JPH0243721B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an adhesive composition for biological hard tissue. More specifically, the present invention relates to medical or dental adhesives for biological hard tissues such as bones and teeth. BACKGROUND OF THE INVENTION Among medical and dental materials, particularly dental materials, amalgams of silver alloys and mercury, silicate cements, and the like have conventionally been used as restorative fillers.
However, although amalgam has excellent physical properties, it has poor adhesion to tooth structure and insufficient impact resistance, so it has poor margin sealing properties and is susceptible to secondary cavities. It may have an adverse effect on living organisms in terms of toxicity. Further, silicate cement has drawbacks such as being soluble, having low adhesion to tooth structure, poor margin sealing properties, and strong pulp irritation. Filling materials based on epoxy resins have also been used, but they have drawbacks such as poor hardness and wear resistance, and high water absorption. Therefore, for example, U.S. Patent No. 3539533
As disclosed in No. 3,926,906, etc., bisphenol A-diglycidyl methacrylate (hereinafter referred to as "Bis-GMA") has superior compressive strength and water resistance than conventional products, and has relatively low pulp irritation. ) and a large amount of inorganic filler as the main components, and a benzoyl peroxide-tertiary amine catalyst as a curing agent (hereinafter referred to as composite resin), which has come to be used particularly as a filling material for restoration of anterior teeth. Although Bis-GMA, which has a hydrophilic group, is used, the adhesion of Bis-GMA to anterior teeth is somewhat poor, and since a large amount of inorganic filler is also used, the viscosity of the composite resin is high and the tooth surface Due to poor wettability to the tooth, the adhesion to the dentin and enamel of the tooth is poor, resulting in the filling material falling off after filling the tooth, and secondary caries due to poor margin sealing. Recently, in order to improve the adhesion of Bis-GMA composite resins to teeth, adhesives based on Bis-GMA that do not contain inorganic fillers have been developed. Methods of using it have also been proposed, but its effectiveness has not yet been fully recognized.In addition, it is used as a caries-preventing filling material or as an orthodontic adhesive for the purpose of adhesion to tooth structure. Adhesives based on α-cyanoacrylate have been developed, but their adhesive strength quickly decreases under humid conditions such as in the oral cavity. To date, no adhesive material has been found that has adhesive strength and can maintain this adhesive strength for a long period of time in a humid and temperature-variable environment such as the inside of the oral cavity. In view of these problems, the authors conducted research on adhesives that have excellent adhesion to the hard tissues of living organisms, and as a result, they completed the present invention. Another object of the present invention is to provide an adhesive material that has a strong and durable adhesive force.Another object of the present invention is to provide an adhesive material that has a strong and durable adhesive force. It is an object of the present invention to provide an excellent adhesive material which provides strong and durable adhesive force between the materials and which does not lose the properties of the preservation/prosthetic material. According to the present invention, the above objects and advantages are achieved by (A) a polymerizable polymer having at least one group selected from the group consisting of carboxyl group, epoxy group, amino group and hydroxyl group; acrylic ester,
Polymerization with 50 to 995% by weight of a methacrylic acid ester, acrylamide derivative, or methacrylamide derivative (hereinafter referred to as component A) and (B) 0.5 to 50% by weight of a titanium compound having an alkoxy group (hereinafter referred to as component B). This can be achieved by an adhesive composition for biological hard tissues, which is characterized in that it contains a catalyst and a promoter. [Component A] The acrylic ester or methacrylic ester used as component A in the present invention may be any acrylic ester or methacrylic ester as long as it has at least one group selected from the group consisting of a carboxy group, an epoxy group, an amino group, and a hydroxyl group. However, in particular, the following formula (1) [In the formula, n is a positive integer of 1 to 3, m is 1 or 2, Y is -OH, _-NH2 ,

[Formula] or -COOH, Z is an (n+m) valent organic group having 1 to 25 carbon atoms, and R ₁ is a hydrogen atom or a methyl group] is preferred. The above group Y imparts hydrophilicity to the acrylic ester or methacrylic ester. A- More preferable examples of such acrylic esters and methacrylic esters include the following. (1) Compound having the following formula 1-A [In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is -CH ₂ CH ₂ -,

