JPH01178569A - Dental adhesive composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which provides excellent adhesion between the tooth tissue of an organism and the material for repair of this tissue, by mixing a specified composition, a radical-polymerizable unsaturated monomer, a polymerizable phosphate compound, and a photopolymerization initiator. CONSTITUTION:A composition (A) is obtained by mixing at least one NCO- containing urethane prepolymer (a) of a molecular weight of 400-50,000 in which the content of ethylene oxide units is preferably 40-80mol.% based on the total of propylene oxide units and ethylene oxide units both constituting the principal chain, and if required, an inert diluent (b). Component A is mixed with at least one radical-polymerizable unsaturated monomer (B) containing no acid group in the molecule, in a weight ratio of A to B of 1-150:150-1, 0.1-30wt.% polymerizable phosphate compound (C) of formula I [wherein R is a group of formula II or III (wherein R1 is alkylene); R' is alkyl; n and m are each 1-2, and l is 0-1, provided that n+m+l=3], and 0.01-25wt.% photopolymerization initiator (D).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for bonding between a living tooth tissue and a material for repairing the tissue (metal material, organic polymer material, ceramic material, etc.). The present invention relates to a dental adhesive composition that can be used and has excellent adhesive properties.

[Prior art]

Traditionally, dental caries (so-called tooth decay) has been used in the field of dental materials.
Various metal materials (e.g., gold, silver, platinum, alloys, amalgam, etc.) are used for tooth restoration such as restoration of missing teeth.
, organic polymer materials (for example, polymethyl methacrylate V-)
, polycarbonate, polyfunctional vinyl cured product, composite resin, etc.), ceramic materials (for example, Beauselen, implant material, etc.), etc. are used. However, these materials do not inherently adhere to living tooth tissue. Therefore, for the purpose of adhesion between the restorative material and the living tooth tissue, we developed an inorganic collagen (protein) containing the main inorganic components such as apatite (calcium phosphate) that forms the tooth tissue.
Dental adhesive compositions containing compounds with various polar groups (phosphoric acid groups, hydroxyl groups, acid anhydride groups, etc.) as adhesive components have been proposed with the intention of improving interaction with organic main components such as ing.

[Problems to be Solved by the Invention] However, the above-mentioned prior art does not have any adhesion performance with living tooth tissue, especially dentin. This is due to physical and chemical structural factors of living dentin. In other words, dentin has a structure in which countless dentinal tubules run and are filled with body fluid, and the ratio of proteins such as collagen is higher than that of enamel, making it difficult to bond. It can be said that the environment is extremely harsh. Therefore, the adhesives according to the prior art are pretreated with apatite, which is an inorganic main component, and an etching agent such as phosphoric acid, in order to achieve a certain degree of adhesion to living dentin through the so-called anchor effect. However, if the adhesive strength is still insufficient and after a long period of time, a gap will form between the restorative material and the dentin, and in some cases, the restorative material may even fall off. It cannot be said that high adhesiveness is obtained.

[Means for solving problems]

The purpose of the present invention is to eliminate the need for complicated pretreatment with etching agents such as phosphoric acid, which was essential in conventional methods, in bonding living tooth tissue, especially dentin, to restorative materials, and to achieve a bond that is sufficient for practical use. An object of the present invention is to provide a novel dental adhesive composition that has high strength and is photopolymerizable.

That is, the dental adhesive composition of the present invention has (a)
(b) a composition comprising one or more V tan prepolymers containing incyanate groups and an inert diluent blended with the urethane prepolymers; (b) one or more radically polymerizable unsaturated monomers containing no acidic groups in the molecule (0 ) photopolymerization initiator and (d) -ceremony (11% formula%), in which OR
1 is an alkylene group. Further, R' is an alkyl group, n is 1 or 2, m is 1 or 2, t is 0 or 1,
Also, n + m + t=3. ) is a polymerizable phosphate ester compound represented by ? Contained as a main component.

