JPH03177470A - Curable adhesive composition for dental titanium or its alloys - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to curable adhesive compositions for titanium, particularly dental titanium or its alloys.

[Conventional technology]

Titanium and its alloys are currently being used as new dental metal materials, and their fields of use are gradually expanding due to their light weight, durability, biocompatibility, and other characteristics. Major areas include (partial) denture bases, implants, etc., where bonding of titanium or its alloys with plastic or other metal materials is often required; There is no suitable adhesive.

[Problem to be solved by the invention]

The object of the present invention is to have high adhesion to titanium or its alloys, and to have excellent adhesion between titanium or its alloys, or between titanium or its alloys and plastics or other metal materials, and particularly as a dental adhesive. An object of the present invention is to provide a curable adhesive composition that can be suitably used.

Furthermore, a curable adhesive composition that has high adhesive strength to titanium or its alloy as described above, has an excellent balance of initial adhesion, adhesive durability, water resistance, etc., and can be particularly suitably used as a dental adhesive. The goal is to provide the following.

[Means to solve the problem]

The present inventors have developed an adhesive that uses trialkyl boron or its partial oxide as a polymerization initiator, which has conventionally had high adhesion and durability as a dental adhesive and has been widely used. It has been discovered that a composition containing a titanate-based coupling agent having an affinity for titanium has high adhesion to titanium or its alloy.

We have arrived at the present invention.

That is, the present invention is the following curable adhesive composition.

(1) A curable adhesive composition comprising a titanate coupling agent (A), a radically polymerizable monomer (8), and a trialkylboron or a partial oxide thereof (C).

(2) A titanate coupling agent (A), a radically polymerizable monomer (B), a trialkylboron or its partial oxide (C), and a polymerizable monomer containing an acidic group (
D) A curable adhesive composition comprising:

The curable adhesive composition of the present invention comprises a titanate coupling agent (A) that has a high affinity for titanium, a radically polymerizable monomer CB), and a trialkylboron that has high polymerization activity at room temperature or its partially oxidized Titanium or Shows excellent adhesion and bond durability for its alloys.

Titanate coupling agent (A) used in the present invention
Specifically, isopropyl triisostearoyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2, 2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyltrioctanoyltitanate, isopropyldimethacrylisostearoyl Titanate, Isopropyl tridecylbenzenesulfonyl titanate, Isopropyl isostearoyl diacryl titanate, Isopropyl tri(dioctyl phosphate)
titanate, isopropyl tricumylphenyl titanate and tetraisopropyl bis(dioctyl phosphite) titanate.

Such titanate coupling agents (A) can be used alone or in combination. Among such titanate coupling agents (A), it is particularly preferable to use isopropyl dimethacrylylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, or isopropyl tri(dioctyl phosphate) titanate.

As the radically polymerizable monomer (B) used in the present invention, a monofunctional monomer (B1) and/or a polyfunctional monomer (B2) can be used.

Specifically, it is preferable to use a monofunctional (meth)acryloyl compound as the monofunctional monomer (B1).

Examples of such monofunctional monomers (B1) include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and dodecyl (meth)acrylate. Hydrocarbon esters of (meth)acrylic acid such as meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and isobornyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate; -Hydroxyalkyl esters of (meth)acrylic acid such as hydroxypropyl (meth)acrylate; ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)
Acrylate, ethylene glycol monododecyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, and polyethylene glycol monoethyl ether (meth)
(Poly)alkylene glycol monoether (meth)acrylate such as acrylate; Fluoroalkyl ester of (meth)acrylic acid such as trifluoroethyl (meth)acrylate and perfluorooctyl (meth)acrylate; γ-(meth)acryloxy Examples include silane compounds having a (meth)acryloxyalkyl group such as propyltrimethoxysilane and γ-(meth)acryloxypropyltri(trimethylsiloxy)silane; tetrahydrofurfuryl (meth)acrylate; and the like.

Examples of the polyfunctional monomer (B2) include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and hexylene glycol di(meth)acrylate. Alkane polyol poly(meth)acrylates such as glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; diethylene glycol di(meth)acrylate, dipropylene (Poly)oxyalkanes such as glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dibutylene glycol di(meth)acrylate, and dipentaerythritol hexa(meth)acrylate Examples include polyol poly(meth)acrylate.