[Formula] or

It is a linear or branched aliphatic hydrocarbon residue having 2 to 6 carbon atoms and which may have a hydroxyl group as a substituent, represented by the formula: l is 1, 2 or 3. ] (2) A phosphoric acid ester of the compound of the above formula 1-A represented by the following formula 1-B, [In the formula, the definitions of R ₁ and R ₂ are the same as in Formula 1-A. However, when the group -R ₂ - has -OH as a substituent, this -OH may also be a phosphoric acid ester. ] (3) A compound represented by the following formula 1-C and its phosphoric acid ester, [In the formula, the definitions of l and R ₁ are the same as in formula 1-A. R ₃ is an alkyl group having 1 to 3 carbon atoms or a phenyl group. ] (4) A compound represented by the following formula 1-D, [In the formula, the definition of R ₁ is the same as in formula 1-A, and X is

[Formula] is an alkylidene group or -SO ₂ -, and E is an oxyalkylene group having 2 to 5 carbon atoms having a hydroxyl group (-OH) as a substituent, or an oxyalkylene group having 1 to 5 carbon atoms having a hydroxyl group as a substituent.
5 alkylidene group] (5) Compound represented by the following formula 1-E [In the formula, R is -CH ₂ CH ₂ -, -CH ₂ CH ₂ O CH ₂ CH ₂ -

【Formula】Also teeth

[Formula]. ] (6) A compound represented by the following formula 1-F, [In the formula, the definition of R ₁ is the same as in the above formula 1-A] (7) A compound represented by the following formula 1-G, [In the formula, the definition of R ₂ is the same as in Formula 1-A. ] (8) A compound represented by the following formula 1-H, [In the formula, the definition of R ₁ is the same as in the above formula 1-A, and p is 0 or a positive integer of 1 to 3. ] Among the above (1) to (8), especially formulas 1-A, 1-C, 1-
Those having a hydroxyl group or an epoxy group represented by D, 1-E, 1-F and 1-H are particularly preferred. A- In addition, the acrylamide derivative or methacrylamide derivative having at least one group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, and a hydroxyl group used in the present invention is represented by the following formula (2). It is preferable that the [In the formula, m is 1 or 2, R ₁ is a hydrogen atom or a methyl group, R ₄ is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, Y is -OH, -NH ₂ ,

【formula】

[B component]

Next, the titanium compound having an alkoxy group used as component B in the present invention will be explained. B- As a titanium compound having an alkoxy group, the following formula (3), [In the formula, R ₆ is an aliphatic hydrocarbon residue having 1 to 20 carbon atoms, and has 1 or 2 hydroxyl groups, an alkoxy group having 1 to 3 carbon atoms, or a di(hydroxyalkyl)amino group (however, an alkyl The number of carbon atoms in the group may be 2 or 3), R ₇ , R ₈ , and R ₉ are each mutually or R ₆
is a hydrocarbon residue which may be the same as or different from R 6 and may have a substituent according to the same definition as R ₆ above, or the following formula (3)′ In the formula, _R10 is

[Formula] (where R ₈ is an olefinic hydrocarbon residue represented by a hydrogen atom or a methyl group, or a saturated aliphatic hydrocarbon residue having 1 to 20 carbon atoms, and this saturated hydrocarbon residue is or two hydroxyl groups (-OH), alkoxy groups (with 1 to 3 carbon atoms), or the formula

A compound represented by the following formula, which may have an acyl group represented by the formula (wherein R ₈ is an alkyl group having 1 to 3 carbon atoms), is preferred. Particularly preferred examples of the titanium compound represented by the above formula (3) are as follows. (11) A compound represented by the following formula 3-A, [In the formula, R _6a , R _6b , R _6c and R _6d may be the same or different and each is an aliphatic hydrocarbon residue having 1 to 20 carbon atoms, and one or two hydroxyl groups as a substituent, It is an alkoxy group or a di(hydroxyethyl)amino group having 1 to 3 carbon atoms. ] (12) A compound represented by the following formula 3-B, [In the formula, f is 1, 2 or 3, the definition of R _6a is the same as in the above formula 3-A, and R _7a is a saturated aliphatic hydrocarbon residue having 1 to 20 carbon atoms; , this saturated hydrocarbon residue is one or two hydroxyl groups, an alkoxy group having 1 to 3 carbon atoms, or an acyl group having 1 to 3 carbon atoms. ] (13) A compound represented by the following formula 3-C, [In the formula, e, g and h are each 1 or 2, the total of e, g and h is 4, the definitions of R _6a and R _7a are the same as in formula 3-B, and R ₁ is a hydrogen atom or a methyl group. ] Among these, tetraalkoxytitanium represented by formula 3-A is particularly advantageous. Among the B components described above, specific examples of suitable ones are shown below. About 3-A

