compound (C) and amine (d
) is used in a ratio outside the above range, sufficient adhesive strength cannot be obtained.

By irradiating the photocurable adhesive of the present invention with light, polymerization occurs and the adhesive is cured. The light beam may be natural light or artificial light, and it is possible to employ light rays from the ultraviolet region to the visible region. As the artificial light, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a halogen lamp, a tungsten lamp, etc. can be used. The temperature during photocuring is usually in the range of 0 to 80°C, preferably 5 to 50°C, and the light irradiation time is usually in the range of 1 to 80°C.
It can be from seconds to 5 minutes.

In addition, when adhering the dental photocurable adhesive of the present invention to tooth dentin, the dentin surface can be appropriately ground and then pretreated with phosphoric acid or citric acid as in the past, but ethylenediamine Pretreatment with a tetraacetic acid solution (hereinafter abbreviated as EDTA), preferably a solution neutralized with sodium hydroxide or the like, is not harmful to the dental pulp and can significantly increase adhesive strength. The preferred EDTAW degree used in this case is usually 0.
The amount is about 1 to 0.5 mol, and the treatment is carried out, for example, by pre-treating for 1 minute and then washing with water for 30 seconds.

[Effects of the Invention] The dental photocurable adhesive according to the present invention has good adhesiveness to tooth structure and maintains high adhesive strength even in water or saliva. Therefore, it has good durability in the oral cavity, and for example, when used as a filler, it is moisturized like in the oral cavity.
Moreover, it adheres strongly to teeth for a long period of time even in environments with rapid temperature changes, and when used as a primer coating agent such as composite resin or orthodontic adhesive, it also adheres firmly to teeth. - It strongly adheres to resins, orthodontic adhesives, etc., thus reliably preventing gaps from forming between teeth, improving margin sealing properties, and preventing secondary caries.

[Examples] Hereinafter, the present invention will be further explained with reference to Examples and Comparative Examples.

(Example 1) Immediately after slaughter, the experimental teeth were obtained by removing the teeth that had been implanted in the jawbone, removing the attached tissue around the teeth, and cutting the crowns and roots of the teeth with a diamond cutter. The tooth was cut using a cutter (MC-Zoo), the crown part of the tooth pulp was removed, and the tooth was frozen and stored, and when necessary, it was thawed and used. The instant-curing resin uses a 1:1 granular copolymer of methyl methacrylate (MMA) and ethyl methacrylate with lfi amount % of benzoyl peroxide added as a powder, and a liquid agent containing N, N- in MMA. Dimethyl-p-toluidine at 0.
A solution containing 5ffi amount % was used.

The composite resin is made of photocurable silax (3M
A Delight Lamp (manufactured by Shofusha) was used as the light irradiator.

The adhesive is 2-methacryloyloxyethyl hydrogen phosphate 4- in triethylene glycol dimethacrylate.
2% by weight of methoxyphenyl, 0.0% of camphorquinone.
5% by weight and 0.5% by weight of N,N-dimethylaminoethyl methacrylate were used.

The dentin of the raw tooth was covered with silicon carbide paper #600 under water injection using Ecomet m (Bueller (B).
After grinding with a 0.5M neutralized EDTA solution (EDTA 2Na salt dissolved in water and adjusted to pH 7.4 with sodium hydroxide) for 1 minute, , and was prepared by washing with water for 10 seconds, and then a cellophane tape with a diameter of 5 cm was applied to define the adhesion area. After one layer of the adhesive was applied to the adhered surface, it was irradiated with light for 1 minute. On top of this, use double-sided adhesive tape with a diameter of 5.5+a.
A silicone rubber plate with a thickness of lI with holes in it was pasted, the spaces were filled with composite resin, and light was irradiated for 1 minute.

After that, using quick-hardening resin, we applied the brush stacking method to a diameter of 6 m.
The acrylic rod was placed perpendicularly to the surface of the hardened composite resin, left at room temperature for 30 minutes, then immersed in water at 37°C for one day. 2.0mm/wi
A tensile test was conducted at n, and the adhesive strength was measured. The tensile test was conducted by holding the tooth and acrylic rod using a testing machine and measuring the adhesive strength between the dentin and the cured composite resin. , and the quick-curing resin and the cured composite resin are strongly adhered to each other, so that they will not break on these surfaces.

The adhesive strength was determined as the average value of 8 test results, and as a result, it showed an adhesive strength of 61 kg/cm'' to dentin.

(Comparative Examples 1.2 and 3) When the adhesive of Example 1 does not contain 2-methacryloyloxyethyl hydrogen phosphate 4-methoxyphenylene (Comparative Example 1), when camphorquinone is absent (Comparative Example 2)
), N,N-dimethylaminoethyl J remethacrylate (Comparative Example 3)), the adhesion strength to dentin was measured in the same manner as in Example 1, and the results are shown in Table 1. .

Table 1 (Comparative Examples 4 and 5) The following (2) was used instead of 2-methacryloyloxyethyl hydrogen phosphate 4-methoxyphenyl in the adhesive of Example 1.
Regarding the use of 2-methacryloyloxyethylphenyl hydrogen phosphate represented by the formula (Comparative Example 4) and the use of 2-methacryloyloxyethyl trimellitic anhydride represented by the following formula (3) (Comparative Example 5), Example 1
The adhesion strength to dentin was measured in the same manner as above and is shown in Table 2.

Table 2 (Examples 2, 3 and 4) In Example 1, 1% by weight of camphorquinone, N,
N-dimethylaminoethyl methacrylate is 1% by weight, and the concentration of 2-methacryloyloxyethyl 4-methoxyphenyl hydrogen phosphate in the adhesive is 1% by weight.
, 5% by weight and 10% by weight, the adhesion strength to dentin was measured in the same manner as in Example 1, and the results were summarized in the third example.
Shown in the table.

Table 3 (Example 5) As a result of performing the bonding operation in the same manner as in Example 1, using natural tooth enamel instead of the natural tooth dentin in Example 1,
The adhesive strength was 71 Kg/c+w''.

(Examples 6 and 7) Instead of pretreating for 1 minute with 0.5M neutralized EDTA solution in Example 1, raw tooth dentin (Example 6) and bovine teeth were pretreated with 65% phosphoric acid for 30 seconds. The bond strength was measured for enamel (Example 7) and the results are shown in Table 4.

Table 4

Claims (1)

[Claims] 1) (a) Radically polymerizable unsaturated monomer, (b) General formula (1) ▲There are numerical formulas, chemical formulas, tables, etc.▼...(1) (However, R_1 is hydrogen atom or methyl group, R_2 is an alkylene group with 2 or 3 carbon atoms, and R_3 is an alkylene group with 1 carbon number.
or 2 alkyl group); (c) an α-ketocarbonyl compound; and (d) an amine. 2) The compound represented by general formula (1) is hydrogen phosphate 2
- methacryloyloxyethyl 4-methoxyphenyl. The photocurable adhesive according to claim 1.