Furthermore, as the polyfunctional monomer (B2), in addition to the above, examples include epoxy (
meth)acrylate (wherein, R represents a hydrogen atom or a methyl group, n represents 0 or a positive integer, and ai represents -(CHz)i-2-(C
Hz)+-t, ); Alicyclic or aromatic di(meth)acrylate represented by the following formula (n) (wherein R represents hydrogen or a methyl group, and R2 represents) ; Alicyclic di(meth)acrylate represented by the following formula (III) (wherein R represents hydrogen or a methyl group;

R3 is shows.

) Compounds such as

Furthermore, as the polyfunctional monomer (B2), a polyfunctional (meth)acrylate having at least 1 urethane bond in the molecule, for example, 1 mol of a diisocyanate compound and 2 mol of a diisocyanate compound.
An adduct with 2 moles of hydroxyl group-containing (meth)acrylate such as -hydroxyethyl (meth)acrylate can also be exemplified. The diisocyanate compound used in this case may be any of aliphatic, alicyclic, and aromatic diisocyanates. Therefore, diisocyanate compounds such as 1, hexamethylene diisocyanate, lysine diisocyanate, 2,2,4-
or 2,4.4-trimethylhexamethylene diisocyanate, dicyclohexyldimethylmethane-P+P-
Diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate,
Examples include diphenylmethane diisocyanate and naphthalene diisocyanate.

Therefore, as the polyfunctional (meth)acrylate having at least one urethane bond in the molecule, specifically (wherein R represents a hydrogen atom or a methyl group).

), (In the formula, R represents a hydrogen atom or a methyl group.

), (In the formula, R represents a hydrogen atom or a methyl group.

), N+1 garden C=1(:)1 Mu (In the formula, R represents a hydrogen atom or a methyl group.

), (During the ceremony.

R represents a hydrogen atom or a methyl group.

) (In the formula, R represents a hydrogen atom or a methyl group.

), (In the formula, R represents a hydrogen atom or a methyl group.

), (In the formula, R represents a hydrogen atom or a methyl group.

), Nt1 0 power Hi (In the formula, R represents a hydrogen atom or a methyl group.

), 0 hustle and bustle N Seki 11 Otsu Enter (In the formula, R represents a hydrogen atom or a methyl group.

) etc. can be given.

As polyfunctional (meth)acrylates, in addition to those exemplified above, compounds represented by the following formula (IV) can be mentioned.

(In the formula, R represents a hydrogen atom or a methyl group, and R4 represents a divalent aromatic residue that has at least one aromatic ring and may have an oxygen atom or a sulfur atom in the molecule. , n and m each represent a positive integer.) Specific examples of the polyfunctional (meth)acrylate represented by formula (IV) include 1 (wherein R represents a hydrogen atom or a methyl group, m =
It is 2-20. ), (wherein, R represents a hydrogen atom or a methyl group, and +n=2 to 20.

), (In the formula, R represents a hydrogen atom or a methyl group, +n=2-20.

).

(During the ceremony.

R represents a hydrogen atom or a methyl group, +n=2-20.

).

(In the formula, R represents a hydrogen atom or a methyl group, +n=2-20.

).

(In the formula, R represents a hydrogen atom or a methyl group, +n=2-20. ) etc. can be given.

Among the examples given above, examples of the monofunctional monomer (B1) include methyl (meth)acrylate, ethyl (meth)acrylate, and
Hydrocarbon esters of (meth)acrylic acid such as acrylate, hexyl (meth)acrylate, dodecyl (meth)acrylate, and isobornyl (meth)acrylate are preferably used.

Further, as the polyfunctional monomer (B2), poly(meth)acrylate of an alkane polyol and poly(meth)acrylate of a (poly)oxyalkane polyol are used.

Epoxy (meth)acrylate, at least 1 in the molecule
Aliphatic or cycloaliphatic (meta) with two urethane bonds
Acrylates and poly(meth)acrylates of (poly)oxyalkane polyols having an aromatic ring are preferred, particularly ethylene glycol di(meth)acrylate,
Neopentyl glycol (meth)acrylate, triethylene glycol di(meth)acrylate, (wherein R represents a hydrogen atom or a methyl group.

), (In the formula, R represents a hydrogen atom or a methyl group.

), (In the formula, R represents a hydrogen atom or a methyl group.

), (In the formula, R represents a hydrogen atom or a methyl group, +n=2-20.

