JPS63132984A - Visible light curable one-component liquid adhesive composition and tooth treatment method using the same - 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 Industrial Applications The present invention relates to adhesive compositions, particularly polymerizable compositions suitable for bonding hard tissues within the body, such as teeth and bones. The composition of the invention is used as a liner into which a restorative tooth filling composition can be applied and as a primer onto which a dental adhesive can be applied for mounting an orthodontic plaque or crown. be able to.

The invention therefore also relates to the use of the composition according to the invention as a primer in methods for tooth repair, bonding or repositioning.

Prior art amalgams and restorative filling compositions do not adhere well to tooth surfaces. During high tooth filling, the problem of poor adhesion can be ameliorated by the preparation of an undercut cavity, which can improve the mechanical retention of the filling. In the case of enamel surfaces, the mechanical fit can be improved by irregularly etching the surface with phosphoric acid. However, a true adhesive system should be able to improve dentists' surgical techniques.
It is. The use of phosphoric acid can be greatly reduced, or even eliminated in some cases, and restorative methods involving dentin removal can be performed with a single, reduced-wear removal of living tissue. , and marginal leakage should be reduced.

The adhesive systems associated with bones and teeth are real substances associated with living, moving tissue, and as such, any adhesive appears to be the result of a compromise between conflicting effects. It will be done. For example, hydrophilic groups are necessary for adhesion to tooth surfaces, but their presence increases the likelihood that the adhesive will become hydrolytically unstable. Nevertheless, many adhesives are available to practitioners, almost all based on organic phosphate esters. It is therefore highly desirable that this active adhesive component has a low concentration in the adhesive composition and therefore this component is necessary to have high adhesive properties. The composition has a low viscosity so that it flows easily over the surfaces to be bonded.

EP 0 074 708 lists a number of patent specifications in which various ethylenically unsaturated phosphoric acid esters are described as adhesives. In this specification, special phosphate esters characterized by long-chain alkyl esters of acrylic and methacrylic acids are described as having improved adhesive properties in dental applications. Specifically, 2-methacryquiloxyethyl dihydrodenephosphate is a relatively poor adhesive component and is highly susceptible to bubble formation in the coating. European patent issued Jji
l! No. 0,115,948 describes the use of organo-ro-11 acid esters as polymerizable adhesive components. European Patent Application Nos. 0058483 and 015
No. 2518 describes the use of bareii acid esters as polymerizable septamers in dental adhesives, these esters containing at least one ethylenically unsaturated functional group and 11IIIA has a chlorine or bromine atom directly bonded to the child.

3% rice allowed! No. 4,044,044 describes the use of phosphate esters of hydroxyac IJV-) as components in anaerobic adhesive compositions. These compositions are said to remain liquid while in contact with air, and are said to harden quickly when exposed to heavy metals with the exclusion of air. These adhesive compositions are useful as anti-sag materials, especially at high pressures.

The adhesive properties associated with polymerizable esters of 4jI acids are
It turns out that it depends on the concentration of impurities in the particular ester.

Thus, when the zohydrodene phosphate ester is substantially free of phosphoric acid, -hydrogen ester and fully esterified ester, the resulting adhesive composition is unexpectedly effective as an adhesive in an aqueous environment. The present invention provides a storage stable adhesive composition that can be rapidly cured in the presence of air.

Means for solving the interlude point According to the present invention, visible light curable one-component liquid adhesive compositions having a viscosity of less than 25 cps at 25°C are obtained, which have the following formula: -C(R-co-0-R"-0F
(0)(OR)'' (in the formula, R1 is a hydrogen atom or a methyl group, and Rs is -CH5-CHs-1-C'Hmaro-C'
H(CH3)-also H-CKca3)-cu,-)
and (b) 98 to 88 parts by weight of at least one ethylenically unsaturated monomer copolymerizable with the phosphate ester and an effective amount of a visible light-activated catalyst. It becomes more.

The II# ester component in the composition of the invention is advantageously 2-
It is methacryloyl derobildich P lodenphosphate. The phosphate nitrate used in the compositions of the invention, for example, the reaction of droxyacrylate (or methacrylate) with at least an equimolar amount of phosphorous oxychloride in the presence of a tertiary adenate, followed by The production speed is increased by the formation of Vm by hydrolysis of the residual chlorine-phosphorus bond. This dihydrophosphate ester is then purified in a series of washing and extraction steps to render the ester substantially pure, i.e., ll! It is free of other esters of acids, so that the concentration of such impurities is less than 5% by weight, preferably less than 2% by weight.

