GB2218104A - Adhesive compositions - Google Patents
Adhesive compositions Download PDFInfo
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- GB2218104A GB2218104A GB8910125A GB8910125A GB2218104A GB 2218104 A GB2218104 A GB 2218104A GB 8910125 A GB8910125 A GB 8910125A GB 8910125 A GB8910125 A GB 8910125A GB 2218104 A GB2218104 A GB 2218104A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dental Preparations (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
.DTD:
g -i- ADHESIVE COMPOSITIONS The present invention relates to adhesive compositions and in particular to polymerlsable compositions suitable for adhering strongly to rigid, hard tissues in the body such as teeth and bones. The 9omposltlons of the invention may be used as liners to which restorative dental filling compositions may be applied and as primers onto which may be applied dental adhesives for mounting for example orthodontic brackets or crowns. The present invention therefore also relates to the use of the present compositions as primers in a method for repairing, adhering to, or altering the position of teeth.
.DTD:
Amalgam and restorative dental filling compositions do not adhere well to tooth surface. In filling a dental cavity, the problem of poor adhesion can be ameliorated by preparing undercut cavities so as improve mechanical retention of the filling. In the case of enamel surfaces, mechanical keying can be improved on a microscopic scale by etching the surface with phosphoric acid. However a truly adhesive system would enable the dentist to improve operative procedures. The use of phosphoric acid could be greatly reduced or even eliminated in some instances; restorative procedures involving removal of dentin could be carried out with a much reduced level of removal of vital tissue marginal leakage might be reduced.
.DTD:
It has to be borne in mind that an adhesive system is associated with bone and teeth which are real materials, that is, it is associated with living, dynamic tissue, and as such any adhesive is likely to be the result of a compromise between competing influences. For example, to adhere to the surface of a tooth requires hydrophilic groups but their presence increases the probability that the adhesive will be hydrolytically unstable. Nevertheless a number of adhesives are available to the practitioner some of which are based on organic phosphate esters. It is highly desirable therefore that the active adhesive component have a low concentration in the adhesive composition and hence that component needs to have high adhesive properties. The composition should have low viscosity so that it readily flows over the surface to be bonded.
.DTD:
European patent specification 0 074 708 discusses a considerable number of patent specifications in which various ethylenically unsaturated phosphorus esters are described as adhesives. In that specification particular phosphate esters based on a long chain alkyl ester of acrylic and methacrylic acids are claimed and said to have improved adhesive properties in dental applications. That specification states that 2methacryloyloxyethyl dlhydrogen phosphate is a comparatively poor adhesive component and causes blistering in a paint film. European patent application 0 115 948 describes the use of organic pyrophosphate esters as polymerlsable adhesive components. European patent applications 0 058 483 and 0 132 318 describe the use of halophosphorus acid esters as polymerisable monomers in a dental adhesive; these esters contain at least one ethylenically unsaturated functional group and a chlorine or bromine atom attached directly to the phosphorus atom.
.DTD:
United States patent specification 4044044 describes the use of phosphate esters of hydroxy acrylates as components in anaerobic adhesive compositions. Those compositions are said to remain in a liquid state as long as they remain in contact with air whilst they are said to cure rapidly by polymerisation under the exclusion of air. Those adhesive compositions are useful as loosening prevention materials particularly at high pressure.
.DTD:
It has now been found that the adhesive properties associated with polymerisable esters of phosphorus acid are not only dependant upon the level of impurity in the particular ester but on the inclusion of a small quantity of a related fine filler.
.DTD:
According to the present invention a single-component, visible llghtcurable liquid adhesive composition is provided which comprises (a) 2 to 20 parts by weight of at least one substantially pure phosphate ester having the formula CH2=C(RI).c0.0.R2.0P(0)(0H)2 in which RI is a hydrogen atom or a methyl group, and R2 is -CH2-CH2-, -CH2-CH(CH3)- or CH(CH3)-C2- and (b) 98 to 80 parts by weight of at least one ethylenically unsaturated monomer copolymerlsable with the phosphate ester,and (c) I to 9% by weight based on a + b of at least one inorganic filler having particle size less than 0.1m, and an effective amount of a visible light activated catalyst.
.DTD:
The phosphorus ester component in the present compositions is preferably 2-methacryloyloxypropyldihydrogen phosphate. The phosphate esters used in the compositions of the present invention may be prepared by for example reacting hydroxy alkylacrylate (or methacrylate) with at least an equimolar amount of phosphorus oxychlorlde in the presence of a tertiary amine, followed by hydrolysis of any remaining chlorine-phosphorus bonds. The dihydrogen phosphorus ester is then purified by a series of wash and extraction stages so that the ester is substantially pure, ie free of other esters of phosphorus acid so that such impurity level is less than 5% by weight, preferably less than 2% by weight.