), (In the formula, R represents a hydrogen atom or a methyl group, +n=2-20. ) etc. are preferred.

These radically polymerizable monomers CB) can be used alone or as a mixture of two or more.

Examples of the trialkylboron or its partial oxide (C) used in the present invention include triethylboron, tri-n-propylboron, triisopropylboron, tri-n-butylboron, triisobutylboron, tri-n-
Examples include -amylboron, triisoamylboron, tri-S-amylboron, and partial oxides thereof.

Among these, tri-n-butylboron or its partial oxide is preferred.

Polymerizable monomer containing acidic group (D
), aromatic polycarboxylic acids having at least one (meth)acryloxy group in the molecule or their acid anhydrides (DI); phosphoric acids or sulfonic acids having at least one (meth)acryloxy group in the molecule; Partial esters (e.g. monoesters, diesters or mixtures thereof of phosphoric acid).

monoester of sulfonic acid, etc.) (D2), etc.

Aromatic polycarboxylic acid or its acid anhydride (01) having at least one (meth)acryloxy group in the molecule
For example, at least one hydroxyl group of an alkane polyol having two or more hydroxyl groups (this polyol may contain an oxygen atom in addition to the hydroxyl groups) is (meth)
It has a structure in which it forms an ester bond with acrylic acid, and at least one hydroxyl group forms an ester bond with one carboxyl group of an aromatic polycarboxylic acid having three or more carboxyl groups (meth) Examples include acryloxy group-containing aromatic polycarboxylic acids and acid anhydrides thereof.

Among the aromatic polycarboxylic acids having three or more carboxyl groups, at least two of the three or more carboxyl groups are bonded to adjacent carbon atoms on the aromatic ring. Specific examples of such aromatic polycarboxylic acids, which are preferably ) Aromatic polycarboxylic acid having an acryloxy group or its acid anhydride (Dl)
Specific examples include, for example, 4-(meth)acryloxymethoxycarbonylphthalic acid or its anhydride;
-(meth)acryloxyethoxycarbonylphthalic acid or its anhydride; 4-(meth)acryloxybutoxycarbonylphthalic acid or its anhydride;
Indicates 12 integers. ); (wherein, R represents a hydrogen atom or a methyl group, and n is 2-
Indicates an integer of 50. ); (wherein, R represents a hydrogen atom or a methyl group, and n is 1 to
4-(2-hydroxycarbonyl)phthalic acid or its acid anhydride; 2,3-bis(3,4
-dicarboxybenzoyloxy)propyl (meth)acrylate or its acid anhydride; 2-(3,4-dicarboxybenzoyloxy)-1,3-dimethacryloxypropane or its anhydride; and the like.

In addition, partial esters of phosphoric acid or sulfonic acid (D
Specific examples of l) include, for example, 2-(meth)acryloxyethyl phenyl acid phosphate; bis[2
-(meth)acryloxyethyl]acidophosphate;
Bis[3-(meth)acryloxypropyl]acidophosphate; 2-(meth)acryloxyethylphenyl phosphate: (In the formula, R represents a hydrogen atom or a methyl group.); (In the formula, R represents a hydrogen atom or 6) Represents a methyl group; (in the formula, R represents a hydrogen atom or a methyl group); tert-butylacrylamide sulfonic acid; > Pseudo O1 crystal 5O3H (in the formula, R represents a hydrogen atom or a methyl group) ;To 0
Examples include A0H (in the formula, R represents a hydrogen atom or a methyl group).

Among the polymerizable monomers (D) containing acidic groups, aromatic polycarboxylic acids containing at least one (meth)acryloxy group in the molecule or their acid anhydrides (Dl) are preferably used.

The acidic group-containing polymerizable monomer (D) can be used alone or as a mixture of two or more.

In addition to the components described above, the composition of the present invention may optionally contain other components such as other polymerizable monomers, organic solvents, powdered inorganic fillers, organic polymers, and polymerization inhibitors. It is possible to contain an appropriate amount of the following.

Examples of the other polymerizable monomers include vinyl halides such as vinyl chloride and vinyl bromide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether; styrene, vinyltoluene,
Examples include alkenylbenzenes such as α-methylstyrene, chloromethylstyrene, and stilbene.

Examples of organic solvents include ethanol, acetone, ethyl acetate, diethyl ether, tetrahydrofuran, N,
Examples include N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and the like.