[Table] 〓〓 Ti(OCH ₂ CHCH ₂ CH ₂ CH ₂ CH ₃ ) ₄

[Table] 〓〓 i−C ₁₇ H ₃₅ CO−Ti

\
(OC C=CH ₂ ) ₂
‖｜
O CH ₃
can be mentioned. The adhesive composition of the present invention has a component A of 30 to 30%.
It is sufficient if the A component is 50 to 99.5 wt% and the B component is 0.5 wt%.
~50% by weight. In the present invention, it is preferable that the A component is 80 to 99.5% by weight, especially 95 to 99.5% by weight, and the B component is 0.5 to 20% by weight, especially 0.5 to 5% by weight. A
Although a certain degree of adhesion to biological hard tissue can be obtained even if only the component acrylic ester and/or methacrylic ester is used as an adhesive material, in order to achieve the purpose of the present invention, it is necessary to use the organic metal component B. If the compound is required at 0.5% by weight or more, and conversely, component B is blended in a large amount exceeding 50% by weight,
The strength of the cured film of the adhesive composition decreases, and for example, when the composition is used as an adhesive between biological hard tissue and a repair filling material, the adhesive force between the two tends to decrease. The adhesive composition for biological hard tissue of the present invention,
When used to bond biological hard tissue preservation and prosthetic materials such as the dental composite resin, which is generally said to be difficult to adhere to biological hard tissue such as teeth, it has an extremely excellent adhesive effect. Although the details of the chemical reaction mechanism to explain the reason for the appearance of
Since it contains 99.5% by weight, it has good leakage to the hard tissue surface and can be applied evenly to uneven parts of the hard tissue surface, and the resin in the hard tissue surface and the preservation/prosthetic material. Forming a strong polymer film between the hard tissue surface and the preservation/prosthetic material with a strong chemical bonding force with the hydrophilic component contained in the component, and preferably 0.5~ The organometallic compound containing an alkoxy group (component B) containing 50% by weight is such that the alkoxy group of the metal compound remains on the hard tissue surface and inhibits the adhesion between the preservation/prosthetic material and the hard tissue surface. It reacts with the trace moisture or water film that is the cause, and removes the trace water or water film from the system, and at the same time, the alkoxy groups that have reacted with the trace water or water film change into hydroxyl groups, thereby reducing the hard tissue. This is thought to be due to strong bonding with hydrophilic groups present on the surface. In particular, component B has extremely high reactivity between the alkoxy group and the trace amount of moisture or moisture film remaining on the hard tissue surface, so even a small amount of the titanium compound component in the composition of the present invention does not adhere to the hard tissue surface. Although the effect is clearly visible, if the titanium compound component increases, the permanent adhesiveness in a wet state may deteriorate, so as mentioned above, the amount of titanium compound added to the composition may be relatively small. it is conceivable that. The adhesive composition for biological hard tissues of the present invention includes:
In practical use, it usually contains, in addition to the above-mentioned composition, a catalyst for polymerizing the composition, a promoter that reacts with the catalyst to generate free radicals, and the like. A method of using such an adhesive material is, for example, by preparing in advance a liquid (liquid A) consisting of the composition and an accelerator, and a liquid (liquid B) consisting of the composition and a catalyst, and then preparing the liquid when used by a doctor. When these two liquids are mixed together, the composition starts polymerization, which is very convenient. The adhesive composition of the present invention can be easily polymerized and cured using a catalyst and a promoter. At this time, applying heat often harms living organisms when used in fields related to living organisms, so it is preferable to use a material that can be cured at room temperature during use. In practical use, the adhesive of the present invention can be made into a two-component system, one of which contains a catalyst and the other a promoter, and the two are mixed immediately before use. It's advantageous. For example, peroxide is suitable as the catalyst,
Preferably, this is used in combination with an accelerator.
