JPH0693236A - Bonding material composition - Google Patents

Abstract

PURPOSE:To obtain an adhesive composition suitable for a dental field, showing bond strength of water resistance especially to noble metals, comprising a COOH-containing polymerizable monomer, a polymerizable monomer containing a mercapto groupcontaining silicon compound and a polymerization initiator. CONSTITUTION:An adhesive composition comprises (A) 0.1-10 pts.wt. mercapto group-containing silicon compound of formula I or formula II [R1, R4 and R6 are 1-20C alkylene; R2, R3 and R5 are 1-5C alkyl; (h) is 1-3 integer; (k) is 1-10 integer], (B) 100 pts.wt. (meth)acrylate-containing polymerizable monomer, containing 1-100wt.% COOH-containing polymerizable monomer of formula III [R7 is alkyl or H; R8 is 2-20C organic residue; (1) os 0 or 1; (m) is 1-3 integer; (n) is 1 or 2; X is COOH (may b acid anhydride group in the case wherein n=2)] (e.g. p-methacryloxybenzoic acid) and (C) 0.01-10 pts.wt. polymerization initiator (e.g. alpha-diketone or organic peroxide and optionally 0.01-10 pts.wt. tertiary amine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition having excellent adhesion to metals, especially noble metals.

[0002]

2. Description of the Related Art In the general industry, adhesives using acrylic monomers and epoxy compounds are used, and they can be cured at room temperature and pressure and are excellent in workability, so they are important in the adhesives field. Occupy a position. On the other hand, introduction of the above materials was also attempted in the field of dentistry, but since the humidity inside the oral cavity was 100%, the adhesive surface could not be dried sufficiently
Moreover, after adhesion, stricter water resistance was required, and satisfactory results could not be obtained.

In recent years, research on adhesives having excellent water resistance has been conducted in the field of dentistry, and for example, JP-A-61-293.
The dental adhesive containing the carboxylic acid acrylate compound disclosed in Japanese Patent No. 951 is made of iron, nickel, chromium,
It has been confirmed that it exhibits sufficient adhesiveness to base metals such as cobalt, tin, aluminum, copper and titanium, and base metal alloys containing these elements as main components.

However, dental castings (inlays,
The adhesive strength of the above adhesives to the noble metal alloys (alloys containing gold, platinum, palladium and silver as the main components) mainly used for applications such as crowns and bridges was inferior to that of the base metal alloys.

In order to solve this problem, a method of performing tin electrodeposition or oxidation treatment on the surface of the noble metal alloy has been adopted.
A simpler method has been desired due to the complexity of the operation.

Recently, N- (4-mercaptophenyl) methacrylamide was previously coated on the surface of a noble metal and then MMA-
It has been reported that adhesion with a tributylborane adhesive improves the adhesion strength to precious metals. (Dental materials
Instrument Vol. 5, pp. 92-105, 1986)

[0007]

As described above, the surface treatment such as tin electrodeposition used for improving the adhesion strength to the noble metal has a problem that the work becomes complicated. Adhesives containing N- (4-mercaptophenyl) methacrylamide that have been developed to solve this point have a problem that the water resistance of the adhesive strength is not practically sufficient.

It is therefore an object of the present invention to find an excellent adhesive for adhering metals, especially noble metals to each other or metals and other substances.

[0009]

Means for Solving the Problems The object is (a) general formula [1] or [2]

[0010]

[Chemical 3]

[In the formula, R ₁ , R ₄ , and R ₆ have 1 to 2 carbon atoms.
An alkylene group of 0, R ₂ , R ₃ and R ₅ have 1 to ₅ carbon atoms.
An alkyl group of, h is an integer of 1 to 3, k is an integer of 1 to 10], a mercapto group-containing silicon compound,
(B) General formula [3]

[0012]

[Chemical 4]

[In the formula, R ₇ is an alkyl group or a hydrogen atom,
R ₈ is an organic residue having 2 to 20 carbon atoms, l is an integer of 0 or 1, m is an integer of 1 to 3, n is an integer of 1 or 2, X is a carboxyl group (when n = 2, X is Each of which may be present as an acid anhydride group]], and a polymerizable monomer containing 1 to 100% by weight of a carboxyl group-containing polymerizable monomer, and (c) a polymerization initiator. This can be achieved by using an adhesive composition characterized by the above.

