JPH02245080A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain a cold-setting adhesive composition showing sufficient adhesiveness to dentine and having a high curing rate by combining a polymerizable monomer with a polymerization initiator containing a specified peroxide. CONSTITUTION:A poymerizable monomer [e.g. methyl (meth)acrylate, ethylene glycol or (meth)acrylic acid] is mixed with a polymerization initiator containing a peroxide of formula I, II or III [wherein R1, R2, and R3 are each H, alkyl, (substituted) phenyl or (substituted) cyclohexyl; X is allylene, vinylene or phenylene; Y is carboxyl, an acid anhydride group, a phosphate group or a borate group; P is (substituted) alkylene] (e.g. a compound of formula IV, V or VI), having an adhesive composition. This composition has excellent curability near ordinary temperature and is effective particularly as dental adhesive. It can also be used in other applications, such as adhesives for the artificial bone and for metal.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to an adhesive composition, and more particularly to an adhesive composition that has excellent curability near room temperature and is particularly effective as a dental adhesive.

Technical Background of the Invention In the medical field such as dental treatment, it is necessary to firmly bond teeth, especially dentin, to other materials such as polymers, metals, dental porcelain, etc., and adhesives for this purpose are required. Already proposed.

Such dental adhesives include (i) methyl methacrylate (MMA) as a polymerizable monomer; and (ii)
) Consisting of a mixed system of benzoyl peroxide and aromatic tertiary amine as a polymerization catalyst or a system in which a sulfinate is added to this mixed system, and (iii) polymethyl methacrylate (PMMA) as a filler. adhesive composition,
Alternatively, (i) MMA as a polymerizable monomer and (1
1) Photosensitizer and (.

an adhesive composition comprising (i) a photopolymerization initiator comprising camphorquinone, and N,N-dimethylaminoethyl methacrylate as a reducing agent; (iii) PMMA as a filler; MMA as a polymerizable monomer and (i) 4-methacryloyloxyethoxycarbonylphthalic anhydride as an adhesion promoting monomer (
4-META), (iii) tri-butylborane oxide (TBBO) as a polymerization catalyst, and (iV)
Adhesive compositions containing PMMA as a filler have been proposed.

In this way, in conventionally known adhesive compositions, various compounds are used as polymerization initiators for polymerizable monomers. power is not obtained.

In addition, in an adhesive composition containing a T B B O type compound as a polymerization initiator, if a large amount of the polymerization initiator is not used,
Sufficient adhesive strength cannot be obtained, the curing speed is slow, and MMA L can hardly be used as a polymerizable monomer.
It was not possible to use methacrylic acid diesters as polymerizable monomers.

As mentioned above, there is a desire for an adhesive composition that exhibits strong adhesion to tooth structure and allows the use of monomers other than MMA as polymerizable monomers.

By the way, the present inventors have discovered that the above-mentioned MMA/PMMA
/4-META/TBBO or MMA/PMMA/
An adhesive composition made of TBBO exhibits a fairly strong adhesion force to the tooth structure, so when we investigated this adhesion mechanism, we found that MMA and 4
- It has been found that relatively strong adhesive force can be obtained because MET A is polymerized from the tooth substance due to the effect of TBBO.

To explain in more detail, MMA/4-META/TBB
With the O-based adhesive composition, the tooth material, particularly the dentin, is pretreated with a 10% citric acid aqueous solution containing 3% ferric chloride, and then the adhesive composition is used to bond the tooth material with, for example, an acrylic high-grade adhesive composition. molecule,
A large adhesive force can be obtained when bonding to metal, whereas a very large adhesive force cannot be obtained if the tooth is left untreated or treated only with an aqueous citric acid solution or an aqueous phosphoric acid solution. This means that in the above adhesive composition,
This means that ferric chloride plays an important role in adhesion. When we investigated the role played by ferric chloride, we found that ferric chloride is adsorbed to the tooth structure, and the ferric chloride adsorbed to the tooth structure acts synergistically with 4-META and TBBO. It was found that the polymerization of MMA was promoted. Since polymerization of MMA starts from the dentin region, the polymerization shrinkage strain there decreases, and the dentin region is strengthened by increasing the molecular weight of the MMA polymer due to the matrix effect of dentin collagen, resulting in strong adhesive strength. I found out that it can be done.

Based on the above findings, the present inventors further investigated and found that a peroxide having an affinity for tooth substance was added to the adhesive composition as a polymerization initiator component. The present inventors have discovered that, by doing so, it is possible to obtain an adhesive composition that exhibits excellent adhesion to tooth structure and that allows the use of a wide variety of compounds as polymerizable monomers, and has completed the present invention. It's arrived.

Purpose of the Invention The present invention aims to solve the problems associated with the prior art as described above, and it exhibits excellent adhesion to tooth tissue, especially dentin, has a high hardening speed, and has a high polymerization rate. The object of the present invention is to provide an adhesive composition in which a wide range of monomers can be used as the adhesive monomer.

Summary of the Invention The adhesive composition according to the present invention includes (A) a polymerizable monomer and (B) a polymerization initiator, in which (13) as the polymerization initiator, at least the following general formula [T
], [H] or [III].

(In the formula, R, R, and R may be the same or different, and are a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group, a cyclohexyl group, or a substituted cyclohexyl group, and X is an alkylene group, (A vinylene group or a phenylene group, Y is a carboxyl group, an acid anhydride group, a phosphoric acid group, or a boric acid group, and P is an alkylene group or a substituted alkylene group.) The adhesive composition according to the present invention includes: Since it contains a peroxide having a reactive group Y as described above as a polymerization initiator, it exhibits excellent adhesion to teeth, especially dentin, has a high curing speed, and is a polymerizable monomer. A wide variety of monomers can be used.

DETAILED DESCRIPTION OF THE INVENTION The adhesive composition according to the present invention will be specifically described below.

The adhesive composition according to the present invention contains (A) a polymerizable monomer and (B) a polymerization initiator, and each component will be explained below.

In the present invention, as the polymerizable monomer (A), a polymerizable compound having an ethylenic double bond is used, and specifically, the following compounds are used.

Methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 3
- Alkyl esters or glycidyl esters of acrylic acid or methacrylic acid such as hydroxypropyl methacrylate; diacrylic esters or dimethacrylic esters such as ethylene glycol, diethylene glycol, toluethylene glycol, tetraethylene glycol, dipropylene glycol, butylene glycol; Triacrylic acid esters or trimethacrylic acid esters such as methylolpropane and 1-IJ methylolethane; triacrylic acid esters or l-remethacrylic acid esters of tetramethylolethane; tetraacrylic acid esters or tetramethacrylic acid esters of tetramethylolethane Esters: bisphenol-A dimethacrylate, bisphenol-A-diglycidyl methacrylate, 2,2-bis(4-methacryloxyethoxyphenyl)propane; acrylic acid, methacrylic acid, methacrylic anhydride, itaconic acid, maleic acid, maleic anhydride acid, p-methacryloxybenzoic acid, N-
2-hydroxy-3-methacryloxypropyl-N-phenylglycine, 4-methacryloyloxyethoxycarbonylphthalic acid, 4-methacryloyloxyethoxycarbonylphthalic anhydride, and the like.

Among these, particularly preferred are alkyl esters of acrylic acid or methacrylic acid such as methyl methacrylate, and esters of diacrylic acid or dimethacrylic acid.

In the present invention, as (B) a polymerization initiator, at least the following general formula [I] (wherein R1R2 and R3 may be the same or different, hydrogen atom, alkyl group, phenyl group,
a substituted phenyl group, a cyclohexyl group, or a substituted cyclohexyl group, X is an alkylene group, a vinylene group, or a phenylene group, Y is a carboxyl group, an acid anhydride group, a phosphoric acid group, or a boric acid group, and P is an alkylene group or a substituted alkylene group. ) Contains the compound shown in

As the compound represented by the above general formula [I], specifically, the following compounds are used.

OOH'' Further, as the compound represented by the above general formula [n], specifically, the following compounds are used.

Further, as the compound represented by the above general formula [111],
Specifically, the following compounds are used.

In the present invention, as the (B) polymerization initiator, general formula [I],
Reactive group Y as shown in [II] or [III]
Since the peroxide having the reactive group Y has excellent affinity with the tooth substance, the adhesive composition according to the present invention has a high affinity with the tooth substance, especially the dentin. It exhibits excellent adhesion to and can be used with a wide variety of monomers as polymerizable monomers.

In the adhesive composition according to the present invention, the above general formula [I], [
The peroxide (B) represented by [II] or [III] is
0.1 to 1 per 100 parts by weight of polymerizable monomer (A)
It is desirable to use an amount of 0 parts by weight, preferably 1 to 6 parts by weight.

Further, in the present invention, as the polymerization initiator (B), it is preferable to use other polymerization initiators in addition to the above-mentioned peroxides to enable normal temperature polymerization. As such other polymerization initiators, the following radical generators and/or photopolymerization initiators are used.

Specifically, the following compounds are used as such radical generators.

(i) Trialkylborane and its analogs Specifically, triethylborane, tripropylborane, triisopropylborane, tri-n-butylborane, triloamylborane, triisoamylborane, tri-5ec-amylborane, etc. are used. Furthermore, trialkylborane analogs in which a portion of these is oxidized can be used.

(i) Aromatic sulfinate salts Specifically, sodium salts, potassium salts, or amine salts of aromatic sulfinic acids such as benzenesulfinic acid, toluenesulfinic acid, butylbenzenesulfinic acid, and octylbenzenesulfinic acid.

(iii) Barbylic acids Specifically, 5-methylbarbylic acid, 5-methylthiobarbylic acid, 5-butylbarbylic acid, 5-butylthiobarbylic acid, 1.3 .54-trimethylbarbituric acid, 1,3.5-trimethylthiobarbituric acid and other barbylic acids or thiobarbituric acids;
Mixtures of copper acetylacetonate or iron acetylacetonate with amine quaternary chlorides such as methacryloylcholine chloride, diethylmethacryloyloxyethylbenzylammonium chloride, dimethylbutyl p-vinylbenzylammonium chloride, tripropyl p-vinylbenzylammonium chloride .

A mixture of barbylic acid or thioparbituric acid derivatives as described above and copper chloride.

Examples of photopolymerization initiators include 2,3-dioxobicyclo[2,2,I]hebutane derivatives, N,N-dimethylaminoethyl methacrylate), N,N-diethylaminoethyl methacrylate, N- phenylglycine,
P-dimethylaminobenzaldehyde, N, amines such as trimethylaniline, or reducing agents such as barbylic acid or thiobarbylic acid derivatives such as L, 3,5-trimethylthiobarbital acid, 5-butylbarbital acid, etc. A combination of these is used.

In addition to the above-mentioned [A] polymerizable monomer and [B] polymerization initiator, the adhesive composition according to the present invention contains 4-methacryloyloxyethoxycarbonylphthalic anhydride, 4-methacryloyloxy as adhesion promoting monomers. Ethoxycarbonylphthalic acid and the like can also be included.

Furthermore, the adhesive composition according to the present invention may contain a polymer filler and a stabilizer, for example, a polymer or copolymer of monofunctional monomers such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, etc. It may be included as a polymer for reducing polymerization shrinkage or adjusting the viscosity of the composition. Further, fillers may include glass beads with a particle size of about 1 to 100 μm, alumina oxide, α-quartz powder, colloidal silica, etc., and stabilizers include hydroquinone monomethyl ether, t-butyl-p-cresol, hydroxymethoxy It may also contain benzophenone and the like.

When bonding tooth material, particularly dentin, and other substances using the adhesive composition according to the present invention, the surface of the tooth material is coated with an aqueous solution containing, for example, citric acid and ferric chloride or a citric acid aqueous solution. In addition, strong adhesion can be obtained by pre-treating enamel with an aqueous phosphoric acid solution.

The adhesive composition according to the present invention is particularly preferably used as an adhesive for dental treatment as described above, but it can also be used for other purposes such as an adhesive for artificial bones or an adhesive for metals.

Effects of the Invention Since the adhesive composition according to the present invention contains a peroxide having the above-mentioned reactive group Y as a polymerization initiator, by combining a polymerization initiator for room temperature polymerization, It exhibits sufficient adhesion to tooth material, has a high curing speed, and can be used with a wide range of polymerizable monomers.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

[Method for evaluating adhesive strength] (1) In the case of room temperature polymerization type, a bovine front tooth was cut with a diamond cutter, and the dentin surface on the layer side was used as an adhesive sample. After treating with a 10% citric acid aqueous solution containing 3% copper chloride for 30 seconds, washing with water for 30 seconds, and drying for 30 seconds, a cellophane tape with a thickness of 50 μm and a circular hole of 5 squares in diameter was attached to define the adhesive area. did. An adhesive composition was placed thereon and an acrylic rod was adhered thereto to prepare an adhesion test sample. Leave at room temperature for 30 minutes, then heat to 37°C.
After being immersed in distilled water for 24 hours, a tensile test was conducted to measure the adhesive strength. The average value of five test pieces was determined.

(2) In the case of visible light polymerization type, the steps up to the point where the adhesive composition is applied are the same as in (1). Glue an acrylic board with a thickness of 31m11 instead of the acrylic stick, leave it for 2 minutes, and then run a visible light irradiator (
Translux (manufactured by Kulxe+)
Irradiated for minutes. Immediately after irradiation, place in water at 37℃ for 24 hours.
After leaving it for a while, an acrylic rod was attached with instant adhesive and a tensile test was performed.

Example 1 Methyl methacrylate (HMA), 0.08% methacryloylcholine chloride, copper acetylacetonate o, o
os% to form a liquid component, and add 2% of 1,3.5-) dimethyl-2-thiobarbylic acid (TMTB) and 1% of 1% to polymethyl methacrylate (PMM^) powder.
- A mixture of butyl peroxymaleic acid (MA) was used as a powder component. The mixture of this powder and liquid at 1=1 is 6
It cured in minutes and 30 seconds.

When dentin was bonded using this mixture, 9
An adhesive force of 4 kg/cd was obtained.

Example 2 The same procedure as in Example 1 was performed except that 4% MA was used, and the curing time was 8 minutes and 30 seconds, and the adhesive strength was 87 kg/co? Met.

Examples 3 to 7 In Example 1, instead of using the monomer peroxyester and reducing agent described in Example 1, MMA of the liquid component was used.
Add 5% 2-hydroxyethyl methacrylate to
The same method as in Example 1 was carried out except that the materials shown in Table 1 were used in the amounts shown in Table 1.

The results are shown in Table 1.

Table 1 SA・1-butylperoxysuccinic acid PA: t-butylperoxyphthalic acid BB: 5-butylbarbital acid Example 8 In Example 1, methacryloylcholine chloride and copper acetylacetonate were replaced with 0 When .02% cupric chloride was used in the same manner as above, the curing time was 7 minutes and the adhesive strength was 90 kg/ad.

Comparative Example 1 The same method as in Example 1 was carried out except that MA was not added, and the curing time was 3 minutes and the adhesive strength was 45 kg/cm.

Example 9 MMA, 1% Camphorquinone (CQ), 1% N
, N-dimethylaminoethyl methacrylate (DMAE
MA) was dissolved and 1% MA was added thereto as a liquid component, and PMMA-based powder as a powder component. By irradiating this 1:1 mixture of powder and liquid with visible light, 40%
Hardened in seconds. When the adhesion force to dentin was measured using this composition, it was 70 kg/at.

Comparative Example 2 The same procedure as in Example 9 was carried out except that MA was not added, and the curing time was 40 seconds and the adhesive strength was 28 kg/ant.

Example 10 In Example 9, 1. , = 1%
Example 9 was carried out in the same manner as in Example 9, except that TMTB was added to the powder component.
It was 6 kg/cn.

Examples 11 to 13 In Example 10, the same method as in Example 10 was carried out except that the type and amount of peroxyester described in Example 10 were changed as shown in Table 2.

The results are shown in Table 2.

Table 2 Example 14 The same procedure as in Example 9 was performed except that DMAEMA was removed and 3% MA was used.
The curing time was 3 minutes and 10 seconds, and the adhesive strength was 89 kg/cffl.

Comparative Example 3 When Example 10 was carried out in the same manner as in Example 10 without adding MA, the curing time was 2 minutes and 40 seconds, and the adhesive strength was 32 kg/cd.

Example 15 Same as Example 10 except that 1% of 77-dimethyl-2,3-dioxobicyclo[2,2,I]hebutane-1-carboxylic acid was used instead of CQ. When I did it in the same way, the curing time was 1 minute and 20 seconds, and the adhesive strength was 110 kg/c! It was I.

Claims (1)

[Scope of Claims] 1. In an adhesive composition containing (A) a polymerizable monomer and (B) a polymerization initiator, at least the following general formula [I
], [II] or [III] Adhesive composition characterized by containing a peroxide represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] ▲Mathematical formulas, chemical formulas, tables, etc. There are▼...[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[III] (In the formula, R_1, R_2, and R_3 may be the same or different, and hydrogen atoms, an alkyl group, a phenyl group, a substituted phenyl group, a cyclohexyl group, or a substituted cyclohexyl group; (P is an alkylene group or a substituted alkylene group.) 2. As the polymerization initiator (B), a radical generator and/or
The adhesive composition according to claim 1, further comprising a photopolymerization initiator.