Examples of peroxide catalysts include diacyl peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, and lauroyl peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide. Examples include peroxide, hydroperoxides such as 2,5-dimethylhexane 2,5-dihydroperoxide, ketone peroxides such as methyl ethyl ketone peroxide, and peroxycarbonates such as tert-butyl peroxybenzoate. . These peroxide catalysts are generally preferably used in a proportion of 0.1 to 3.5 wt% based on the total weight of the polymerizable monomer of the formula () or () of the present invention. Furthermore, promoters that can be used in combination with this peroxide include, for example, N,N-bis-(2-hydroxyethyl)-4-methylaniline, N,N-bis-(2-hydroxyethyl) −
3,4-dimethylaniline, N,N-bis-(2
-hydroxyethyl)-3,5-dimethylaniline, N-methyl-N-(2-hydroxyethyl)-
Tertiary amines such as 4-methylaniline, N,N-dimethyl-P-toluidine, N,N-dimethylaniline, triethanolamine, other transition metal ions such as cobalt naphthenate and cobalt octoate, P-toluene Examples include amine salts of sulfonic acid and sulfinic acid. These accelerators can generally be used in a proportion of 0.1 to 3.5 wt% based on the total weight of the polymerizable monomer. The adhesive composition of the present invention not only has strong and durable adhesion to biological hard tissue, but also has strong and durable adhesive strength between biological hard tissue preservation/prosthetic materials and biological hard tissue. Provides strong adhesive strength. The adhesive composition of the present invention can be used in combination with any conventionally known medical or dental resin forming materials or composite resins. When the adhesive composition of the present invention is used to fill a tooth with a dental composite resin that has conventionally had almost no adhesive strength to the tooth structure, excellent adhesive strength can be obtained and the sealing properties of the cavity can be improved. It can be significantly improved. Representative examples of conventionally known monomers for forming medical or dental resins and composite resins using such monomers include the following U.S. patents, British patents, and Japanese Patent Application Publications, U.S. Patents 3541068; 3597389; 3810938; 3923740;
4067853; 3825518; 3862920; 3853962; British patent 1451262 Japanese Patent Application Publication No. 48-96332; Japanese Patent Application Publication No. 116581/1977, etc., the details of which are given priority on the same day as the present application by the present inventors. It is introduced in the specification of the pending patent application (CO-pending patent application) with the filing date. The present inventors also used the following formula () as a monomer for forming medical or dental resins: [However, in the formula, Z is a hydrogen atom or the following formula R ₁ , R ₂ , R ₃ and R ₄ may each be the same or different and are a hydrogen atom, a methyl group, an ethyl group, or an n- or iso-propyl group. It has been discovered that at least one compound that Furthermore, many inorganic fillers such as quartz powder, glass powder, glass beads, aluminum oxide, borosilicate glass, barium glass, hydroxyapatite, aluminosilicate, etc. have been known as fillers for the above-mentioned composite resins. The inventors have determined that the material is made of a nitride of at least one metal selected from Group B, Group B of the Periodic Table of Elements, and the group consisting of boron, aluminum, and silicon, and has a Mohs hardness of at least 7. It has been discovered that a filler characterized by the following characteristics, especially a powder having a particle size of 50 microns or less, is extremely excellent as a filler for forming the composite resin, and details of these inventions are described in the above-mentioned pending patent application of the present inventors. CO-pending Patent
(Application) detailed in the specification. The adhesive composition of the present invention comprises a medical or dental resin-forming monomer of the above formula () according to the invention of the present inventors, or a conventionally known inorganic filler in such a monomer, or a monomer according to the invention of the present inventors. The new composite resin containing the metal nitride filler can be used to fill teeth. In this case, the physical properties of the new composite resin, such as compressive strength, hardness, and abrasion resistance, are comparable to those of amalgam, and its adhesion to the tooth structure is significantly improved, so conventionally only amalgam could be used. The present invention provides a completely new dental material as a filling material for molar tooth restoration, which has not been possible previously. The adhesive composition of the present invention takes advantage of its excellent adhesion to biological hard tissues, and can be used, for example, in bone cements, artificial bones, etc. in the fields of orthopedics and plastic surgery, or as crown restoration materials in the fields of dental conservation and prosthetics. It can be applied to abutment construction materials, bonding materials, filling materials, caries prevention sealants, etc. Hereinafter, the present invention will be specifically explained with reference to Examples. In the examples, "parts" and "%" mean "parts by weight" and "% by weight" unless otherwise specified. In the examples, the adhesive strength and percolation tests were measured according to the following methods. (1) Adhesion test method The anterior crown of a fresh bovine tooth embedded in an acrylic resin square rod was ground horizontally to expose the enamel, stored in water, and removed from the water immediately before performing the adhesion test. , wipe off moisture and remove enamel part by 50%
After treatment with aqueous phosphoric acid for 1 minute, all samples were dried with a stream of air. Next, after applying the adhesive composition to the tooth surface, a composite resin consisting mainly of a curable resin and a large amount of inorganic filler is placed on the surface of the bovine tooth enamel, and an acrylic square rod is placed on top of the enamel. Butt it against the surface, press it gently, leave it at room temperature for 15 minutes, and then immerse it in water at 37℃.
Soaked for 24 hours. The tensile adhesive strength of the sample taken out was measured at both ends of the acrylic square bar at a speed of 1 mm/min. Adhesive strength is shown as an average value of 10 points each. In addition, the green sealing property test method in the examples was conducted in accordance with the following method. (2) Percolation test Thoroughly clean the surface of a freshly extracted healthy human tooth.
Four simple 2 mm cylindrical cavities reaching the dentin with a diameter of approximately 3.5 mm were formed for each sample tooth, and then the cavities were immersed in physiological saline for storage. Immediately before this test, the above-mentioned extracted tooth was taken out of physiological saline, washed with distilled water, cleaned with ethanol, and dried. Thereafter, only the enamel part in the cavity was etched with a 40% phosphoric acid aqueous solution for 1 minute, and then washed with water and dried. Thereafter, an arbitrary adhesive composition was applied to the cavity surface, and then an arbitrary composite resin was filled and pressed with a polyester strip until hardened. After curing, it was immersed in artificial aeration and left for 14 days. Thereafter, the apical foramen of the tooth was sealed with ionomer cement, and then immersed alternately in water heated to 60°C and a 0.2% fuchsin aqueous solution cooled to 4°C for 1 minute each, and this operation was repeated 120 times. Thereafter, the fuchsin adhering to the tooth surface was washed off with water, and the filled part was then cut vertically with a diamond disc, and the depth of penetration of fuchsin from the edge of the cavity was observed using a microscope. At that time, the ratio of the length of fuchsin penetration to the length of the cavity wall perpendicular to the tooth surface was evaluated as the degree of fuchsin penetration. Example 1 Twelve types of adhesive compositions shown in Table 1 were prepared. In each case, the main ingredients are 98 parts of various monomers corresponding to the A component of the present invention listed in Table 1 and 2 parts of tetraisopropyl titanate corresponding to the B component of the present invention, which harden at room temperature at the time of use. It is a two-component system so that one side (liquid A) has an accelerator.
NN-bis-(2-hydroxyethyl)-4-methylaniline (hereinafter referred to as DEPT), the other (b
(liquid) was mixed with benzoyl peroxide (hereinafter referred to as BPO) as a peroxidation catalyst and 2,5-di-tertiarybutyl 4-methylphenol (hereinafter referred to as BHT) as a storage stabilizer.
(b) Mix a portion of the two solutions at a ratio of 1:1 between coverslips, let stand at 24℃, and adjust the amount of catalyst and other additives so that it takes 3 minutes for the coverslips to stop moving. were appropriately prepared as shown in Table 1. A specific example of the composition of the sample adhesive composition is shown in the table below. (Table 1 No. 1
in the case of).