In the above general formulas [1] and [2], R ₁ ,
R ₄ and R _{6 each} represent an alkylene group, and specific examples thereof include a propylene group and a decylene group. When the carbon number is 3 to 12, it is more preferable because the adhesiveness is particularly excellent.

Further, R ₂ , R ₃ and R _{5 each} represent an alkyl group, and specific examples thereof include a methyl group, an ethyl group and a propyl group.

Specific examples of the mercapto group-containing silicon compound represented by the general formula [1] or [2] include the following.

[0017]

[Chemical 5]

The mercapto group-containing silicon compound is
It is usually used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of all polymerizable monomers described below.

Further, in the general formula [3], when R ₇ represents an alkyl group, examples of R ₇ include a methyl group and an ethyl group. When the carbon number of the organic residue of R ₈ is 2 to 20, not only does the adhesive strength increase due to the increase in the strength of the cured product formed at the adhesive interface,
It is preferable because the adhesion durability under wet condition is enhanced and the material is easily available. It is more preferable that the carbon number of R ₈ is 4 to 20 because the adhesiveness is further excellent. And
The organic residue may be aliphatic or aromatic, and may be partially substituted with a substituent such as halogen, amino group or hydroxyl group.

Carboxyl group-containing polymerizable monomer represented by the general formula [3] (hereinafter referred to as carboxyl group monomer)
Specifically, p-methacryloxybenzoic acid,
1 in the molecule of p-vinylbenzoic acid, 2-methacryloxyethyl phthalic acid, 2-methacryloxyethyl succinic acid, etc.
Radical polymerizable monomer having one carboxyl group, 7
-Methacryloxy-1,1-heptanedicarboxylic acid, 1
Two carboxyl groups in the molecule such as 1-methacryloxy-1,1-undecanedicarboxylic acid, 13-methacryloxy-1,1-tridecanedicarboxylic acid, 4- (β-methacryloxyethyl) trimellitic acid ester and anhydride. And a radically polymerizable monomer having In the present invention, these carboxyl group monomers may be used alone or in combination of two or more.

The carboxyl group monomer is essential for adhesive strength and water resistance and may be used alone, but it is usually a polymerizable monomer typified by a (meth) acrylate-based monomer described later. Used as a mixture with. Such a carboxyl group monomer is contained in an amount of 1 to 100% by weight, preferably 5 to 30% by weight, based on the entire polymerizable monomers.

As the (meth) acrylate-based monomer, known ones are used without particular limitation.

Specific examples of generally suitable ones are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, glycidyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate and other monofunctional radically polymerizable monomers; ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate , Tri ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol (meth)
Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, bisphenol A di (Meth) acrylate, 2,
2'-bis [((meth) acryloyloxypolyethoxyphenyl] propane, 2,2'-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane, trimethylolpropane (meth) acrylate, tri A polyfunctional radically polymerizable monomer such as methylolethane tri (meth) acrylate or tetramethylolmethane tetra (meth) acrylate is used.

Further, a polymerization initiator is added to the adhesive composition of the present invention. As this polymerization initiator, a known radical polymerization initiator capable of polymerizing a polymerizable monomer by a radical mechanism is used without limitation.

Examples of the polymerization initiator include photopolymerization initiators and chemical polymerization initiators such as organic peroxides. When an organic peroxide is used, it is preferable to use a tertiary amine in combination because polymerization can be performed at room temperature.

As the organic peroxide of the chemical polymerization initiator,
For example, dibenzoyl peroxide, diacyl peroxide such as 2,4-dichlorobenzoyl peroxide, dilauroyl peroxide, dioctanoyl peroxide and decanoyl peroxide, hydrolyzate such as cumene hydroperoxide and t-butyl hydroperoxide. Ketone peroxides such as peroxides, cyclohexanone peroxide, and methyl ethyl ketone peroxide can be used alone or in combination of two or more. Of the organic peroxides exemplified here,
Acyl peroxides such as dibenzoyl peroxide are preferred.

