JPS60250080A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide an adhesive compsn. consisting of a 4-vinylbenzoic ester compd. and a vinyl compd. as essential components, which can be prepd. at a readily controllable polymerization rate, is inexpensive and is suitable as dental material. CONSTITUTION:The adhesive compsn. is prepd. by blending about 0.1-10wt% (A) compd. of formula I [where R1 is H or a methyl group; R2 is H, a 1-5C (halogenated) alkyl group, a 2-4C (halogenated) alkylene oxide group, a group of formula II (where n is 1-4) which may be substituted with halogen or a methyl group] (e.g. methyl 4-vinyl benzoate), about 85-99wt% (B) vinyl compd. (e.g. methyl methacrylate) and preferably about 2-3wt% (C) free radical generator and/or photosensitizer (e.g. benzoyl peroxide or benzoin methyl ether).

Description

[Detailed description of the invention]

(a) Technical Field The present invention relates to a novel adhesive composition, particularly an adhesive composition suitable for dental materials. (b) Particle powder"L

Megumi 2-cyanoacrylic acid ester, epoxy, and cyanoacrylic acid esters have been known as adhesive compositions, but these have the disadvantage of poor water resistance and durability, especially for teeth. It was unsuitable as an adhesive due to the harsh conditions of the oral cavity. In addition, methyl methacrylate polymers and copolymers of vinyl compounds such as 2,2-bis(4-(2-hydroxy-3-methacryloxypropoxy)phenyl)propane and 1-lyethylene glycol dimethacrylate are used as tooth adhesives. have been used, but these alone do not have sufficient adhesion to the tooth, so the tooth must be treated with strong acid beforehand, which can cause unnecessary dissolution loss of the tooth surface and complicate dental treatment. Recently, adhesive compositions containing 4-methacryloxyethyl trimellitic anhydride, which have excellent water resistance and durability and can withstand use in the oral cavity, have been proposed. It became used as a dental adhesive, and this substance exhibits adhesive properties as it polymerizes.
When a redox polymerization catalyst, for example, is used as a room temperature polymerization catalyst, charge transfer occurs between the aromatic tertiary amine that should serve as an accelerator in this catalyst system and the acid anhydride group of 4-methacryloxethyl trimellitic anhydride. Because it forms a complex and becomes unable to perform its original polymerization catalyst function, making polymerization impossible, the room-temperature polymerization catalyst used in this adhesive system is generally limited to tri-n-butylborane oxide. Ta. Although this material has the advantage of providing strong adhesion to tooth dentin, the polymerization reaction is slow and it may take several minutes for final hardening in some cases, and it is extremely unstable in air. There were many problems from a dental clinical standpoint, such as the difficulty in handling it. -Means for solving the 911 point The inventors of the present invention have conducted extensive research to solve the above-mentioned problems with conventional adhesives, and have found that ('A') general formula (I
), [wherein R is hydrogen or a methyl group, R2 is hydrogen, an alkyl group having 1 to 5 carbon atoms that may be substituted with a halogen, or an alkylene having 2 to 4 carbon atoms that may be substituted with a halogen. may be substituted with an oxide group, or with a halogen or methyl group (CH2CH20 H group (n=
(an integer from 1 to 4)], (B) a vinyl compound, and optionally (C) a free radical generator and/or a photosensitizer as adhesive constituents. Tree n, which has a slow polymerization reaction and is conventionally used as a room-temperature polymerization catalyst,
It has been found that instead of -butylborane oxide, so-called common free radical generators can be used as catalysts, and that the adhesion effect is excellent. This free radical generator, especially a redox polymerization catalyst that combines peroxide with an aromatic tertiary amine compound, does not have adhesive properties to tooth dentin, but in addition to being inexpensive, it can moderate the polymerization rate. It is clinically advantageous as it is adjustable and easy to handle. There have been cases in the past where this redox polymerization catalyst has been used in adhesive compositions containing phosphate ester compounds, but in those cases, the polymerization of benzoyl peroxide, etc. may be due to poor polymerizability of the composition. It uses a redox catalyst consisting of peroxide and an aromatic tertiary amine compound together with other polymerization catalysts such as P-toluenesulfinic acid.