【table】

[Table] Nos. 2 to 12 in Table 1 were also prepared in the same manner as above. As a comparative example, a bonding agent "adaptic" manufactured by J&J (code No. 20012) was used. The above various adhesive compositions were applied to the phosphoric acid-etched bovine tooth enamel surface based on the above-mentioned "adhesion test method", and then paste a and paste b of Bis-GMA composite resin having the following composition were mixed at a ratio of 1:1. After kneading with a ratio of These results are shown in Table 1. For comparison, the results when the same composite resin was directly adhered to bovine tooth enamel without applying an adhesive composition are also shown.

【table】

【table】

[Table] From the above table, in order to improve the adhesion of Bis-GMA composite resin to tooth structure, it was found that tetraisopropyl titanate (2 parts), which corresponds to component B of the adhesive composition of the invention, and the adhesive of the invention When various compositions containing each compound listed in Table 1 (98 parts) corresponding to component A of the composition are used as adhesives, in either case, direct filling of composite resin or conventionally known adhesives is possible. It can be seen that this method is extremely effective compared to the case where a chemical agent is used. In addition, as component A of the adhesive composition of the present invention,
It can be seen that the compounds represented by the formulas 1-A and 1-H shown in the detailed description of the specification are particularly suitable. Example 2 Eleven types of adhesive compositions shown in Table 2 were prepared. In each case, 2-hydroxyethyl methacrylate corresponding to component A of the composition of the present invention
A two-component system containing 98 parts and 2 parts of various titanium compounds corresponding to component B of the composition of the present invention listed in Table 2 as the main components as in Example 1 was prepared, and the amount of catalyst etc. was adjusted as appropriate. . A specific example of the composition of the sample adhesive composition is as follows. (For No. 2 in Table 2)

[Table] Samples No. 1 and No. 3 to No. 11 were also prepared in the same manner as above. In addition, as comparative examples, No. 1 to No. 11 were also shown in the case where dimethacrylethylene titanate, which is a titanium compound that does not correspond to the B component of the composition of the present invention, was used as the B component, and in the case where 2-hydroxyethyl methacrylate alone was used. Prepared in a similar manner. Adhesive strength was measured in the same manner as in Example 1 using the various adhesive compositions described above. The results are shown in Table 2.

【table】

Claims (1)

[Claims] 1 (A) A polymerizable acrylic ester, methacrylic ester, acrylamide derivative, or methacrylamide having at least one group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, and a hydroxyl group. At least one derivative (component A) 50-995% by weight
(B) 50 to 0.5% by weight of a titanium compound having an alkoxy group (component B); and a polymerization catalyst and an accelerator. 2 The acrylic ester or methacrylic ester has the following formula (1) [In the formula, n is a positive integer of 1 to 3, m is 1 or 2, Y is -OH, _-NH2 , or -COOH, Z is an (n+m) valent organic group having 1 to 25 carbon atoms, and R ₁ is a hydrogen atom or a methyl group. Claim 1: The adhesive composition described in . 3. The adhesive composition according to claim 2, wherein in the above formula (1), Y is -OH, _-NH2 , or [Formula]. 4 The acrylamide derivative or methacrylamide derivative has the following formula (2) [In the formula, m is 1 or 2, R ₁ is a hydrogen atom or a methyl group, R ₄ is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, Y is -OH, -NH ₂ , or -COOH, and X is a (m+1)-valent organic group having 1 to 25 carbon atoms. ] The adhesive composition according to claim 1, which is a compound represented by: 5. The adhesive composition according to claim 4, wherein Y in the above formula (2) is a carboxyl group or a hydroxyl group. 6 The titanium compound having the alkoxy group has the following formula (3), [In the formula, R ₃ is an aliphatic hydrocarbon residue having 1 to 20 carbon atoms, 1 or 2 hydroxyl groups, 1 carbon number
It may have ~3 alkoxy groups or di(hydroxyalkyl)amino groups (however, the alkyl group has 2 or 3 carbon atoms). R ₄ , R ₅ and R ₆ may each be the same or different from each other or R ₃ and are hydrocarbon residues which may have a substituent according to the same definition as R ₃ above, or the following: Equation (3)′ In the formula, R ₇ is an olefinic hydrocarbon residue represented by the formula (where R ₈ is a hydrogen atom or a methyl group) or a saturated aliphatic hydrocarbon residue having 1 to 20 carbon atoms; The saturated hydrocarbon residue has one or two hydroxyl groups (-OH), alkoxy groups (with 1 to 3 carbon atoms), or the formula [formula] (where R ₈ is an alkyl group with 1 to 3 carbon atoms). It may have an acyl group represented by The adhesive composition according to claim 1, which is a compound represented by the following. 7. The adhesive material contains the acrylic ester and/or methacrylic ester as component (A).
99.5% by weight and the titanium compound as component (B)
Claim 1 containing 0.5 to 20% by weight
The adhesive composition described in Section. 8 The adhesive composition is a two-component type, one of which contains
In addition to the two components (A) and (B), a catalyst is blended,
2. The adhesive composition according to claim 1, wherein the other liquid contains an accelerator in addition to the two components (A) and (B).