Examples of powdered inorganic fillers include kaolin, talc,
Clay, calcium carbonate, silica, silica/alumina,
Calcium phosphate, glass powder.

Examples include quartz powder.

Examples of the organic polymer include wax; homopolymers such as ethylene/vinyl acetate copolymers, methyl diacrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate, and copolymers thereof.

The curable adhesive composition of the present invention comprises: (1) a titanate coupling agent (A), a radically polymerizable monomer (B), and a trialkylboron or a partial oxide thereof (C), or (2) It consists of a titanate coupling agent (A), a radically polymerizable monomer (B), a trialkyl boron or its partial oxide (C), and a polymerizable monomer containing an acidic group (D), and further contains the above-mentioned The composition (1) or (2) may contain the other additives as necessary.

The amounts of each of the components (A), (B), (C) and (D) can be varied over a wide range depending on the intended use.

In the curable adhesive composition of the present invention, the titanate coupling agent (A) is a radically polymerizable monomer (B) t
It is desirable to use it in an amount usually in the range of 0.1 to 100 parts by weight, preferably 1 to 20 parts by weight, based on 0 parts by weight.

The amount of trialkylboron or its partial oxide (C) is based on 100 parts by weight of the radically polymerizable monomer (B).

It is desirable to use the amount usually in the range of 1 to 100 parts by weight, preferably 10 to 50 parts by weight.

By blending components (A) to C) in the amounts described above, it is possible to obtain a curable adhesive composition of the present invention having excellent adhesion to titanium or its alloy.

By further blending component (D) into such a curable adhesive composition, it has excellent adhesion to titanium or its alloy, and also has a good balance of initial adhesion, adhesive durability, water resistance, etc. An excellent curable adhesive composition can be obtained.

In this case, the polymerizable monomer (D) containing an acidic group is
Based on 100 parts by weight of radically polymerizable monomer (B).

It is generally desirable to use the amount in an amount of 50 parts by weight or less, preferably in a range of 0.1 to 20 parts by weight.

The curable adhesive composition of the present invention can be prepared by mixing components (A) to C) and other components as necessary, or by mixing components (A) to D) and other components as necessary. It is obtained by Therefore, when using the curable adhesive composition of the present invention, a mixture of each component is applied to the adhesive surface and bonded. Another method of adhesion is to apply the titanate coupling agent (A) to a suitable solvent.
For example, a solution dissolved in methyl methacrylate, etc., is applied to the adhesive surface, and a titanate coupling agent (
After forming the coating film of A), it is also possible to apply a mixture of each component except for the titanate coupling agent (A) onto the coating film for adhesion.

When trialkylboron or its partial oxide (C) is mixed with monomers such as components (A) and (B), it usually loses its polymerization activity within a few seconds to several tens of minutes, but it does not start polymerization. Therefore, trialkylboron or its partial oxide CC) is usually stored separately from the components (A) and (B), as well as component (D), and is preferably mixed immediately before use.

The curable adhesive composition of the present invention can be used, for example, as a dental adhesive, and can be used in the same manner as commonly used dental adhesive compositions.

Furthermore, the curable adhesive composition of the present invention can be suitably used as a coating composition or other coating composition, for example.

〔Effect of the invention〕

According to the present invention, since the component (A) or C) is contained, it has high adhesive strength to titanium or its alloy, and can be bonded to titanium or its alloy to each other, or to titanium or its alloy to plastic or A curable adhesive composition can be obtained that has excellent adhesive properties with other metal materials and can be particularly suitably used as a dental adhesive.

In addition, since the component (D) is further included in the component (A) or C), it has high adhesion to titanium or its alloy as described above, and has excellent initial adhesion, adhesive durability, and water resistance. A curable adhesive composition is obtained that has excellent balance in properties and the like and can be particularly suitably used as a dental adhesive.

〔Example〕

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way. In addition,
In each example, the headings have the following meanings:

MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
(manufactured by Ajinomoto Co., Inc., special grade) PDMST: Isoprobyl dimethacrylylisostearoyl titanate (manufactured by Ajinomoto Co., Inc., R-
7. Trademark) NPC: Neopentyl glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester NPC1 trademark) U
DMA: (manufactured by Kigami Kogyo Co., Ltd., Art Resin 5H-50O8, trademark) PMMA: Polymethyl methacrylate (Sun Medical Co., Ltd. 1!!, Super Bond Opaque Eye Poly-powder) Co., Ltd.) TBB-0: Partial oxide of tri-n-butyl boron (
Manufactured by Sun Medical Co., Ltd., Superbond Catalyst,
41) Example 1 The surfaces of a pure titanium disk with a diameter of Loam and a thickness of 3!1111 and a pure titanium disk with a diameter of 6 mm and a thickness of 3 mm were sandblasted, and a mixture I of 98 parts by weight of MMA and 2 parts by weight of PDMST was applied. was applied to the surface of the disc.