Further, as the tertiary amine, for example,
Toluidine derivatives such as N, N-dimer-p-toluidine, N, N-dihydroxyethyl-p-toluidine, 4-
(N, N-diethylamino) benzoic acid, 4- (N, N-
Dimethylamino) ethyl benzoate, aminobenzoic acid derivatives such as 4- (N, N-dimethylamino) benzoic acid isoamyl ester, 4- (N, N-dimethylamino) benzaldehyde, 4- (N, N-diethylamino) benzaldehyde , 4- (methylhexylamino) benzaldehyde and other aminobenzaldehyde derivatives, N, N-dimethyl-m-anisidine, N, N-dimethyl-p-anisidine, N, N-diethyl-p-anisidine and other anisidine derivatives, N , N-dimethyl-m-aminophenol,
Aminophenol derivatives such as N, N-diel-m-aminophenol, p-propoxy-N, N-dimethylaniline, p-butoxy-N, N-dimethylaniline, p-
Aniline derivatives such as hexyloxy-N, N-dimethylaniline can be used alone or in combination of two or more.

On the other hand, as the photopolymerization initiator, diacetyl,
2,3-pentadione, 2,3-hexadione, benzyl, 4,4'-dimethoxybenzyl, 4,4'-diethoxybenzyl, α-naphthyl, β-naphthyl, camphorquinone, etc., alone or in combination of two or more. It can be blended and used.

When the above α-diketone is used as a polymerization initiator, it is preferable to use a tertiary amine in combination with the α-diketone because the curing time can be shortened.

The above-mentioned polymerization initiator is the total polymerizable monomer 100.
0.01 to 10 parts by weight, preferably 0.
05 to 5 parts by weight is compounded. The mixing ratio of the tertiary amine when used in combination can be appropriately determined within the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of all the polymerizable monomers.

The adhesive composition of the present invention preferably contains a filler depending on the material to be adhered. When a filler is added, the opportunistic strength and water resistance are improved, and the fluidity and coatability can be controlled.

As this filler, known fillers can be used without limitation. Examples of the filler include quartz, amorphous silica, silica zirconia, fluoroaluminosilicate, clay, aluminum oxide, talc, mica, kaolin, glass, barium sulfate, zirconium oxide, titanium oxide, silicon nitride, aluminum nitride, titanium. From inorganic substances such as titanium oxide, silicon carbide, boron carbide, calcium carbonate, hydroxyapatite, calcium phosphate, etc., organic substances such as polymethyl methacrylate, polyethyl methacrylate, polyvinyl chloride, polystyrene, polyester, nylon, etc. These fillers, organic-inorganic composite fillers, etc. can be used alone or in combination of two or more. The inorganic filler is usually preferably treated with a silane coupling agent such as γ-methacryloyloxypropyltrimethoxysilane or vinyltriethoxysilane.

The mixing ratio of the filler is not particularly limited, but it is preferably 1 to 300% by weight based on the total amount of all polymerizable monomers in the adhesive composition.

Furthermore, a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether or butylhydroxytoluene may be added to the adhesive composition of the present invention, if necessary.

The adhesive composition of the present invention comprises the above-mentioned mercapto group-containing silicon compound, a polymerizable monomer containing a carboxyl group monomer, and a polymerization initiator as essential components, and optionally a filler and other additives. However, it is not always necessary that all components are present in the same package. That is, a composition A containing a mercapto group-containing silicon compound as an essential component and optionally a (meth) acrylate monomer, a filler, and a polymerization initiator, and a carboxyl group monomer as an essential component, if necessary. The composition (B) containing the (meth) acrylate-based monomer, the filler, and the polymerization initiator may be separately packaged to form a divided packaging adhesive composition.

In this case, both compositions are mixed immediately before adhesion,
It may be applied to the surface to be adhered.

Furthermore, a mercapto group-containing silicon compound alone or a composition C prepared by dissolving the compound in a solvent and other essential components such as a polymerizable monomer containing a carboxyl group monomer and a polymerization initiator are added. A mode is also possible in which it is separately packaged with the composition D containing it, the composition C is first applied to the surface to be adhered, and then the composition D is applied to adhere the desired substances to each other.