Even so, there are still problems, such as a considerable amount of unpolymerized portion remaining, particularly in the surface layer of the adhesive that comes into contact with air. In the present invention, m
There is also the advantage that such unpolymerized portions are small even if only a redox catalyst is used. The present invention relates to (A) general formula (■). [In the formula, R1 is hydrogen or a methyl group, R2 is hydrogen, an alkyl group having 1 to 5 carbon atoms that may be substituted with a halogen, an alkylene oxide group having 2 to 4 carbon atoms that may be substituted with a halogen, or CCH2CH20)nH group (n=
(B) a vinyl compound; optionally, CC) a free radical generator and/or a photosensitizer. The 4-vinylbenzoic acid used in the present invention has been taken up as a substance in a series of dental adhesive research studies in the past, but it has not been put to practical use as an adhesive composition and/or a dental material. Not done. In other words, it is known that an ethanol solution of 4-vinylbenzoic acid alone is used as a dental adhesive, but in that case, if a quick-curing resin is placed on top of the ethanol without evaporating it, it cannot participate in the polymerization reaction. Ethanol may remain at the adhesive interface, causing poor adhesion, and residual ethanol may inhibit the polymerization reaction itself.
It is necessary to evaporate the ethanol. However, since 4-vinylbenzoic acid remains as crystals on the coated surface after ethanol evaporates, the polymerization (adhesion) reaction becomes uneven even if quick-curing resin is applied to the adhesive surface, causing partial adhesion failure.
The adhesive force is reduced accordingly, making it impractical. Furthermore, 4-vinylbenzoic acid-methyl metatarylate (V
It is also known that a chloroform solution of BA-MMA) copolymer was used as a dental adhesive, but in this case as well, the solvent chloroform needs to be evaporated like the ethanol mentioned above. VBA-M
Since the MA copolymer is made by copolymerizing VBA-MMA in advance in a sealed tube in a nitrogen stream, the reaction activity of adhesion-related substances, such as the reactivity of carboxyl groups to tooth calcium, or the It is conceivable that the reaction (copolymerization) with the instant hardening resin to be applied will be reduced, and therefore the adhesive strength will be reduced. The present invention is the first to commercialize an adhesive composition, especially as a dental material, which contains the compound represented by the general formula CI) and a vinyl compound as main components and which can also use a free radical generator, such as a redox polymerization catalyst. It has been done. In the present invention, a method may be adopted in which the adhesive composition containing 4-vinylbenzoic acids and a vinyl compound with a high boiling point is diluted with a solvent, but even if the solvent is evaporated, the 4- Crystallization of vinyl benzoic acids does not occur, a uniform polymerization (adhesion) reaction occurs, and the adhesiveness is good. Furthermore, since the adhesion-related substances are in the form of monomers, the reaction activity of carboxyl groups and the ability to react (copolymerize) with quick-curing resins are greater than with copolymers, which also allows for good results to be obtained. It is thought that the factor is -. In the present invention, (A) the compound of general formula (1,) is R,
In the case of =H, specifically 4-vinylbenzoic acid, methyl 4-vinylbenzoate, 4-vinyl l. Chloromethyl fragrant, bromomethyl 4-vinylbenzoate,
Ethyl 4-vinylbenzoate, 2-chloroethyl 4-vinylbenzoate, 2-bromoethyl 4-vinylbenzoate, 4
-n-propyl vinylbenzoate, 4-vinylbenzoic acid 3
-Chloqpropyl, 3-bromopropyl 4-pinylbenzoate, isopropyl 4-vinylbenzoate, 1-(chloromethyl)ethyl 4-vinylbenzoate, 1-(bromomethyl)ethyl 4-vinylbenzoate, 4-vinyl benzoin an
-butyl, 4-chlorobutyl 4-vinylbenzoate, 4-
4-bromobutyl vinylbenzoate, isobutyl 4-vinylbenzoate, 3-chloro-1-methylpropyl 4-vinylbenzoate, 3-bromo-1-methylpropyl 4-vinylbenzoate, n-pentyl 4-vinylbenzoate , 5-chloropentyl 4-vinylbenzoate, 5-bromopentyl 4-vinylbenzoate, impentyl 4-vinylbenzoate, 4-chloro-1-methylbutyl 4-vinylbenzoate,
4-Bromo-1-methylbutyl 4-vinylbenzoate, 4
-Epoxyethyl vinylbenzoate, 2,3-epoxyprobyl 4-vinylbenzoate, 2,3-vinylbenzoate
-Epoxybutyl, 2,3-epoxy-4-chlorobutyl 4-vinylbenzoate, 2,3-epoxy-4-bromobutyl 4-vinylbenzoate, 2-hydroxyethyl 4-vinylbenzoate, 2-hydroxyethyl 4-vinylbenzoate -Hydroxy-
2-methylethyl, 2-(2-hydroxyethoxy)ethyl 4-vinylbenzoate, 2-(2-vinylbenzoate)
-hydroxypropoxy)ethyl, 2-chloro-2-(2-hydroxyethoxy)ethyl 4-vinylbenzoate,
2-Bromo-2-(2-hydroxyethoxy)ethyl 4-vinylbenzoate, 3,6-thioxer-8-hydroxyoctyl 4-vinylbenzoate, 3°6-thioxer-8-hydroxynonyl 4-vinylbenzoate, 4 -5-chloro3,6-thioxor-8-hydroxyoctyl vinylbenzoate, 5-bromo3,6-thioxer-8-hydroxyoctyl 4-vinylbenzoate, 3,6-vinylbenzoate
．． 9-1-lioxer 11-hydroxyundecyl, 4
-vinylbenzoic acid 3.6.9-)-lioxer 11-hydroxydodecyl, 4-vinylbenzoic acid 8-chloro-1
1-hydroxy-3,6,9-trioxaundecyl,
4-vinyl Yasui, fragrant 8-bromo 11-hydroxy-
Examples include 3,6,9-trioxaundecyl. In addition, in the case of R,=CH3, 4- of the above-mentioned 4-vinylbenzoic acids
Specific examples include 4-allylbenzoic acids in which the vinyl group is changed to a 4-allyl group. These can be used alone or as a mixture; for example, a mixture of 4-vinylbenzoic acid or 4-allylbenzoic acid and other compounds of general formula (I) can be used. (A) Used in combination with a compound represented by general formula (I) (
B) Vinyl compounds include methyl methacrylate, ethyl methacrylate, butyl methacrylate, polyethylene glycol dimethacrylates, and 2-hydroxyethyl methacrylate. Tetrahydrofurfuryl methacrylate-1-,2,2-bis(4-(2-methacryloxyethoxy)phenyl)propane, acrylonitrile, vinyl acetate, 2-cyanoacrylate, styrene, divinylbenzene, polymethyl methacrylate, poly Examples include ethyl methacrylate, which may be used alone or in combination. Among them, triethylene glycol dimethacrylate and 2,2-bis(4-(2-methacryloxyethoxy))
Phenyl]propane is preferably used. In the present invention, the proportions of (A) the compound represented by general formula (I) and CB) various vinyl compounds can be changed depending on the purpose of use of the adhesive and/or dental material, but generally (A) It is preferable that the compound represented by the general formula (T) accounts for 0.1 to 10% by weight based on the total amount of the various vinyl compounds (B). Examples of the free radical generating agent (C) used include various peroxides such as benzoyl peroxide and dicumyl peroxide, and azobisisobutyronitrile, but in the case of polymerization bonding at room temperature, benzoyl peroxide is used. Redox polymerization catalysts include combinations of various peroxides such as peroxides and aromatic tertiary amines such as N,N-dimethyl-p-+heluidine, N,N-diethanol-p-toluidine, etc. Benzoyl peroxide-N,N-jetanol-p-toluidine is preferably used. Furthermore, (C) photosensitizers include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. when polymerized and bonded under ultraviolet irradiation; N,N-dimethylaminoethyl methacrylate-1~
is preferably used. . The amount of these (C) used is 0 with respect to the total amount of (A) the compound represented by general formula (I) and (B) various vinyl compounds.
．． It is about 1 to 5% by weight. (A), (B), (C) in the adhesive composition of the present invention
To summarize the blending range of (A)O,
t~10% by weight, (B) 85~99% by weight, (C) 0.
The amount is 1 to 5% by weight, and the preferred range is (A) 2 to 5% by weight.
5% by weight, (B) 92-96% by weight, (C) 2. ,~
It is 3-fold view%. In the present invention, the adhesive composition ('C) not containing a free radical generator and/or photosensitizer is different from other adhesive compositions containing a free radical generator and/or photosensitizer. Can be used in combination. The adhesive composition of the present invention may further contain other additives, such as inorganic powder fillers such as kaolin, tar, clay, silica, alumina, and glass, other viscosity-imparting agents, polymerization accelerators, and polymerization regulators. Agents, polymerization inhibitors, etc. can also be blended. Tackifiers include wax, ethylene-vinyl acetate copolymer, polymethyl methacrylate,
Polyethyl methacrylate and the like also fall under this category, and polymethyl methacrylate and polyethyl methacrylate are also used as aggregates in the same way as inorganic powder fillers. Examples of polymerization accelerators include so-called free radical generators, and examples of polymerization regulators include nitro compounds such as nitrobenzene. Examples of the polymerization inhibitor include hydroquinone, hydroquinone methyl ether, butylated hydroxytoluene, and 2-hydroxy-3-methoxybenzophenone. The adhesive of the present invention generally does not require a particular solvent, and (A
) A preferred method is to use the compound represented by the general formula (I) in a state in which it is uniformly dissolved in the vinyl compound (B). However, when an adhesive composition containing (A) a compound represented by the general formula (■), (B) a vinyl compound, and (C) a free radical generator and/or a photosensitizer is used in a solvent such as alcohol or ketone, or an adhesive containing (A) a compound represented by general formula (1) and (B) a vinyl compound. The composition is dissolved in a solvent such as alcohol or ketone, the solution is first applied to an adherend, the solvent is evaporated, and (C) other adhesives containing free radical generators and/or photosensitizers are applied. A method of copolymerization and adhesion by coating or building up the agent composition can also be adopted. As a preferred embodiment, for example, (A) general formula (I
) is mixed with (+3) methyl methacrylate-1- and polymethyl methacrylate at room temperature in the presence of (C) benzoyl peroxide-N,N-jetanol-p-toluidine to form an adhesive layer. Similarly, (A) a compound represented by the general formula (1) is prepared in the presence of (C) benzoyl peroxide-N,N-jetanol-p-toluidine (,B) 2,2-bis[
A method of forming an adhesive layer by mixing 4-(2-methacryloxyethoxy)phenyl]propane, triethylene glycol dimethacrylate and silica at room temperature; 2.2
-Bis(/1-(2-methacryloxyethoxy)phenyl)propane, triethylene glycol dimethacrylate, and alcohol are mixed at room temperature, the alcohol is evaporated, and dental materials such as so-called composite resins are built up. A method of copolymerization adhesion, etc. is a method of bonding (A) the compound represented by the general formula N) and (B) of the present invention.
Adhesives containing vinyl compounds have extremely high adhesive properties, particularly excellent water resistance and durability, and can be used for various purposes. Among these, it is suitable for teeth, metals, porcelains, and as an undercoat for paints. As mentioned above, conventional dental adhesives include methyl methacrylate polymers and copolymers of vinyl compounds such as 2,2-bis(4-(2-methacryloxyethoxy)phenyl)propane and triethylene glycol dimethacrylate. are known, but since these have insufficient adhesion to teeth, the teeth have been treated with strong acid before use.On the other hand, in the present invention, (A) general formula (T) The adhesive between the expressed compound and (B) various vinyl compounds has a sufficiently strong adhesion force to teeth, so it does not necessarily require strong acid treatment as in the past. Its value is also significant in the sense of preventing dissolution loss of the present invention.Also, as mentioned above, adhesives with similar functions to the present invention are known, but the polymerization method is limited to some extent, and the polymerization rate is slow. Problems such as slow polymerization and large unpolymerized portions have also been pointed out.For example, in the case of room-temperature polymerization, the present invention uses the simplest so-called redox system such as benzoyl peroxide-N,N-jetanol-P-toluidine. A polymerization catalyst can be used, the polymerization rate can be appropriately controlled, and there are few unpolymerized parts, which is extremely advantageous in terms of adhesion. However, the present invention is not limited thereto.Example: A powder-liquid composition as an adhesive is prepared and used as part A.Part A: Powder composition Part by weight Polymethyl methacrylate fine powder 98. 