In the incyanate group-containing urethane prepolymer which is component (a) of the present invention, alkylene oxide such as propylene oxide or ethylene oxide is added to a low molecular compound having two or more hydroxyl groups in the molecule such as glycol, glycerin, norbitol, or sucrose. For polyols such as polyether polyols made by addition polymerization of polyester polyols, or compounds with hydroxyl groups at the terminals by polycondensation of dibasic acids such as adipic acid and glyfurs such as ethylene glycol, A compound having two or more incyanate groups (C-Nco')t, ie, a polyincyanate, is obtained by reacting so that some of all incyanate groups remain.

As polyols, those having a hydroxyl group at the end are preferred in order to obtain excellent adhesion to the frame.

As a specific example, by a known method, an alkali catalyst such as caustic potash or caustic soda is added to an active hydrogen compound such as ethylene glycol, propylene glycol, or 1°6-hexanediol, and then ethylene oxide, propylene oxide, butylene oxide, etc. Tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, etc. are added to polyoxyalkylene diol obtained by addition polymerizing the alkylene oxide of Organic diisocyanate-1-i such as hexamethylene diisocyanate, NCo in which the NCo group is in an excessive amount
Examples include those obtained by reacting at a 10H equivalent ratio.

Among these urethane prepolymers, the following structural formulas (2) and (3) are obtained using glopylene glycol as an active hydrogen compound and diol obtained by addition polymerizing ethylene oxide and propylene oxide. Prepolymers represented by (4) and (4) are preferably used.

In particular, urethane prepolymers containing incyanate groups at both ends obtained by using tolylene diincyanate, 4,4-diphenylmethane diiso7anate or hexamethylene diincyanate as the terminal ink anating agent have particularly high adhesion. This is preferable because it provides strength.

0...-(3) ■ ■ -0-N-(C!H,)6-NCo...(4)(
In the formula, m is an integer of 1 to 100, n is an integer of 0 to 100, and may be randomly bonded to the propylene oxide unit and the ethylene oxide unit. ) The molecular weight of these urethane prepolymers is 400 to 5[ ], 000 to 50,000 to obtain mixed solubility and excellent adhesion to radically polymerizable unsaturated monomers.
It is preferably 0, especially 400 to 2 (Looo
It is particularly preferable that

In addition, these incyanate group-containing urethane prepolymers can be made hydrophilic or water-soluble by adjusting the ratio of ethylene oxide units to 40 to 80 mol% of the total amount of propylene oxide units and ethylene oxide units constituting the main chain of the prepolymer. Preferably, it is a modified polymer V polymer.

The urethane prepolymer contains incyanate groups present in the molecule, organic components (particularly collagen that contains many active hydrogen groups in its molecules), which is the main component of dentin in living tooth tissue, and water (body fluid). It is the ninth type that develops adhesiveness with the restorative material through the reaction of It is something.

Although it is possible to use the inocyanate group-containing urethane prepolymer alone, in order to improve workability when using the composition, diluents that are inert with respect to isocyanate groups, such as acetone, methyl ethyl ketone, ethyl acetate,
Toluene, carbon dioxide, trichloroethane, etc. may be added.

In the dental adhesive composition of the present invention, if there is no need to consider shortening the curing time, sufficient adhesive strength can basically be obtained with component U (a) alone. Furthermore, as a result of intensive research on improving it, we were surprised to find that ((
1) Component Polymerizable Phosphate Compound 'k It has been found that even stronger adhesive strength can be obtained by using it in combination with component (a). Specific examples of the polymerizable phosphoric acid ester compound include H0 H H R il H, etc. Among these polymeric phosphoric acid ester compounds, methacryloxyethyl phosphate dimethacryloxyethyl heptophosphate is particularly preferred. preferable.

However, when adhesive work is intended, for example in the oral cavity, there are often time constraints on curing the adhesive layer. However, the radically polymerizable unsaturated monomer that does not contain an acidic group in the molecule, which is the component (c) of the present invention, has the ability to quickly solidify the adhesive layer by light irradiation in the presence of the photopolymerization initiator, which is the component (c). (a)
Any monomer that does not limit the adhesive performance of component (c) and component (c) can be used, and monofunctional or polyfunctional monomers may be used.

Specific examples of monofunctional unsaturated materials include methyl acrylate, methyl methacrylate, ethyl acrylate,
Ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, hentyl methacrylate, hexyl acrylate, hexyl methacrylate, hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, vinyl acetate, styrene, acrylonitrile, glycidyl methacrylate, benzyl methacrylate Among them, methyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate and vinyl acetate are preferably used.

In addition, as a bifunctional unsaturated upper group, the following general formula (5) (wherein, HIH hydrogen atom or methyl group, p is 1 to 20
is an integer. ) Polyethylene glycol di(meth)acrylate etc. can be used, and specific examples include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrynaute, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. Ethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate,
meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate
Acrylate, decaethylene glycol di(meth)acrylate, polyethylene glycol (meth) with p=14
diacrylate, polyethylene glycol di(meth)acrylate with p of 17, polyethylene glycol di(meth)acrylate with p of 19, among others, ethylene glycol di(meth)acrylate,
Triethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, p is 14
Polyethylene glycol (meth)acrylate is preferably used.

Furthermore, t6-hexanethiol di(meth)acrylate, neobentylglycol di(meth)acrylate,
Trimethylolpropane tri(meth)acrylate and methacrylate can also be used, and among them, trimethylolpropane triacrylate and 1,6-hexanediol di(meth)acrylate are preferably used.

Further, the following general formula (6) (in the formula, R, ijH or methyl group, and p is an integer of 1 to 20) and the following general formula (OHCH).

Bisphenol A diglycidyl (meth)acrylates represented by 0H...(7) (wherein R1 is a methyl group and p is an integer of 1 to 20) can also be used, and their specific examples are as follows: Examples include 2,2'-bis(4-methacryloyloxyphenyl)furopane, 2,2'-bix[a-(5-methacryloyloxicu2-hydroxyproboxylic]phenyl)furopane, t2- Bis[3-(meth)acryloyloxy-2-hydroxypropoxy]ethane, pre-4-bis[3-(meth)acryloyloxy-2-hydroxypropoxy]butane, and the like are preferably used.

Further, general formula (8) Bird [wherein n represents an integer of 1 to 1o, and R1 and R1 represent a hydrogen atom or a methyl group. ] It is also possible to use hexafunctional urethane-based methacrylates and acrylates with an incyanuric acid skeleton represented by the formula (8), where n = 6, R8 is a hydrogen atom, and R1 is a methyl group. The shown hexafunctional urethane acrylate (hereinafter abbreviated as U-7SRm) and n = 6, R1
A hexafunctional urethane methacrylate (hereinafter abbreviated as U-6H) in which both R1's are methyl groups is preferably used.

Further, general formula (9) (wherein R, *R, t'!El or a methyl group, Xi, -
C horse-, -C horse CH, -e -(cal, -, -(O
B, -1. ) It is also possible to use tetrafunctional urethane (meth)acrylates represented by the general formula (9).
), R1 is a hydrogen atom, R1 is a methyl group, and X is -(
Oh,). - Tetrafunctional urethane (meth)acrylate (hereinafter abbreviated as U-4H) and 4 in which R1 and R are both methyl groups and X is -(CHl)8-
Functional methacrylate (hereinafter abbreviated as U-4H) is preferably used.

The amount of the polymerizable phosphoric acid ester compound is usually 11 to 30 parts by weight, preferably α5 to 10 parts by weight, and more preferably 1.0 parts by weight, based on all the radically polymerizable unsaturated monomers.
~10 parts by weight.

As the photopolymerization initiator, component (c) of the present invention, conventionally known ultraviolet polymerization initiators (gAli! benzophenone, etc.) or visible light polymerization initiators can be used depending on the purpose of use. When used indoors, 400 to 1200
A photopolymerization initiator that initiates polymerization by visible light in the wavelength range of about 100 nm is preferably used. Therefore, the photosensitizer in the photopolymerization initiator is preferably one that can be excited by wavelengths around 400 to 1200 nm, and α-diketone compounds can be mentioned as one example of such compounds. Specific examples of the α-diketone compound include camphorquinone, benzyl, diacetyl, etc. Among them, camphorquinone is preferably used because it exhibits high polymerization activity.

The visible light polymerization initiator of the present invention can be used in combination with such a sensitizer and a reducing agent such as a tertiary amine.
This is desirable in order to obtain the desired excellent photopolymerizability. Third
Specific examples of class amine compounds include trimethylamine,
Aliphatic amines such as triethylamine and tripropylamine: and isoamyl 4-(N,N-dimethylamino)benzoate, hexyl 4-(N,N-dimethylamine)benzoate, 4-(LM-dimethylamino)benzoic acid hebutyl, octyl 4-(N,N-dimethylamino)benzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone and 4,4'-bis(dibutylamino) Aromatic amines such as benzophenone can be mentioned, among which aromatic tertiary amines are preferably used, especially 4-(N,
Isoamyl N-dimethylamino)benzoate 4.4
1-bis(dimethylamino)benzophenone is the most preferred because it exhibits excellent visible light polymerizability when used in combination with camphorquinone.

Appropriate amounts of these visible light polymerization initiators are present depending on the frame and the types of photosensitizers and reducing agents used. For example, in a system of can-7-arquinone and inamyl 4-(N,N-dimethylamino)benzoate, the addition of can-7-arquinone to all radically polymerizable unsaturated monomers
i[The range by weight is preferably 101 to 25, particularly 105
The range of 15 to 15% by weight is suitable, and the amount of isoamyl 4-(N,N-dimethylamino)benzoate to be added is 5 to 3% by weight.
A range of 0 weight ratio is preferred, and a range of α1 to 25 weight ratio is particularly preferably used. For example, in a system of camphorquinone and 4,4'-bis(dimethylamino)benzophenone, 7% of the total radically polymerizable unsaturated monomers are used.
The amount of archinone added is preferably in the range of α005 to 30]i, particularly preferably the range of LO3 to 20, and the amount of 4.41-bis(dimethylamino)benzophenone to be added is 101 to 25. A range of 105 to 20% by weight is particularly preferably used.

The weight ratio of component (a) and component (1) of the present invention is preferably in the range of 1:150 to 150:1, especially 1:10.
A ratio of 0 to 100:1 is preferred, and a ratio of 1:50 to 50:1 is particularly preferred in order to obtain practical adhesion.

The dental adhesive composition of the present invention is composed of the above-mentioned four components as main components, but may also include inorganic fillers (for example, porcelain powder, quartz powder, various glass powders, etc.), organic polymers (for example, methyl methacrylate, polysterene, etc.)
, colorants, polymerization inhibitors (eg, hydrogynone, methylphenol, etc.), oxidation stabilizers, ultraviolet absorbers, pigments, dyes, and the like can also be blended.

It is convenient to store the dental adhesive composition of the present invention in a state in which the above-mentioned four components are usually mixed until the time of use. It may be stored and mixed at the time of use.

A light source for curing the dental adhesive composition of the present invention in a short time, particularly a visible light source, is a light source with a wavelength of 450 emitted from a halogen lamp, a xenon lamp, a mercury lamp, a fluorescent lamp, etc.
Light @ Gold can be used by 0 to 12,000 people.

In addition, the dental adhesive composition of the present invention can be applied to various restorative materials, including composite resins (composite materials containing polyfunctional monomers and inorganic fillers), which are common as prosthetic materials in the industry. In addition to thermosetting materials such as resins for dental crowns, thermoplastic resins such as polymethyl methacrylate, polysulfone, and polycarbonate, which are used as resins for denture bases, various cement materials, amalgam, alumina, gold, and alloys. Excellent adhesion to materials can be obtained.

〔Effect of the invention〕

According to the dental adhesive composition of the present invention, living tooth tissue,
In particular, when bonding dentin and a restorative material, there is no need for complicated pretreatment with an etching agent such as 9IJ acid, which is essential in conventional techniques, and it is possible to obtain a practically sufficient bonding force. Also, since it has photopolymerizability, it can be solidified in a short time by light irradiation before its original adhesive strength is exerted, and it is also easy to handle in the oral cavity.

[Embodiments of the invention]

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these implementations.

[Manufacture of reconstitution material-A (visible light curing composite resin)]

A mixture (paste) consisting of a polyfunctional monomer, an inorganic filler, and a visible light polymerization initiator shown in the above formulation.
That is, a visible light curing composite L/JIN was produced in a dark room to obtain a restorative material.

[Manufacture of restorative material-B (visible light curing resin for dental crowns)]

A mixture of the polyfunctional monomer and visible light polymerization initiator shown in the above formulation, that is, a visible light curing resin for dental crowns, was produced in a dark room to obtain Restorative Material-B.

[Adhesiveness evaluation method and adhesive strength measurement method] (1) Cut a fresh bovine front tooth immediately after tooth extraction with a precision cutter (Isomet, manufactured by Buehler) to expose the dentin plane and enamel plane, and measure the exposed plane t. -Klooo Polish thoroughly under water using waterproof abrasive paper.

(2) A dental adhesive composition is applied to the polishing surface, and if volatile components such as a solvent are present, the volatile components are evaporated and scattered by blowing air for about 10 seconds.

(3) After installing a cylindrical silicone ring (one side can be opened) with an inner diameter of about 51 cm, a height of about 5 cm, and a wall thickness of about 3 mm on the flat surface coated with the dental adhesive composition, inside this silicon ring The liquid restorative material is filled to a height of about 5 mm.

(4) Touch the upper end of the silicone ring filled with the restorative material with the irradiation port of a visible light irradiator (aC light, manufactured by Menshi Dental Industry ■), and irradiate it with visible light for t-60 seconds to remove the restorative material and adhesive. harden.

(5) After about 10 minutes, remove the silicone ring,
Obtain an adhesive test piece in which the repair material is adhered to the surface of the sample to be adhered.

(6) After storing the entire adhesive test piece in water at 37°C for a predetermined period of time, a spacer for adhesion testing (an acrylic rod with the same diameter as the restoration material) was placed on top of the restoration material. First, manufactured by Menshi Dental Industry ■) was used to adhere the adhesive, and the adhesive was set in a predetermined test holder, and a tensile test was conducted to measure the adhesive strength. The measurement conditions are shown below.

Tensile testing machine: Toyo Baldwin Tencron cross head speed (Tensile speed): (L 5 wm
/ min Chart speed: 10 wa / min full scale = 5 watts or 20 watts [Synthesis of urethane prepolymer containing icanate group] Using propylene glycol as an active hydrogen compound,
The ring-opening copolymerization of propylene oxide and ethylene oxide by a known method resulted in the production of compounds in Table 1 in which the molar ratios and average molecular weights of ethylene oxide units (hereinafter abbreviated as KO) and propylene oxide units (hereinafter abbreviated as PO) are different. Various polyether glycols described in 1. were produced.

Next, tolylene diincyanate (2,4/2.6 isomer ratio = 80/20, hereinafter referred to as TD
4,4-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) and hexamethylene diicanate (hereinafter abbreviated as IiD) in a molar ratio of polyether glycol and incyanating agent of 1:2. The reaction was carried out to obtain various urethane prepolymers containing isocyanate groups at both terminals and having the abbreviations shown in Table 1.

[Preparation of a mixture of a radically polymerizable unsaturated monomer containing no acidic group in the molecule (hereinafter abbreviated as monomer X), a polymerizable phosphate ester compound (hereinafter abbreviated as monomer 2), and a visible light polymerization initiator] Various monomers A mixture of X, monomer 2, and a visible light polymerization initiator was prepared in a general-purpose mixer in a dark room. Table 2 shows the composition and abbreviations of these mixtures.

Examples 1 to 52 LC of various urethane prepolymers containing incyanate groups at both ends produced in [Synthesis of prepolymers] and mixtures of monomer X, monomer 2, and visible light polymerization initiator! -9 were mixed in the same weight amounts to obtain an adhesive composition.

These adhesive compositions were evaluated for adhesion to Chitose and dentin surfaces without etching treatment according to the above-mentioned adhesive evaluation method and adhesive strength measurement method, and the results are shown in Table 3. Ta.

Similarly, the evaluation results for nine adhesive compositions using 'LC-4t- are shown in Table 4.

Examples 55 to 62 TPT-11+, a urethane prepolymer containing incyanate groups at both ends, produced by prepolymer synthesis! -, various monomers X, monomer 2, and a visible light polymerization initiator mixture were mixed in equal weight amounts to obtain an adhesive composition.

These adhesive compositions were evaluated for adhesion to restorative materials in the same manner as in Example 911, and the results are shown in Table 5.

Table 5 ゝThe number of test specimens n = 5.

Examples 63 to 72 TPT-11, a urethane prepolymer containing isocyanate groups at both ends produced by prepolymer synthesis, and LO-13, a mixture of various monomers X, monomer 2, and visible light polymerization initiator shown in Table 6. -LC-22 were mixed in the same weight amounts to obtain an adhesive composition.

These adhesive compositions were evaluated for adhesion between the restorative material and the human body in the same manner as in Example 1, and the results are shown in Table 6.

Comparative Examples 1 to 14 Adhesive compositions were prepared in exactly the same manner as in Example 1, except that instead of the urethane prepolymer containing isone anate groups at both ends, various polyether glycols used in the synthesis of the prepolymer were used. The adhesion was evaluated.

The results are shown in Table 7.

Table 7 ``The test was conducted with the number of test samples n = 3.

Comparative Examples 15 to 26 Adhesive compositions containing only a mixture of various monomers X, monomer 2, and a visible light polymerization initiator were obtained, and their adhesive properties were evaluated in exactly the same manner as in Example 1. The results are shown in Table 8.

Table 8 "Double-terminated isocyanate produced by synthesis of 27-3° prepolymer conducted with test sample number n = 5, 9 comparison rows"
TPT-11, a 1-group-containing urethane prepolymer, and LC-23 to LC-26, which are mixtures of various monomers A drug composition was obtained.

The adhesion of these adhesive compositions to restorative materials was evaluated in the same manner as in Example 1, and the results are shown in Table 10.

Table 9 Feng: The number of test samples n = 3.

Examples 73 to 78 Adhesives were prepared in the same manner as in Example 1, except that the blending weight ratio of the urethane V polymer containing incyanate groups at both ends and the monomer X/monomer 2/visible light polymerization initiator mixture was changed. A composition was obtained and its adhesive properties were evaluated. The results are shown in Table 11.

Table 11 ``The test was conducted with the number of test samples n = 3.

Examples 79 to 82 Using the adhesive composition obtained in Example 10, the adhesiveness to various repair materials was evaluated in the same manner as in Example 1. The results are shown in Table 12.

Table 12 *1: Bone 2 Niocrasin, manufactured by Iax Co., Ltd. Tested with n=3 specimens after 1 day of storage in water at 37°C

Claims (1)

[Scope of Claims] 1) (a) a composition comprising one or more isocyanate group-containing urethane prepolymers or the urethane prepolymers blended with an inert diluent; (b) a radically polymerizable composition containing no acidic groups in the molecule; One or more unsaturated monomers (c) Photopolymerization initiator and (d) General formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (1) (In the formula, R is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ These are selected from the group consisting of, and R_1 in these formulas is an alkylene group. Further, R' is an alkyl group, n is 1 or 2, m is 1 or 2, l is 0 or 1, and n+m+l=3. ) A dental adhesive composition containing a polymerizable phosphate ester compound as a main component.