The adhesive composition of the present invention contains at least one ethylenically unsaturated monomer copolymerizable with a phosphate ester. The viscosity properties of this composition, such as the viscosity itself and the flow and wetting properties, are determined to a large extent by those of the monomers. The viscosity of the resulting composition is 25 at 25°C.
A wide variety of monomers are suitable for the compositions of the present invention, provided that the cp is below. The seven most commonly used salts include (meth)acrylates, vinyl urethanes and styrenic types and vinyl acetate. However, other drugs such as (meth)acrylamide,
Vinyl ethers, fumarates, maleates, vinyl ketones, vinylnitrile, vinylgin and vinylnaphthalene can also be used, alone or in combination, provided the viscosity parameters of the composition are satisfied. Advantageously, the concentration of phosphate ester in the adhesive composition is at least 5% by weight, but not more than 15% by weight.

Vinyl esters suitable for use in the process of the invention include, for example, vinyl acetate and structure CH, -CH-CO
Esters of acrylic acid having OR' (Ce "t" R5117, aryl, alkaryl, aralkyl or cycloalkyl group) are included. For example, R3 can be an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Special vinyl ethers which may be mentioned, such as methyl acrylate, ethyl acrylate, n- and indecvir-acrylate and n-11
- and butyl acrylate.

Suitable vinyl esters include, for example, esters of the formula: % where R4 is methyl.

In this ester of formula: can-C(R')COOR3, R3 and R4 may be the same or different.

Special vinyl esters that may be mentioned include, for example, methyl methacrylate, ethyl methacrylate, n-methacrylate
and isodeagyl, n-11-, and 7'' methyl methacrylate vinyl esters such as n-hexyl-, cyclohexyl-, and tetrahydrofurfuryl-acrylates and methacrylates. These monomers should have low toxicity. Suitable aromatic vinyl compounds of the styrenic type include, for example, styrene and its derivatives, ie the α-alkyl derivatives of styrene such as α-methylstyrene and -dilutoluene.

Suitable vinyl nitriles include, for example, acrylonitrile and its derivatives such as methacrylate.

Other suitable unsaturated monomers include ♂ylpyrrolidone, hydroxyalkyl acrylates and methacrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate, diethyl methacrylate and hydroxypropyl acrylate in human 1:I.

Polyfunctional monomers, ie, monomers having 211 or more vinyl groups, are also favorable as polymerizable materials.

Suitable monomers include, for example, glycol dimethacrylate, diallyl phthalate and triallyl cyanurate.

The ethylenically unsaturated material may include at least one ethylenically unsaturated polymer, advantageously in combination with at least one ethylenically unsaturated polymer.

Advantageously, the compositions of the invention do not contain volatile solvents. However, if a solvent is included, the following polymerizable materials may also be present, provided the viscosity of the composition is less than 25 cp at 25°C.

Such polymerizable substances are advantageously liquid ethylenically unsaturated substances, such as British Patent No. 1,552,063;
1! 1465 097, DE 1 498 421 and DE 2 419 887, and diols such as vinylurethanes or glycols, such as nibisphenols, for example in US Pat. 5066112
It is a reaction product with glycidyl alkyl acrylate as described in No. 4131729 and No. 4131729.

Preferred reaction products of glycidyl alkyl acrylates with diols have the following formula: The preferred vinyl urethanes described in the above-mentioned British patent and West German patent specification contain acrylic acid or methacrylic acid and at least 2 carbon atoms. It is a reaction product of an ester with a hydroxyalkanol and a urethane prepolymer, which has the structure (XN-Rδ-diisocyanate (where R5 is a divalent hydrocarl group) and the structure HO-
It is a reaction product of a diol of Re-OH (where R6 is the residue of a condensate of an alkylene diol and an organic compound having two phenolic or alcoholic groups).

Other suitable vinyl urethanes include those left by the reaction of alkyl, aryl, especially alkyl diisocyanates with hydroxyalkyl acrylates and alkyl acrylates, such as GB 1,401,805;
428672 and those described in the same specification No. 145CI505 are included.

The dental composition of the present invention advantageously has a composition of from 400 mμ to
It is cured by irradiation with visible light having a wavelength of 500 mμ. Curing of this composition is difficult to achieve to the extent that the composition contains a catalyst that is activated with visible light. Such a catalyst is
Preferably selected from fluorenone and diketones, at least one ketone and at least one organic peroxide.

Ketones suitable for use in the compositions of the invention also exhibit some photocatalytic activity on their own without the presence of organic peroxyl. Such activity of ketones is due to fI
It is strengthened by the addition of a reducing agent as described in Japanese Patent Application No. 2,251,048. Therefore, the ketone is
selected from fluorenone and α-diketones and their derivatives, which, with the keto ν excited,
However, in the absence of organic peroxides, it catalyzes the curing of ethylenically unsaturated materials when mixed with small amounts of available amines capable of reducing ketones. Evidence of hardening is usually
The change in viscosity of a mixture of ethylenically unsaturated substances containing at least 1% by weight of ketone and organic amine relative to the ethylenically unsaturated substance was measured using an oscillatory rheometer (Oscilla).
ting reometsr) 1. (The thickness of the sample can be determined by testing the 211 IB% mixture with light having a wavelength of 400-500 m#). Such tests are based on British Standard No. 5199 (B9).
75) The method described in Section 6.4 can be put into practice, provided that it is possible to direct visible light onto the mixture. Advantageously, this ketone is
With an irradiance of 1000 W/m”, for example Macam
Radiometer (Macam Photo+ome)
trics Lta, Edinburgh, a=ot
land) has a curing time of less than 15 minutes, measured at a height of 470 mμ and a band width of ±8 mμ.

Diketones have the following formula: where the radicals A may be the same or different and may be linked with a hydrocarbyl or substituted hydrocarbyl group or where the radical A becomes -1 to form a fused aromatic may form a ring system].

Group A may be an aliphatic or aromatic group.

Included within the scope of the term "digital truncated group" are alicyclic groups and aliphatic or aralkyl groups having aromatic substituents. Similarly, the term "aromatic group" includes within its scope groups having alkyl substituents, ie, alkaryl groups. The term "aromatic group" includes heterocyclic groups.

It may be a non-benzenoid cyclic group that is recognized as having the characteristics of a benzenoid aromatic group.

The radical A, especially if it is an aromatic radical, may have substituents other than andpacarbyl, such as halogen or alkoxy. Substituents other than a-carbyl can have the effect of inhibiting polymerization of ethylenically unsaturated materials, and if the α-diketone has such a substituent, this may be present in the photopolymerizable composition. Advantageously, it is not present in a concentration that substantially inhibits polymerization of the ethylenically incapable material in the composition.

The group A may additionally be a group O, either by a direct bond or by a divalent group, such as a divalent hydrocarbyl group. The group A may be further bonded to form a ring system. For example, when the group A is an aromatic group, the α-diketone has the structure: or derivatives thereof in which one or two hydrogen atoms are replaced by hydrocarbyl groups. The groups Y may be taken together to form a fused aromatic ring system.

In general, α-diketones are in the 9-spectrum, i.e. 40-
It can be excited by radiation with a wavelength longer than 0 m#, for example between 400 mμ and 500 mμ.

For the present invention, the α-diketone should be highly volatile so as to reduce odor and concentration fluctuations. Suitable diketones include pencil in which both radicals A are phenyl, α-diketones in which one of the radicals A is an M aromatic radical such as α-naphthyl and β-naphthyl, and α-diketones in which both radicals A are alkyl radicals such as p -) lyl α-diketones are included. Examples of suitable α-diketones in which group A is a non-benzenoid aromatic include furyl, such as 2:2'-furyl. Derivatives of α-diketones in which the group A has a non-hydrocarbyl group, such as pe 1)'-dialkoxypencyl, tbpe p'-dimethoxypenzyl or 1)
m p'-di/% el benzyl e.g. pe 1)'
- may be mixed with dichlorobenzyl or p-nitrobenzole. The group A may be directly bonded or may be linked with a divalent hydrocarbyl group to form a ring system. For example, the group A may be aliphatic. If the α-diketone is camphoraquinone, the α-diketone may be camphorquinone.

An example of an α-diketone having structure 1 is phenanthraquinone attached to an aromatic root.

Preferred derivatives include 1,2-zolomo, 2-nitro-14
-Nitro-13-ac! -12*7-sinitro, 1
-Methyl-7-itupropylphenanthraquinone.

The α-diketone may be an acenaphtituquinone in which the groups A together form a fused aromatic ring system.

Ketones include fluorenone and its derivatives such as especially 2-
It may also be an ester having a lower alkyl (C1-6), halo, nitro, or carboxylic acid at the 4-position, or an ester of hiso.

The ketone may be, for example, 0.0 of the polymerizable material in the composition.
They may be present in concentrations ranging from 1 to 2 parts by weight, although concentrations outside this range can be used if desired. Ketones are
0.1-1% by weight of ethylenically unsaturated substances in the composition
, more preferably in a concentration of 0.5 to 1 wt. The ketone should be lubricated in the polymerizable material, the concentration being related to the solution concentration.

Organic peroxides suitable for use in the compositions of the present invention have the formula: % where R? may be the same or different, hydrogen,
Alkyl, aryl or acyl groups in which more than one of the radicals R is not hydrogen. The term "acyl" means one having the formula: R8-C0-, where R8 is an alkyl, aryl, alkoxy or aryloxy group. The terms “alkyl” and “
"Rir" represents the above-mentioned group AKIJ, and includes alkyl and aryl substituted with 1.

Examples of organic peroxides suitable for use in the compositions of the invention include diacetyl peroxide, dibenzoyl peroxide, butyl peroxide, dilauroyl peroxide.

decylperpenzoe), V -t -ff lucip
oHexylperdicaldonate is included.

The organic peroxide may be present in the composition, for example, in the range of 0.1 to 10% by weight of the polymerizable material in the composition, although concentrations outside this range may also be used if desired. Can be used.

Peroxide reactivity is often measured in terms of the "10 hour range temperature", ie the temperature at which half of the oxygen is utilized within 10 hours. The peroxy r in the compositions of the invention is below 150°C, preferably below 100°C.
It has a temperature in the 0 hour time range.

The rate at which the compositions of the invention cure under the action of visible light can be increased by incorporating into the composition a reducing agent capable of reducing the ketones when they are in the excited state. Suitable reducing agents are described, for example, in FF1R Patent Application Publication No. 2251048, and include organic amines, phosphites, and sulfinic acids.

Generally, non-basic reducing agents are preferred. This is because they are difficult to react with phosphate esters. Suitable non-basic reducing agents include aldehyde r and formula: %formula%) [where n and m are integers of 1.2 or 3, n+m5
w4, R9 is an alkyl or alkenyl group having 1 to 18 carbon atoms, and RlO is R9 or R9C0
- or has the formula: ((R')s8n)I.

] is included.

Mixing of the components can be accomplished by stirring together the polymerizable material and any fillers. the catalyst component,
It is useful to first dissolve it in a polymerizable material, which may be conventional, but it is less advantageous to improve the solubility of the catalyst components by diluting with a suitable diluent. Once mixing has taken place, the diluent can optionally be removed, for example by distillation. Desirably, the compositions of the invention are substantially solvent-free. This is because their presence hinders adhesion and increases toxicity problems. Photosensitive catalysts impart sensitivity to light in the visible range of 400 mμ to 500 mμ to polymerizable substances and monomers, Part of the preparation and handling or filling of the containers of the compositions of the invention to which the catalytic catalyst has been added should be carried out in the substantial absence of light in this range. Most conventionally, the production can be carried out using light outside said range, for example light emitted from sodium vapor discharge lamps.

According to another aspect of the invention, the composition of the invention contains 4
A curing method is provided which consists of irradiation with visible light having a wavelength of 00 mμ to 500 mμ. The process can be carried out at any conventional temperature, provided that the composition does not crystallize and fracture (at too low a temperature) or volatilize excessively (at too high a temperature). can. The process is advantageously carried out at room temperature, for example from 15°C to 40°C.

It will be appreciated that the tooth surface is coated with the composition of the invention and then cured under a visible light source, advantageously the composition is cured under a portasolic light source.

It is advantageous to package the dental composition according to the invention in a single small container (eg 10 g content) to facilitate viewing in surgery and to reduce the risk of unwanted hardening due to eg stray light.

For cosmetic purposes, dental compositions may have the appearance of colored, stained or natural teeth, and the compositions of the invention therefore contain small amounts of pigments, opacifying agents and the like. It's okay. The composition may also include minor amounts of other materials, such as antioxidants and stabilizers, provided they do not substantially adversely affect curing.

Example The invention is illustrated in detail with reference to the following examples.

Example 1 (a) Production of phosphate ester oxychloride l1
1 (b27,911: 0.85 mol) was mixed with methylene chloride (600+7). This mixture was stirred at 0°C.
It was cooled to To this phosphorus oxychloride mixture was added 1-P roxiderovir methacrylate (b20, P, 0.83 mol),
A mixture of pyricine (65.8 g, 0.83 mol) and methylene chloride (40017) was added dropwise over 45 minutes while maintaining the reaction temperature in the range 0-5''C.

The mixture was stirred in this temperature range for 2 hours.Then, the reaction mixture was poured into 1 portion of ice-cold water, the methylene chloride layer was separated and washed twice with water.Then, the methylene chloride solution was poured into water. The methylene chloride was completely removed using a rotary evaporator to remove the aqueous phase and water-insoluble solids.The aqueous layer was washed twice with methylene chloride, and then acidified with careful stirring and added with 1208 ml of salt W. ), extract the aqueous phase with ethyl acetate (BT), and discard the aqueous phase. The concentration of the phosphate ester was then estimated and analysis by acid-base titration revealed that it contained less than 2% ester impurity by weight of 2-methacryloyloxyderopyl dihydrogen phosphate.6 The final composition was then determined as desired. The amount of ethylenically unsaturated monomer (comonomer) was added depending on the relative concentration required in the product. Ethyl acetate was then removed using a rotary evaporator at 65° C. and under vacuum of 50 m Hg.

(b) The production of vinyl urethane (YU) was carried out using the method described in EP 0059649.

(C) A number of formulations were prepared with comonomer concentrations and compositions as described in Table 1. To this monomer mixture, the following catalyst components were added: W/W% camphorquinone 0.73 dimethylaminoethyl-methacrylate (DMAIICM) 0.
49 to decyl perpenzoate 0.98 Topanol O at 200 pant to the final composition This addition and subsequent surgery using this composition were performed under a sodium vapor discharge lamp.

The repair composition material used with the adhesive composition was occlusin (0
cclua, in ; Imperial Chemi
CalIndustrie PLC product name)
rnal 1984.95-95 using the method described. The sample was passed through a tuned reflector and a dichronic filter to remove ultraviolet light.
Irradiation from a tungsten halogen lamp with
Hardened in seconds.

Dopanol is Imperial
Dopanol O, a product name of Chemical Industries PLC, is 2.6-di butyl-4.
- Methylphenol.

Example 2 An adhesive formulation containing the following formula was prepared as described in Example 1: Parts by weight of phosphate ester (Example 1a) 9.78T
gGM90.22 camphorquinone 0.73 diptyltin dilaure) 0.49 butyl perbenzoic acid 0.98 dopanol 0
A sample of the composition was fully cured to 200 ppm and evaluated as described in Example 1 and was found to have the same adhesive strength as in Table 1(b).

Example 6 Using tin compounds in the range instead of DMAM,
A series of adhesive compositions were prepared as described in . Samples of this composition were evaluated for cure time using the oscillatory rheometer method described above.

Part by weight Phosphate ester (Example 1a) 15TEGDM
85 Camphuaquinone
0.75 tin compound
0.5 Tin compound Curing time (seconds) None 126 Zodecyltin diacetate 96 Didetyltin zolaurate 90 Zoctyltin zoacetate 75 Tributyl diacetate 30 Tridecyltin methacrylate 45 Tributyltin oxide 60 Tridecyltin methoxide 244 to 0.5 %
According to DMAEM, the same result is also obtained.

Claims (1)

[Claims] 1. A visible light-curable one-component liquid adhesive composition having a viscosity lower than 25 cp at 25°C, which has the following formula: (a) the formula: CH_2=C(R^1). CO・O・R＾2
・OP(O)(OH)^2 (in the formula, R^1 is a hydrogen atom or a methyl group, and R^2 is -CH_2-CH_2-, C
H_2-CH(CH_3)- or -CH(CH_3)-
(b) 98 to 80 parts by weight of at least one ethylenically unsaturated monomer copolymerizable with the phosphate ester and an effective amount of A visible light-curable one-component liquid adhesive composition comprising a visible light-activated catalyst. 2. The composition according to claim 1, wherein R^1 is a methyl group. 3. R^2 is a propylene group, claim 1
The composition according to item 1 or 2. 4. The composition according to any one of claims 1 to 3, wherein the visible light activated catalyst contains an α-diketone. 5. The composition according to claim 4, wherein the diketone is camphorquinone. 6. The composition according to any one of claims 1 to 5, wherein the visible light activated catalyst contains an organic tin compound. 7. The composition according to any one of claims 1 to 6, wherein the visible light activated catalyst contains an organic peroxide. 8. The composition according to any one of claims 1 to 7, wherein the impurity concentration of the phosphate ester is lower than 2% by weight. 9. Any one of claims 1 to 8, wherein the concentration of the phosphate ester is 5% by weight or more.
Compositions as described in Section. 10, Formula (a): CH_2=C(R^1)・CO・O・
R^2・OP(O)(OH)^2 (In the formula, R^1 is a hydrogen atom or a methyl group, and R^2 is -CH_2, -CH_
2-CH(CH_3)- or -CH(CH_3)-CH
(b) 98 to 80 parts by weight of at least one ethylenically unsaturated monomer copolymerizable with the phosphate ester and an effective amount of A visible light-curable one-component liquid adhesive composition characterized by a visible light-activated catalyst is applied to the tooth surface, and visible light having a wavelength of 400 nm to 500 nm is applied to the composition at room temperature. A dental treatment method characterized by irradiation.