After the mixture ■ had dried, 100 parts by weight of HMA, TB
A mixture (1) of 40 parts by weight of B-0 and 60 parts by weight of PMMA was applied onto both coatings of the mixture I, and both surfaces were adhered.

Next, after repeating a heat cycle of alternately soaking in 4°C cold water and 60°C hot water for 1 minute each a predetermined number of times, a universal testing machine (manufactured by Shimadzu Corporation, Autograph DO5-500) was used.
The shear adhesive strength between pure titanium was measured using a crosshead speed of 0.50/win. The results are shown in Table 1.

Example 2 Pure titanium disk with a diameter of 10 mm and a thickness of 3 mm and a diameter of 6
The surface of each pure titanium disk with a thickness of 3 mm was sandblasted, and 98 parts by weight of HMA and PD
Mixture I containing 2 parts by weight of MST was applied to the surface of the disk.

After mixture ① was dried, 95 parts by weight of HMA, 4-ME
TA5 parts by weight, TBB-040 parts by weight and PMMA
60 parts by weight of Mixture (1) was applied onto both coatings of Mixture I, and both surfaces were adhered.

Next, the shear adhesive strength was measured in the same manner as in Example 1. The results are shown in Table 1.

Example 3 The surfaces of a pure titanium disk with a diameter of 10 mo+-3 mm and a pure titanium disk with a diameter of 6 mm and a thickness of 3 mm were sandblasted, and 98 parts by weight of HMA and PD were applied.
Mixture I containing 2 parts by weight of MST was applied to the surface of the disk.

After mixture I has dried, 75 parts by weight of HMA, NPG
20 parts by weight, 5 parts by weight of 4-META, TBB-0
A mixture (1) of 40 parts by weight and 60 parts by weight of PMMA was applied onto both coatings of the mixture I, and both surfaces were adhered.

Next, the shear adhesive strength was measured in the same manner as in Example 1. The results are shown in Table 1.

Example 4 The surfaces of a pure titanium disk with a diameter of 10++m and a thickness of 3IIIm and a pure titanium disk with a diameter of 6 mm and a thickness of 3 mm were sandblasted, and a mixture ■ of 98 parts by weight of HMA and 2 parts by weight of PDMST was applied to the surface of the disks. It was applied to.

After mixture I was dry, 65 parts by weight of HMA, UDMA
30 parts by weight, 5 parts by weight of 4-META, TBB-040
Parts by weight of mixture (1) and 60 parts by weight of PHMA were applied onto both coatings of mixture (2), and both surfaces were adhered.

Next, the shear adhesive strength was measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 The surfaces of a pure titanium disk with a diameter of 10t+a and a thickness of 3 mm and a pure titanium disk with a diameter of 6 mm and a thickness of 3 mm were each sandblasted.

Next, a mixture of 95 parts by weight of HMA, 40 parts by weight of TBB-0 and 60 parts by weight of PMMA was applied to each sandblasted surface and then bonded.

Next, the shear adhesive strength was measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 The surfaces of a pure titanium disk with a diameter of 110 mm and a thickness of 3+ am and a pure titanium disk with a diameter of 6 mm and a thickness of 3+ m were subjected to sandblasting.

Next, 75 parts by weight of HMA, 20 parts by weight of NPo, TBB
After applying a mixture of -040 parts by weight and 60 parts by weight of PMMA to each sandblasted surface,
Glued.

Next, the shear adhesive strength was measured in the same manner as in Example 1. The results are shown in Table 1.

Claims (2)

[Claims] (1) A curable adhesive composition comprising a titanate coupling agent (A), a radically polymerizable monomer (B), and a trialkylboron or a partial oxide thereof (C). (2) A titanate coupling agent (A), a radically polymerizable monomer (B), a trialkylboron or its partial oxide (C), and a polymerizable monomer containing an acidic group (
D) A curable adhesive composition comprising: