JPH0699528B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is excellent in low-temperature curability near room temperature and water-resistant adhesion, and is also excellent in adhesion to teeth such as enamel and dentin and dental alloys. The present invention relates to a curable composition which has properties and is effective as a dental adhesive without adverse effects such as irritation to dental pulp.

[Conventional technology]

Many adhesives for orthodontics or restoration of teeth, which are composed of radically polymerizable monomers such as (meth) acrylate vinyl monomers and catalysts, have been proposed.
A curable composition (JP-A-60-44508) comprising a (meth) acrylic acid ester vinyl monomer, a (meth) acryloyloxyl group-containing aromatic carboxylic acid (anhydride), an amine and a sulfinic acid (salt), and room temperature And liquid (meta)
Adhesive composed of acrylic acid ester, amine, sulfinic acid (salt), and peroxide (JP-A-53-39331), MMA, 4-M
Adhesives composed of ETA and tributylborane (Nippon Hoho, 28 , 452-478 (1985)) and the like have been reported. However, it has been difficult for conventional adhesives and curable compositions to obtain sufficient adhesion to dentine, particularly to dentin treated with a mild etching agent such as EDTA.

[Problems to be Solved by the Invention] The inventors of the present invention have excellent low-temperature curability near room temperature and excellent water-resistant adhesiveness, and are excellent for teeth such as enamel, dentin and dental alloys, especially dentin. As a result of diligent study of a curable composition having adhesive properties, having no adverse effects such as irritation to dental pulp, and being excellent as a dental adhesive in the restoration of teeth, [A] monofunctional (meth) acrylate-based monomer Body, [B] specific polyfunctional (meth) acrylate-based monomer,
The inventors have found that a curable composition comprising [C] a specific acidic group-containing (meth) acrylate-based monomer and [D] trialkylboron or an oxide thereof can achieve the above objects, and have reached the present invention.

[Means for Solving Problems] and [Operation] According to the present invention, [A] a monofunctional (meth) acrylate monomer, [B] a polyfunctional (meth) acrylate monomer [however,
Polyfunctional (meth) acrylate-based monomer having at least one urethane bond in one molecule and general formula [I] (In the formula, R ¹ represents a divalent aromatic residue having at least one aromatic ring and optionally having an oxygen atom or a sulfur atom in the molecule, and R ² and R ³ are respectively A hydrogen atom or a methyl group, and n and m are positive integers), excluding polyfunctional (meth) acrylate monomers], [C] at least one (meth) acryloyl in one molecule. A curable composition comprising an acid group-containing (meth) acrylate-based monomer containing an oxyl group and [D] trialkylboron or an oxide thereof is provided.

The monofunctional (meth) acrylate-based monomer [A] used in the curable composition of the present invention may contain a functional group other than an acidic group in the molecule, and specifically, methyl (meth) ) Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth)
Hydrocarbon group-containing (meth) acrylates such as acrylate and isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxyl group-containing (meth) acrylates such as 2-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, polyethylene glycol monoethyl ether (meth) acrylate, etc. Ethylene glycol unit-containing (meth) acrylate, trifluoroethyl (meth) acrylate, perfluoro Fluorine substituent-containing (meth) acrylates such as octyl (meth) acrylate, γ-
Examples thereof include silane-based (meth) acrylates such as (meth) acryloyloxypropyltrimethoxysilane and γ- (meth) acryloyloxypropyltri (trimethylsiloxy) silane, and tetrahydrofurfuryl (meth) acrylate, which may be used alone or Two or more kinds can be mixed and used. Among these, methyl (meth) acrylate, ethyl (meth) acrylate,
Alkyl (meth) acrylate such as hexyl (meth) acrylate, dodecyl (meth) acrylate or 2-
Hydroxyl group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferred, and methyl methacrylate, n-hexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate alone or these Preference is given to using mixtures.

The polyfunctional (meth) acrylate-based monomer [B] contained in the curable composition of the present invention is a polyfunctional (meth) acrylate-based monomer having at least two (meth) acryloyloxyl groups in one molecule. And polyfunctional (meth) acrylate-based monomer having at least one urethane bond in one molecule and general formula (In the formula, R ¹ represents a divalent aromatic residue having at least one aromatic ring and optionally having an oxygen atom or a sulfur atom in the molecule, and R ² and R ³ are respectively A polyfunctional (meth) acrylate-based monomer excluding a polyfunctional (meth) acrylate-based monomer represented by a hydrogen atom or a methyl group, and n and m are positive integers. Specific examples of the polyfunctional (meth) acrylate monomer [B] include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, hexylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, poly (meth) acrylate of alkane polyol such as pentaerythritol tetra (meth) acrylate, diethylene glycol di ( (Meth) acrylate,
(Poly) oxy such as dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dibutylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate Poly (meth) acrylate of alkane polyol, general formula [I] (R ₁ is H or CH ₃ , n is 0 or a positive integer, R ₂ is CH _{2 2} , CH _{2 4} , Is. ) Epoxy (meth) acrylate represented by the general formula [II] (R ₁ is H or CH ₃ , R ₂ is Is. A) an alicyclic or aromatic di (meth) acrylate compound represented by the general formula [III] (R ₁ is H or CH ₃ and R ₂ is Is. The alicyclic di (meth) acrylate-type compound represented by these can be illustrated.

Among these, poly (meth) acrylates of alkane polyols, poly (meth) acrylates of (poly) oxyalkane polyols and epoxy (meth) acrylates are preferably used, and particularly ethylene glycol di (meth) acrylate and neopentyl are used. Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, (R ₁ is H or CH ₃ ) is preferably used.

The (meth) acrylate-based monomer [B] can be used as a mixture of two or more kinds.

The acidic group-containing (meth) acrylate-based monomer [C] containing at least one (meth) acryloyloxyl group in one molecule used in the cured positive composition of the present invention has at least one in one molecule. Aromatic polycarboxylic acid containing one (meth) acryloyloxyl group or its acid anhydride (C ₁ ) or phosphoric acid or sulfonic acid containing at least one (meth) acryloyloxyl group in one molecule Partial ester (monoester of phosphoric acid, diester or mixture thereof, monoester of sulfonic acid)
And the like (C ₂ ). More specifically, as the aromatic polycarboxylic acid (C ₁ ) containing at least one (meth) acryloyloxyl group in one molecule, 1
At least one hydroxyl group of an alkane polyol having at least two hydroxyl groups in the molecule and optionally containing an oxygen atom forms an ester of (meth) acrylic acid, and at least one hydroxyl group Is a (meth) acryloyloxyl group-containing aromatic polycarboxylic acid having a structure in which an ester is formed with one carboxyl group of an aromatic polycarboxylic acid having at least three carboxyl groups, or an anhydride thereof. Among the aromatic polycarboxylic acids having at least 3 carboxyl groups, an aromatic compound in which at least 2 carboxyl groups among at least 3 or more carboxyl groups are bonded to adjacent carbon atoms on the aromatic nucleus. A polycarboxylic acid is preferable, and specific examples thereof include hemimellitic acid, trimellitic acid, prenitic acid, merophanic acid, and pyromellitic acid.

Examples of the (meth) acryloyloxyl group-containing aromatic polycarboxylic acid or acid anhydride thereof include 4- (meth) acryloyloxymethoxycarbonylphthalic acid or acid anhydride thereof, 4- (meth) acryloyloxyethoxycarbonylphthalic acid or Its acid anhydride, 4- (meth) acryloyloxybutoxycarbonylphthalic acid or its acid anhydride, (N is an integer of 6 to 12, R is H or CH ₃ ) (N is an integer of 2 to 50, R is H or CH ₃ ) (N is an integer of 1 to 50, R is H or CH ₃ ) 4- [2-hydroxy-3- (meth) acryloyloxypropoxycarbonyl] phthalic acid or its acid anhydride, 2,3-
Examples include bis (3,4-dicarboxybenzoyloxy) propyl (meth) acrylate or its acid anhydride, 2- (3,4-dicarboxybenzoyloxy) 1,3-dimethacryloyloxypropane or its acid anhydride. can do.

Also, as a partial ester of phosphoric acid or sulfonic acid containing at least one (meth) acryloyloxyl group in one molecule (monoester of phosphoric acid, diester or mixture thereof, monoester of sulfonic acid) (C ₂ ). Specifically, 2- (meth) acryloyloxyethylphenyl acid phosphate, bis [2- (meth) acryloyloxyethyl] acid phosphate, bis [3- (meth))
Acryloxypropyl] acid phosphate, 2- (meth) acryloyloxyethylphenylphosphonate, (R is H or CH ₃ ) (R is H or CH ₃ ) (R is H or CH ₃ ) (R is H or CH ₃ ) (R is H or CH ₃ ) (R is H or CH ₃ ) and the like.

Among these acidic group-containing (meth) acrylate-based monomers [C] containing at least one (meth) acryloyloxyl group in one molecule, at least one (meth) acryloyloxyl in one molecule An aromatic polycarboxylic acid containing a group or an acid anhydride thereof (C ₁ ) is preferable, and among these, 4- (meth) acryloyloxyethoxycarbonylphthalic acid or an acid anhydride thereof is preferable, and 4-methacryloyloxy is particularly preferable. The use of ethoxycarbonyl phthalic anhydride is preferable because it improves the adhesion to teeth, water resistance and the like.

Specific examples of the trialkylboron or its oxide [D] used in the cured positive composition of the present invention include triethylboron, tripropylboron, triisopropylboron, tri-n-butylboron, tri-n-amylbore. Elemental, triisoamylboron, tri-sec-amylboron, or a trialkylboron oxide in which a part thereof is oxidized can be used. Of these, tri-n-butylboron or its partial oxide is preferably used.

The mixing ratio of the monofunctional (meth) acrylate-based monomer [A] and the polyfunctional (meth) acrylate-based monomer [B] to be added to the curable composition of the present invention is not particularly limited,
Usually, monofunctional (meth) acrylate monomer [A] is 5 to 95% by weight, polyfunctional (meth) acrylate monomer [B] is 95 to 5% by weight, preferably monofunctional (meth) acrylate monomer. Body [A] 10 to 95% by weight, polyfunctional (meth) acrylate monomer [B] 90 to 5% by weight, particularly preferably monofunctional (meth) acrylate monomer [A] 40 to 80% by weight When the polyfunctional (meth) acrylate-based monomer [B] is in the range of 60 to 20% by weight, the adhesive force to teeth, water resistance, especially when the etching treatment for dentin uses a mild acid such as EDTA. It is also preferable because it has high adhesive strength and water resistance.

The amount of the acidic group-containing (meth) acrylate-based monomer [C] blended in the curable composition of the present invention is the same as that of the monofunctional (meth) acrylate-based monomer [A] and the polyfunctional monomer (A). Total of 10 functional (meth) acrylate monomers [B]
It is usually 1 to 50 parts by weight, preferably 3 to 0 parts by weight.
To 30 parts by weight, particularly preferably 5 to 15 parts by weight.

Furthermore, the amount of the trialkylboron or its oxide [D] blended in the curable composition of the present invention is such that the monofunctional (meth) acrylate-based monomer [A] and the polyfunctional (meth) Usually 2 to 100 parts by weight, preferably 5 to 7 parts by weight, based on 100 parts by weight of the total of the acrylate-based monomer [B] and the acidic group-containing (meth) acrylate-based monomer [C].
It is 0 part by weight, particularly preferably 5 to 50 parts by weight. The trialkylboron or its oxide [D] is usually the (meth) acrylate-based monomer [A], [B],
When mixed with [C], a polymerization reaction is started within a few seconds to several tens of minutes. Therefore, it is stored separately from [A], [B] and [C] and mixed immediately before use. .

In addition to the above-mentioned essential components, the curable composition of the present invention may optionally contain other components such as a powdered inorganic filler and a polymerization inhibitor. Specific examples of the powdery inorganic filler include kaolin, talc, clay, calcium carbonate, silica, silica-alumina, alumina, titanium oxide, calcium phosphate, glass powder and quartz powder.

〔The invention's effect〕

The curable composition of the present invention is excellent in low-temperature curability near room temperature and water-resistant adhesion performance, and further exhibits excellent adhesion performance to tooth substances such as enamel and dentin and dental alloys, and to pulp. Since it has a non-irritating characteristic, it can be used as a bonding agent for dental composite resin, hard resin, etc., and also used for various precision machining composite applications other than teeth. it can.
Among these, it is most preferable to use it as a bonding agent for dental composite resin.

〔Example〕

 Next, the present invention will be specifically described with reference to examples.

In addition, the curable composition evaluation method and examples of the present invention,
A production example of the photocurable composite resin used in Comparative Example is shown below. The following abbreviations used in the following Examples and Comparative Examples respectively represent the following compounds.

MMA ・ ・ ・ Methyl methacrylate HMA ・ ・ ・ n-Hexyl methacrylate HEMA ・ ・ 2-Hydroxyethyl methacrylate HPMA ・ ・ 2-Hydroxypropyl methacrylate NPG ・ ・ ・ Neopentyl glycol dimethacrylate2G ... ・ Diethylene glycol methacrylate TBB ・ O ・ ・ ・ Partial oxide of tri-n-butylboron DEPT ・ ・ ・ ・ Diethanolparatoluidine BPO ・ ・ ・ Benzoyl peroxide PTSNa ・ ・ ・ Sodium paratoluenesulfinate HQME ・ ・ ・ ・ Hydroquinone monomethyl Ether (I) Adhesion Evaluation Method The enamel surface or dentin surface of the anterior labial surface of cattle is # 600 d.
Polish it well with merry paper, smooth the surface, and then
Melt is 65% phosphoric acid aqueous solution for 30 seconds, dentin is 0.3M EDT
Etching treatment with A ・ 2Na-0.2M EDTA ・ Fe.Na aqueous solution for 60 seconds
Made sense. After sufficiently washing with water, air the etching surface.
Blow and dry, then cello with a 5 mm diameter hole
Hantape (approx. 13mm x 13mm) was put on. Example or ratio
Apply the bonding agent described in the comparative example to the circular hole and lightly
Teflon metal mold (direct
A cylinder with a diameter of 5 mm and a depth of 2 mm), and the photopolymerizable composite described below.
After filling with resin and covering the surface with cellophane paper,
On top of that, use a visible light irradiator (Kulzer, Translux)
And irradiate visible light for 30 seconds to cure the composite resin.
Let Then the cured surface of the composite resin and the acrylic
Le Bond and Super Bond C & B (Sun Medical Company
The adhesive test piece was prepared by adhering the same. After leaving at room temperature for 30 minutes
After soaking the adhesive test piece in 37 ° C water for 24 hours, empty it at a temperature of 23 ° C.
After leaving it in the air for 10 minutes, at a temperature of 23 ° C and a speed of 2 mm / min
A tensile test was conducted to measure the adhesive force. After adhesion test
All fracture surfaces were bovine tooth destruction and aggregation of composites resin.
No destruction or interface failure between composite resin and dentin
I was there.

(II) Preparation of photo-curable composituto resin: Triethylene glycol dimethacrylate 7.5 g, 1,3-bis (methacryloxyethoxy) benzene 7.5 g, 2,2,4-trimethylhexamethylenediamine diisocyanate 1 mol and 2 -15 g of an adduct with 2 mol of hydroxyethyl methacrylate, 40 g of a composite filler synthesized by the method described below, 30 g of finely powdered silica RM-50 (finely powdered silica manufactured by Nippon Aerosil Co., Ltd.), 4 mg of hydroquinone monomethyl ether.
Was kneaded with two rolls at 35 ° C. to prepare a composition. 10 g of this composition was thoroughly mixed with 45 mg of camphorquinone and 45 mg of 4-diethylaminobenzoic acid with a spatula to prepare a photocurable composite resin.

(III) Production Example of Composite Filler A solution of 0.1 g of benzoyl peroxide dissolved in 10 g of trimethacrylate of trimethylolpropane was placed in a mortar mortar, and finely divided silica (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd., average particle size 6 mμ) ) Was added little by little and mixed. The mixture was hung on a small rubber roll when the viscosity gradually increased and became dull, and the amount of finely divided silica added was 9.5 g. The obtained paste was removed from the roll and heat-cured at a mold temperature of 110 ° C. for 10 minutes at a pressure of 150 kg / cm ² to 200 kg / cm ² . The cured product was crushed with a ball mill to obtain 18.0 g of a composite filler that passed through a 230 mesh sieve. The average particle size of this composite filler is 1
It was 1μ.

Example 1 6 g of methyl methacrylate (MMA), 3 g of neopentyl glycol dimethacrylate (NPG), 1 g of 4-methacryloxyethoxycarbonylphthalic anhydride (4-META) and 2 mg of hydroquinone monomethyl ether (HQME) were mixed at room temperature. A monomer mixed liquid (A) was prepared. To 2 parts by weight of this (A) solution, 1 part by weight of a partial oxide of tri-n-butylboron (TBB · O, manufactured by Sunmedical Co., Ltd.) was mixed to prepare a curable composition, which was applied to teeth. An adhesive test piece was prepared by the above-mentioned method by applying thinly with a small brush. The results are shown in Table 1.
It was shown to.

Examples 2-8, Comparative Example 1, Comparative Examples 3-4 In Example 1, instead of using the monomer described in Example 1, the monomer mixture described in Table 1 was used in an amount described in Table 1 (A) was prepared, and the liquid (A) and a partial acid compound of tri-n-butylboron (TBB · O, manufactured by Sunmedical Co., Ltd.) were mixed in the amounts shown in Table 1 to prepare a curable composition. Then, an adhesion test piece was prepared by the method described in Example 1. The results are shown in Table 1.

Comparative Example 2 Instead of preparing the monomer liquid (A) using the monomer described in Comparative Example 1 in Comparative Example 1, 100 parts by weight of MMA, 11 parts by weight of 4-META, polymethylmethacrylate (for Superbond CB, Sun A monomer liquid (A) consisting of 80 parts by weight (made by Medicare) and 2 mg of hydroquinone monomethyl ether was prepared. Comparative Example 1 except that a curable composition was prepared by mixing the liquid (A) and a partial oxide of tri-n-butylboron (TBB · O, manufactured by Sunmedical Co., Ltd.) in the amounts shown in Table 1. An adhesion test was prepared by The results are shown in Table 1.

Comparative Example 5 MMA6g, NPG3g, 4-META1g, BPO0.2g and HQME2mg were mixed at room temperature to prepare a monomer solution (A). Then DEPT0.
Liquid consisting of 1 g, PTSNa 0.4 g, 99% ethanol 9.5 g (B)
Was produced. Equal amounts of (A) and (B) were mixed at room temperature to prepare a cured composition, which was applied to a tooth with a small brush. Then, an adhesion test piece was prepared by the method described in Example 1.
The results are shown in Table 1. Was produced. The results are shown in Table 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08F 220/38 MMU 230/02 MNS 299/02 MRS C09J 4/02 JBL

Claims (1)

[Claims] 1. A monofunctional (meth) acrylate-based monomer [A], a polyfunctional (meth) acrylate-based monomer [B] [provided that at least one urethane bond is contained in one molecule. (Meth) acrylate-based monomer and general formula (In the formula, R ¹ represents a divalent aromatic residue having at least one aromatic ring and optionally having an oxygen atom or a sulfur atom in the molecule, and R ² and R ³ are respectively A hydrogen atom or a methyl group, and n and m are positive integers), excluding polyfunctional (meth) acrylate monomers], [C] at least one (meth) acryloyl in one molecule. A curable composition comprising an acid group-containing (meth) acrylate-based monomer containing an oxyl group and [D] trialkylboron or an oxide thereof.