5 Benzoyl peroxide 1.5 Liquid composition Methyl methacrylate 97.5 4-vinylbenzoic acid 1.5 N,N-getanol-P-toluidine 1.0 The anterior labial surface of a cow was thoroughly polished with No. 610 emery paper. After smoothing the surface well, a vinyl tape (10 mm in diameter) with a circular hole of 6 mm in diameter was pasted on it.After applying Agent A to the circular hole in a slightly thick layer using the so-called brush stacking method using a small brush, an acrylic tape with a diameter of 6+ nm was applied. The rod was adhered. After 1 hour, the natural tooth with the acrylic rod still attached was immersed in water at 37°C. After 24 hours, the natural tooth was taken out of the water and the adhesive force was measured using an autograph. Adhesive strength is 54.2Kg/
As a comparative example, the liquid composition of Agent A of Example 1 did not contain 1.5 parts by weight of 4-vinylbenzoic acid, but contained 99.0 parts by weight of methyl methacrylate and N,N-jetanol. -p-1
- Prepare a solution of 1.0 parts by weight of Shiidin, and
The procedure of Example 1 was repeated using a similar composition. The adhesive force was 0 kg 7 cm2. Example 2 A composition consisting of a powder liquid similar to the A agent of Example 1 was prepared,
Use as agent B. Part B: Powder composition Weight part Polymethyl methacrylate fine powder 98.5 Benzoyl peroxide 1.5 Liquid composition Methyl methacrylate 97.5 Ethyl 4-vinylbenzoate 1.5 N,N-jetanol-pt -Luidine 1.0 Example 1 was repeated using Part B in place of Part A of Example 1. The adhesive strength was 43.5 Kg/cm2. Example 3 A powder-liquid composition was prepared as an adhesive and used as agent C. Agent C: Powder composition Part by weight Silane-treated fine silica powder 98.5 Benzoyl peroxide 1.5 Liquid composition 2.2-Bis(4-(2-methacryloxyethoxy)phenyl)propane 62.0 Triethylene glycol dimethacrylate 35.5 4-vinylbenzoic acid 1.5 N,N-jetanol-p-toluidine 1.0× Silica powder with particle size distribution of 35 to 1 micron, 95%
A solution prepared by adjusting ethanol to pH 4.5 to 5.5 with acetic acid and adding 1-methacryloxypropyltrimeth-1-xysilane to a concentration of 2% by weight is used for treatment. This silica powder slurry was dried at 120° C. to remove moisture and adhere silane. No. 1 metal piece with a flat surface of approximately 10 mm x 10 mm. The surface was well polished with No. 1 emery paper to obtain a certain smooth surface condition, and a vinyl tape (10 mm in diameter) with circular holes of 6 mm in diameter was pasted thereon. C in the circular hole using the brush stacking method
After applying the agent somewhat thickly, a stainless steel rod with a diameter of 6 mm was adhered. After L hours had passed, the metal piece with the stainless steel rod still attached was immersed in water at 37°C. After 24 hours, the metal piece was taken out of the water and the adhesive strength was measured using an autograph. The results are shown in Table 1. As a comparative example, in the liquid composition of Agent C of Example 3, 1.5 parts by weight of 4-vinylbenzoic acid was not included, and 2°2-bis[
4-(2-methacryloxyethoxy)phenyl 3103
262.0 parts by weight, 37.0 parts by weight of triethylene glycol dimethacrylate and N,N-jetanol-
Prepare a solution of 1.0 parts by weight of P-toluidine,
The procedure of Example 3 was repeated using C powder composition. The results are also shown in Table 1. Table 1 The composition of the metal pieces in the table is as follows. Cobachrome: Cobalt-chromium alloy for dental casting Ninestar: Nickel-chromium alloy for dental casting Tooth grinding metal Para 1
2: Gold-palladium alloy for dental casting Paragold: Silver-palladium alloy for dental casting Both manufactured by Nihon Denken Kogyo Co., Ltd.
Product ★: The adhesive layer was destroyed in the adhesive force measurement. Example 4 According to the method of Example 3, a metal piece with a stainless steel rod attached was immersed in water at 37°C for 24 hours, and then immersed in water at 4°C and 60°C alternately for 1 minute each 60 times for a total of 2 hours. Then, the adhesive strength was measured. The results are shown in Table 2. As a comparative example, Example 4 was repeated using the same material as that of the comparative example of Example 3. The results are also shown in Table 2. Table 2 Example 5 The bottom of a cylindrical fired dental porcelain (product name: VITAVMK"68", vrTA!!B) with a diameter of 10 mm and a height of about 8 mm was coated with No. 1 emery paper. The surface was polished to a certain level of smoothness, and a vinyl tape (diameter 10n+n+) with six circular holes in diameter was pasted thereon. After a somewhat thick coating of agent C was applied to the circular hole using the rod stacking method, a stainless steel rod with a diameter of 6 mm was adhered. After 1 hour,
The porcelain material with the stainless steel rod still attached was immersed in water at 37°C. After 24 hours, the porcelain was taken out of the water and the adhesive strength was measured using an autograph. Adhesive strength is 50.3Kg
/cm2, the adhesive layer was destroyed. As a comparative example, the operation of Example 5 was repeated using the same material as that of the comparative example of Example 3. Adhesive strength is 1.8Kg
/cm2. Example 6 A liquid composition was prepared as a coating agent and used as Agent D. Agent D: 2.2-bis(4-(2-methacryloxyethoxy))
Phenyl]propane 30.0 Triethylene glycol dimethacrylate-1-18,0 4-vinylbenzoic acid 2. Q Ethyl alcohol 5'0.0 Two bases consisting of a vinyl compound as a filler, an inorganic filler, and a polymerization initiator were prepared, and P,
paste, P2 paste, and P paste. P, paste: 2.2-bis(4-(2-methacryloxe 1 hexy)
Phenyl]propane 2[,. Triethylene glycol dimethacrylate 6.0 Silanized silica powder 71. O N, N-jethanol-pt luidine 2. QP2 paste: 2.2-bis[4-(2-methacryloxyl-xy)
Phenyl]propane 21.0 1-lyethylene glycol dimethacrylate 6.0 Silanized silica powder 71.5 Benzoyl peroxide 1.5 *The same silica powder as in Example 5 as agent C was used. Using the molar region of a freshly extracted human tooth, a cavity with a diameter of approximately 4 mm and a depth of 311 m was formed in the tooth neck using an air turbine, and the enamel region was treated with a 40% phosphoric acid aqueous solution, thoroughly rinsed with water, and thoroughly dried with air. . Next, after applying a thin layer of agent D to the window wall and blowing off the solvent with air, agent P was filled into the cavity. Cure time was approximately 3 minutes. This thing is 4℃ and 6
60 times for 1 minute each, alternately, in the Tsukusin solution at 0 °C, 4 times.
Margin sealability was evaluated by observing the state of dye penetration after soaking for 12 hours. As a result, there was no intrusion at all, and the sealing properties were excellent. As a comparative example, 2.2-bis(4-
(2-methacryloxyethoxy)phenyl]propane 3
0.0 parts by weight, 20.0 parts by weight of 1-liethyl/glycol dimethacrylate and 50.0 parts by weight of ethyl alcohol.
A solution of part by weight was prepared, and the process of Example 6 was repeated using this solution. As a result, pigment invasion was seen everywhere, and there was no effect of margin sealing. Agent Akitoshi Hitotaka Agent Akiko Otawa

Claims (3)

[Claims] (1) (A) General formula (T), [wherein R1 is hydrogen or a methyl group, and R2 is hydrogen. An alkyl group having 1 to 5 carbon atoms that may be substituted with a halogen, an alkylene oxide group having 2 to 4 carbon atoms that may be substituted with a halogen, or an alkylene oxide group having 2 to 4 carbon atoms that may be substituted with a halogen or a methyl group (CH2CH207T' I
H group (n = an integer of 1 to 4)], (B) a vinyl compound, and optionally (C) an adhesive composition containing a free radical generator and/or a photosensitizer. . (2) The adhesive composition according to claim 1, which is a dental adhesive composition. (3) The adhesive composition according to claim 1 or 2, wherein the free radical generator (C) is a redox polymerization catalyst.