Examples of such a solvent include toluene, tetrahydrofuran, hexane, methyl ethyl ketone, ethanol, methylene chloride and the like, but the above-mentioned (meth) acrylate type monomer can also be used. When using a mercapto group-containing silicon compound dissolved in a solvent,
The concentration is usually in the range of 1% by weight to 20% by weight.

[0039]

The adhesive composition of the present invention is suitable for use in the dentistry field because it exhibits excellent water-resistant adhesive strength, especially to precious metals. For example, when a noble metal casting such as an inlay, a crown, or a bridge is bonded to a tooth, a simpler and superior improvement in adhesion can be achieved as compared with the conventional case.

The adhesive composition of the present invention is used not only in the field of dentistry but also in any industrial field where adhesion of metal or metal oxide is required.

[0041]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The structures and abbreviations of the polymerizable monomer, the carboxyl group monomer and the mercapto group-containing silicon compound used in Examples and Comparative Examples are shown below.

[0043]

[Chemical 6]

[0044]

[Chemical 7]

[0045]

[Chemical 8]

Examples 1 to 7 and Comparative Example 1 Each of the various mercapto group-containing silicon compounds shown in Table 1 was used to examine the adhesive strength to a noble metal. These compounds were made into toluene solutions having the concentrations shown in Table 1, and the adherend gold-silver-palladium alloy was polished with No. 800 silicon carbide polishing paper and subjected to alumina sandblasting, and then double-sided tape with an inner diameter of 4 mmφ. Was applied and applied to the inner surface. After 1 minute, the excess was removed by air, the two pastes shown in Table 2 were kneaded and applied, and the aluminum rod was sandblasted (6 mm
φ, 20 mm) was pressed. After 1 hour from the adhesion, the adhesion sample was immersed in 37 ° C. water for 24 hours to measure the tensile adhesion strength. The results are also shown in Table 1.

[0047]

[Table 1]

[0048]

[Table 2]

Examples 8 to 14, Comparative Examples 2 to 4 In the same manner as in Example 1 except that the compound shown in Table 3 was used in place of the compound A as the carboxyl group monomer in the paste I of Table 1. The adhesive strength to the precious metal was measured. The results are also shown in Table 3.

[0050]

[Table 3]

Examples 15 to 19 An adhesive composition consisting of the following two-paste packaging was prepared,
After the pastes III and IV were sampled in equal weights and kneaded, the pastes were applied to a gold-silver-palladium alloy that had been ground and sandblasted in the same manner as in Example 1, and a stainless steel rod was pressed.
The carboxyl group monomer and the mercapto group-containing silicon compound used are shown in Table 4. After 1 hour from the adhesion, the adhesion sample was immersed in 37 ° C. water for 24 hours to measure the tensile adhesion strength. The results are also shown in Table 4.

Paste III Carboxyl group monomer shown in Table 4 12 parts by weight Compound J 8 〃 Neopentyl glycol dimethacrylate 10 〃 Silica zirconia powder 70 〃 Benzoyl peroxide 0.3 〃 Hydroquinone monomethyl ether 0.01 〃 Paste IV Table 4 parts by weight of the mercapto group-containing silicon compound shown in 4 Compound J 17 〃 Neopentyl glycol dimethacrylate 12 〃 Silica zirconia powder 70 〃 N, N-dimethyl-p-toluidine 0.3 〃 Hydroquinone monomethyl ether 0.01 〃

[0053]

[Table 4]

Claims (1)

[Claims] 1. (a) General formula [1] or [2]: [In the formula, R ₁ , R ₄ , and R ₆ are alkylene groups having 1 to 20 carbon atoms, R ₂ , R ₃ , and R ₅ are alkyl groups having 1 to ₅ carbon atoms, and h is an integer of 1 to 3, k represents an integer of 1 to 10], and a mercapto group-containing silicon compound represented by the formula (b), a general formula [3] [In the formula, R ₇ is an alkyl group or a hydrogen atom, R ₈ is an organic residue having 2 to 20 carbon atoms, l is an integer of 0 or 1, and m is 1 to 3
Is an integer, n is an integer of 1 or 2, X is a carboxyl group (n
= 2, X may represent an acid anhydride group respectively)], and a polymerizable monomer containing 1 to 100% by weight of a carboxyl group-containing polymerizable monomer represented by ) An adhesive composition containing a polymerization initiator.