JPH0352844A - Maleic acid monoester compound and adhesive containing the same - Google Patents

Abstract

NEW MATERIAL:The maleic acid monoester compound of formula I (R1 and R2 are H or CH3; m and n are 1, 2 or 3). USE:Useful as an industrial adhesive, thermosetting coating, paperprocessing chemicals, additive for lubricant, etc., as well as a dental adhesive. It contains hydrophilic group and hydrophobic group in well-balanced state and has excellent properties required as a dental adhesive, e.g. hardness, compression strength and water-absorption. It exhibits high adhesivity to dentine and durability in oral cavity. It can be used also as a resin cement. PREPARATION:The compound of formula I can be produced according to the reaction formula by reacting maleic anhydride with equimolar amount of a hydroxyalkyl (meth)acrylate of formula II at 50-70 deg.C under heating and stirring.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel maleic acid monoester compound and a dental adhesive containing the same.

More specifically, it can be used as an adhesive dental filling material, adhesive resin cement, or orthodontic adhesive, etc., or as a dental material that enhances the bond between ordinary composite resin fillings, dental materials, etc., and teeth. related to adhesives.

[Conventional technology]

In recent years, composite resins have been developed as an alternative to dental cements such as zinc phosphate cement and silicate cement for the treatment of teeth with caries. Some are now being made in colors that are indistinguishable from natural teeth. However, composite resin does not essentially adhere to the tooth enamel and dentin, so over a long period of time, gaps will form between the tooth structure and the filled composite resin, making it easy for secondary caries to occur. Eventually, the composite resin would fall off.

In the past, various adhesion enhancers such as adhesive liners have been developed to improve the adhesion between such composite resins and cavity walls. Various dental adhesive assemblies have been proposed for the purpose of adhering to teeth.

[Problem to be solved by the invention]

However, few of these conventional adhesives adhere strongly to teeth over a long period of time in environments that are humid and subject to rapid temperature changes, such as the inside of the oral cavity.

For example, adhesives containing α-cyanoacrylate as a main ingredient have been developed as caries-preventing fillers and orthodontic adhesives that are intended to adhere to tooth structure, but It is said that there are problems with durability and operability during use.

On the other hand, fillers in which bisphenol A diglycidyl methacrylate is the main component of a resin and are cured using a benzoylamine peroxide catalyst have been widely used in recent years. However, since this material does not have adhesive properties to dentin and enamel, when it is filled into the cavity of a tooth, the filling material may fall off after a while and may even cause secondary caries. .

Furthermore, an adhesive containing 2-methacryloyloxyethyltrimellitic anhydride has been proposed as having excellent water resistance and durability, and being sufficiently durable for use in the oral cavity. However, the room temperature polymerization catalyst used in this adhesive is
Usually limited in nature to tri-n-butylborane oxide,
Although it has the advantage of having strong adhesion to tooth dentin, it has a slow polymerization reaction rate, takes more than 10 minutes to final harden, and is extremely unstable in air, making it difficult to handle. It is said that there are many problems from a dental clinical standpoint.

As mentioned above, there is currently no dental material that has adhesive strength to both dentin and enamel and that exhibits strong adhesive strength for a long period of time even in the moist state of the oral cavity and in environments with rapid temperature changes. It has not been.

In view of the above-mentioned prior art, the present inventors have discovered that a dental adhesive has the scientific and engineering properties necessary for a dental adhesive, such as hardness, compressive strength, and water absorption, and has excellent adhesion to dentin and enamel. We conducted extensive research in order to obtain a dental adhesive with strength.

As a result, a product obtained by polymerizing and curing a maleic acid monoester compound with a specific structure has strong adhesive strength with teeth even in water, and a polymer of a maleic acid monoester compound or a maleic acid monoester compound When used as a tooth filling material, the copolymer with other polymerizable monomers will strongly adhere to the tooth wall and will not form gaps or fall off due to poor adhesion. Also, when used as a liniment or adhesive for fillings such as composite resin, it can significantly improve margin sealing properties and effectively prevent the occurrence of secondary caries. The present invention was developed based on the discovery that it is suitable for bonding.

[Means to solve the problem]

According to the present invention, the following general formula (1) (wherein R or R2 represents -H or -CHff, m
or n represents 1, 2 or 3. ) A maleic acid monoester compound is provided,
Also provided is a dental adhesive containing the maleic acid monoester compound or its polymer.

The present invention will be explained in detail below.

The compound represented by the above general formula (1) is a new compound, and is usually synthesized from maleic anhydride and a hydroxyalkyl ester of acrylic (or methacrylic) acid as shown in the following formula (2).

COCI{=CI1COOl{ (2) In general, a mixture of approximately equimolar amounts of raw material maleic anhydride and hydroxyanolekyl ester of acrylic (or methacrylic) acid is heated and stirred at a temperature of 50 to 70°C. Obtained by reaction.

The obtained maleic acid monoester compound has an infrared absorption spectrum (I
It's called R. ) wave number (ν,, This shows that the compound clearly has an acryloyl (methacryloyl) group and an oxyalkyl group in the molecule.The more detailed structure can be seen in the nuclear magnetic resonance spectrum (N
MR).

The maleic acid monoester compound of the present invention obtained by the above method is useful as a dental adhesive.
It can also be used for industrial adhesives, thermosetting paints, gluing processing, lubricating oil additives, fiber treatment agents (antistatic, etc.), flame retardant agents, metal binding solvents, metal extractants, etc. General formula (1
) A dental adhesive containing a maleic acid monoester compound or a polymer represented by the above formula may contain a maleic acid monoester compound alone or together with other polymerizable monomers as a polymerizable monomer. It may also contain a homopolymer of a maleic acid monoester compound or a copolymer with other polymerizable monomers, or it may contain a mixture of these polymers and a polymerizable monomer. But that's fine. Usually, it is bonded to the tooth by curing it during use.

The tooth adhesive of the present invention is characterized in that it is a maleic acid monoester represented by formula (1), and it has the effect of the maleic acid residue and other functional groups of the maleic acid monoester compound, as well as the enamel. It exhibits excellent adhesive strength with dentin while maintaining its adhesive strength. The reason for its excellent adhesion to dentin is (1)
It is presumed that this is due to the balance between the hydrophilic groups and hydrophobic groups of the maleic acid monoester compound of the formula (2) being suitably arranged in terms of affinity for organic substances such as collagen.

Examples of the compound represented by formula (1) useful in the dental adhesive of the present invention include the following compounds (1) to (2).

I OCOCH=CHCOOl{ 0 C O C I = C I1 C O O HC
H2=C}l-Coo (CHz) zCH- (CH
z) z-OCOCtl=(Hz ■[OCOCH=CHCOO}! In addition to the above-mentioned components, the dental adhesive of the present invention may also contain known components that are usually blended depending on the type of material to be bonded and the purpose of use. Can be used in combination.

For example, when used as an adhesive filler, only the maleic acid monoester compound of formula (1) is used as a polymerizable monomer, and the adhesive filler is formed by polymerizing and curing in the presence of a curing agent at the time of use. It can be used as

However, usually a mixture of the maleic acid monoester compound of formula (1) and other polymerizable monomers is used, which is polymerized and cured in the presence of a curing agent before use. In this case, other polymerizable monomers include methyl methacrylate, hydroxyethyl methacrylate, ethylene glycol-di methacrylate, di- or tri- or tetraethylene glycol-di methacrylate, glycidyl methacrylate, 2,2-bis(4-methacryloxyphenyl) Propane, 2,2-bis[4-(3-methacryloxy-2-
Hydroxybroboxy)phenyl]propane, styrene, 1,3-butanediol dimethacrylate, tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate, bisoxyethylated bisphenol A diacrylate, and the like are used.

Further, if necessary, a polymerizable monomer and/or oligomer containing a maleic acid monoester compound of formula (1) may be blended to adjust the viscosity, curing rate, polycondensation, etc. Furthermore, inorganic fillers such as silica, glass beads, alumina, and quartz powder (preferably those with a particle size of 100 μm or less), or T-methacryloxypropyltrimethoxysilane or T-methacryloxypropyl trimethoxysilane, are used to improve the bonding properties with the resin.
Desired additives such as those treated with a silane coupling agent such as vinyltrichlorosilane and vinyltriethoxysilane, a curing agent, a polymerization inhibitor, a coloring agent, an antioxidant, and an ultraviolet absorber may be used.

When using a combination of two types of curing agent, such as ξan and peroxide or P-}luenesulfinate and peroxide, a maleic acid monoester compound of formula (1) is used as the polymerizable monomer. Divide into two equal parts, add a curing agent such as amine or p-}luenesulfinate to one side, add a curing agent such as peroxide to the other, and add the maleic acid monoester compound of formula (1) and other When used in combination with a polymerizable monomer, similarly add one of the curing agents to each half of the other polymerizable monomer, and add the maleic acid monoester compound of formula (1). It is preferable to mix it with one or both of the two halves of the other polymerizable monomer to which the curing agent is added.

These curing agents are usually mixed together during use.

The blending amount of the maleic acid monoester compound of formula (1) is:
Although not particularly limited, when used together with other polymerizable monomers, it is preferably 10 to 100% (wt%, same hereinafter), preferably 20 to 90%, based on the other polymerizable monomers. 1
If it is less than 0%, the adhesive effect will be poor and undesirable. The blending amount of the polymerizable monomer is 15 to 100% based on the entire adhesive composition.
%, the amount of inorganic filler is O based on the entire adhesive composition.
It is preferable to set it to 85%.

When the dental adhesive of the present invention is used as an adhesive between a tooth and a conventional filler such as a composite resin, a maleic acid monoester compound of formula (1) is added to an organic solvent such as ethyl ether or chloroform. It can be used with a content of 20 to 90%.

Further, the maleic acid monoester compound of the formula (1) may be contained in the other polymerizable monomer in an amount of 20 to 90%. It can also be used in the same manner as the filler described above.

When the dental adhesive of the present invention is used as a filling agent, the adhesive is filled into a cavity to be filled and allowed to harden. When used to bond a dental filling to a tooth, for example, after shaping a cavity, the adhesive is applied to the wall of the cavity, then a prescribed filling is filled, and then hardened. be able to.

〔Example〕

Hereinafter, the present invention will be explained in further detail based on Examples. However, the present invention is not limited to these Examples.

In addition, the analysis and measurement of the compound, etc. in this example was carried out by the following method.

[11 Elemental Analysis (EA) Carbon,
Measure hydrogen.

[2] Infrared absorption spectrum (IR) Measured by the liquid film method using a sodium chloride plate with a Perkin Elmer model 1750 infrared absorption spectrograph.

[3] Nuclear magnetic resonance spectrum (NMR) JEOL G
Measured using an X-270 nuclear magnetic resonance spectrometer using deuterochloroform as a solvent and tetramethylsilane as a reference substance.

Example 1 The above compound ■ } OCOCI{=CIICOOH was jointly admonished.

2-Hydroxy-1,3-dimethacryloxypropane 4
5. 7 g and 1 maleic anhydride 9. 6 g was heated and stirred at 60''C for 48 hours to react.

After the reaction, the mixture was allowed to cool, and 350 grams of a 5% aqueous sodium carbonate solution was added to form an aqueous solution. The aqueous solution was washed with 500 ml of ethyl ether in four portions. After washing, 5% hydrochloric acid was added to this aqueous solution until the pl was 12 to 3, and the oily layer was separated from the aqueous layer. This oil was extracted with 250 d of ethyl acetate.

The extract was washed with distilled water and then dehydrated and dried over sodium sulfate overnight.

Thereafter, ethyl acetate was removed by distillation under reduced pressure to obtain an oily substance.
．． I got 9g.

The analysis results of the obtained oily substance were as follows.

EA (χ): C55.35, H5.41 Theoretical value: C55
．． 21, H5.56 NMI? (CDClff); δ(ppm)
:1 0. 1 0 (bs IH;-Cool{
)6. 3 5 (s 2H ;-CH=CH-)6.
1 0, 5. 6 0 (d 411 .CH2・
)5. 4 5 (m IH ;-CH-)4. 4
0 (m 4H ;-COOCt{z-)1. 9
5 (s 6H ;-CH3)IR I'w+*x
(cm-'): l730, 1640, l460,
1170 Example 2 [Preparation of adhesive] Compound ■ obtained in Example 1 60%, 2-hydroxyethyl methacrylate (hereinafter referred to as H-MA) 10%
, 2,2-bis(4-(3-methacryloxy2-hydroxypropoxy)phenyl)propane (hereinafter referred to as Bis-
It's called GMA. ) 15%, triethylene glycol dimethacrylate (hereinafter referred to as TEGDMA) 14%, and benzoyl peroxide (hereinafter referred to as BP○) 1% is called solution A, and on the other hand, sodium p-toluenesulfinate 4 % and dimethyl-p- }Luidine 1%
A two-component adhesive was prepared using an ethanol solution containing the following as liquid B.

[Adhesion of dentin and composite resin] To obtain experimental teeth, bovine teeth were obtained immediately after slaughter and implanted in the jawbone, and the attached tissues around the teeth were removed, and the crowns and The roots of the teeth were cut using a diamond cutter (Marto Canter MC-100), the pulp of the crowns of the teeth was removed, and the resulting pieces were frozen and stored, and thawed and used when necessary.

Hereinafter, the adhesion method and adhesion test method will be explained in detail based on the example shown in FIG.

Bovine dentin was coated with water-resistant silicon carbide paper ranging from coarse to #600 under water injection using Ecomet II [(Ecomet
After grinding with I [[Buehler) and etching with 65% phosphoric acid for 30 seconds,
Test bovine teeth were prepared by washing with water for 30 seconds.

In Fig. 1, the diameter of the bovine tooth 1 adjusted as described above is 4 mm.
A cellophane tape 2 with a hole of mm is pasted to define the area to be adhered, and an inner diameter of 6 mnI,
A plastic ring 3 with a height of 5 mm was fixed with paraffin wax 4.

Next, one layer of an adhesive prepared by mixing equal amounts of liquid A and liquid B prepared above is applied to the surface to be adhered 5, and after volatilizing the ethanol with an air gun, a photopolymerizable composite resin: bi-mouth fill is applied. Light Bond Front Teeth Universal @ (manufactured by Sankin Kogyo ■) was filled into the plastisoc ring 3 to a height of approximately 2 mm, and irradiated with light for 30 seconds using a light irradiator: Suncure Light @ (manufactured by Sankin Kogyo ■). The packed bed 6 was formed.

Furthermore, a chemically polymerized composite resin: Pie Mouth Fill Bond for Front Teeth @ (manufactured by Sankin Kogyo) is filled on top of the filling layer 6 to shape the filling layer 7, and before it hardens, a metal hook 8 is filled. It was fixed in layer 7. After 10 minutes, it was immersed in water at 37°C. After 24 hours of immersion, the test bovine teeth were taken out and subjected to a tensile test to measure the adhesive strength.

The tensile test was performed using Autograph DDS- manufactured by Shimadzu Corporation.
Using a 500 type testing machine, the bovine tooth 1 and the metal hook 8 were grasped, and the bovine dentin 1 and the photopolymerized composite resin filling layer 6 were grasped at a crosshead speed of 2.0 mm/rain.
The adhesive strength was measured. In this case, the photopolymerizable composite resin filling layer 6 and the chemical polymerization type composite resin filling layer 7 are strongly adhered to each other, so that they do not break at the interface between the filling layers 6 and 7. Moreover, the metal hook 8 does not come off from the filling layer 7.

The adhesive strength was 39 kg/cm2, which was the average value of the tensile test results of 8 test bovine teeth prepared as described above.

Comparative Example 1 A test bovine tooth was made in the same manner as in Example 6, except that the adhesive of the present invention was not used when making the test bovine tooth, and the bovine tooth was bonded to a direct photopolymerizable composite resin. Then, the adhesive strength was measured in the same manner. The adhesive strength was 0 kg/cm''.

Comparative Example 2 HEMAIO% as A liquid, Bis-GMA 4
Adhesive strength was measured in the same manner as in Example 2, except that a composition consisting of 5% TEGDMA4, 4% TEGDMA4, and 4% BPOI was used. The adhesive strength was 0 kg/cm''.

Comparative Example 3 Maleic acid monoester compound 60 of the following formula (■) as liquid A
%, HEMAIO%, Bis-GMA 15%, TE
Adhesive strength was measured in the same manner as in Example 2, except that a composite consisting of 14% GDMA and % BPOI was used. The adhesive strength was 19 kg/cm''.

CHz2C (CI+) -COOCHzCHzOCOC
H=CH-COOH ■Example 3 Compound ■89%, HEAMIO% and BPO as liquid A
Adhesive strength was measured in the same manner as in Example 2, except that a composite material made of I% was used. The adhesive strength was 32 kg/c-.

Example 4 [Adhesion between enamel and composite resin] The adhesive strength was measured in the same manner as in Example 2, except that bovine tooth enamel was used instead of bovine dentin. Adhesive strength is 18
6 kg/cm".

Example 5 (Adhesion of Co-Cr alloy and composite resin 1) Same as Example 2 except that Co-Cr alloy: Sancorium (manufactured by Sankin Kogyo ■) was used instead of bovine dentin. The adhesive strength was measured. The adhesive strength was 145 kg/cm''.

As a pretreatment for the Co-Cr alloy, as in Example 2, it was polished with water-resistant silicon carbide paper to #800 under water injection, followed by sandblasting, and then ultrasonic cleaning in acetone for 5 minutes.

〔Effect of the invention〕

The maleic acid monoester compound of the present invention is a new compound, and because it has a well-balanced presence of hydrophilic groups and hydrophobic groups, it has particularly good physical properties necessary for dental adhesives, such as hardness, compressive strength, and water absorption. It has excellent properties.

Furthermore, the adhesive containing the maleic acid monoester compound of the present invention has high adhesive strength even in water or saliva because the polymer of the maleic acid monoester compound represented by formula (1) has good adhesiveness to tooth structure. can be maintained for a long period of time. Therefore, it has good durability in the oral cavity and, for example, when used as a filling material, it firmly adheres to teeth for a long period of time even in the moist state of the oral cavity and in an environment with severe temperature changes. Furthermore, when used as a primer coating agent for composite resins, orthodontic adhesives, etc., it strongly adheres to teeth, and also strongly adheres to composite resins, orthodontic adhesives, etc. Therefore, the gap between the tooth and the tooth can be reliably prevented, the margin sealability is also improved, and secondary caries can be completely prevented.

It can also be used as a resin cement that does not dissolve in saliva in place of zinc phosphate cement for bonding restorations to abutment teeth.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of a test bovine tooth used to measure the adhesive properties of the compounds of the present invention. 1... Bovine tooth 2... Cellophane tape 3... Plastic ring 4... Paraffin wax 5... Adhesive surface 6... Photopolymerizable composite resin filling layer 7...
Chemical polymerization type composite resin filling layer 8...Metal hook

Claims (2)

[Claims] (1) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (However, R_1 or R_2 represents -H or -CH_3, and m or n represents 1, 2 or 3.) maleic acid monoester compound. (2) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (However, R_1 or R_2 represents -H or -CH_3, and m or n represents 1, 2 or 3.) A dental adhesive comprising a maleic acid monoester compound or polymer.