.DTD:
The adhesive compositions of the present invention contain at least one ethylenlcally unsaturated monomer copolymerisable with the phosphate ester. The most frequently used monomers include those of the (meth)acrylate, vinyl urethane and styrene types and vinyl acetate. However other monomers such as (meth)acrylamldes, vinyl ethers, fumarates, maleates, vinyl ketones, vinyl nitriles, vinyl pyridines and vinyl naphthalenes may also be used either alone or in combination provided that the viscosity parameter of the composition is fulfilled. The concentration of phosphate ester in the adhesive composition is preferably 5 parts by weight or more, and preferably no greater than 15 parts by weight.
.DTD:
Vinyl esters suitable for use in the method of the invention include, for example, vinyl acetate and esters of acrylic acid having the structure CH2=CH-COOR3, where R3 is an alkyl, aryl, alkaryl, aralkyl or cycloalkyl group. For example, R3 may be an alkyl group having from I to 20, and preferably i to i0 carbon atoms. Particular vinyl esters which may be mentioned include, for example, methyl acrylate, ethyl acrylate, n- and isopropyl-acrylates, and n--, iso- and tertiary butyl acrylates.
.DTD:
Other suitable vinyl esters include, for example, of the formula esters CH2=C(R4)C00R3 where R4 is methyl. In the ester of formula CH2=C(R4)COOR3 R3 and R4 may be the same or different.
.DTD:
Particular vinyl esters which may be mentioned include, for example, methyl methacrylate, ethyl methacrylate, n- and isopropylmethacrylate, and n-, iso- and tertiary butyl methacrylate vinyl esters such as n-hexyl, cyclohexyl and tetrahydrofurfuryl acrylates and methacrylates. The monomers should have low toxicity. Suitable aromatic vinyl compounds of the styrene type include, for example, styrene and derivatives thereof, e. g. =-alkyl derivatives of styrene, e.g. =-methyl styrene, and vinyl toluene.
.DTD:
Suitable vinyl nitriles include, for example, acrylonitrile and derivatives thereof, e.g. methacrylonitrile.
.DTD:
Other suitable ethylenically unsaturated monomers include vinyl pyrrollidone, and hydroxyalkyl acrylates and methacrylates, e.g. hydroxyethyl acrylate, hydroxypropyl-acrylate, hydroxyethylmethacrylate and hydroxypropyl-methacrylate.
.DTD:
Polyfunctional monomers are also suitable as polymerisation materials, that is, monomers containing two or more vinyl groups. Suitable monomers include, for example, glycol dimethacrylate, diallyl phthalate, and triallyl cyanurate.
.DTD:
The e=hylenically unsaturated material may include at least one ethylenlcally unsaturated polymer, suitably in combination with at least one ethylenically unsaturated monomer.
.DTD:
solvent.
.DTD:
The present composition is preferably free from volatile Such polymerisable materials are preferably liquid ethylenically unsaturated material such as vinyl urethane for example those described in British patent specifications 1352063, 1465097, 1498421 and German Offenlegungsschrlft 2419887 or the reaction product of a diol such as glycol but particularly a blsphenol with a glycidyl alkacrylate such as those described for example in United States patent specifications 3066112 and 4131729 (the disclosure in these specifications are incorporated herein by way of reference).
.DTD:
A preferred reaction product of a glycldyl alkacrylate and a diol has the formula:
.DTD:
Preferred vinyl urethanes described described in the aforesaid British patent specifications and German Offenlegungsschrift are the reaction product of a urethane prepolymer and an ester of acrylic or methacryllc acid with a hydroxy alkanol of at least 2 carbon atoms, the urethane prepolymer being the reaction product of a dllsocyanate of the structure OCN--R5-NCO and a dlol of the structure HO--R6-OH wherein R5 is a divalent hydrocarbyl group and R6 is the residue of a condensate of an alkylene oxide with an organic compound containing two phenolic or alcoholic groups.
.DTD:
Other suitable vinyl urethanes include those made by the reaction of alkyl and aryl, preferably alkyl, dlisocyanates with hydroxy alkyl acrylates and alkacrylates such as those described in British patent specifications 1401805, 1428672 and 1430303 (the disclosures of which are included herein by way of reference).
.DTD:
The dental compositions of the present invention are cured by irradiating the composition with visible radiation, preferably that having a wavelength in the range 400m to 500m. In order that curing of the compositions may be achieved in that range the compositions contain a catalyst which is activated by visible light.
.DTD:
Such a catalyst preferably contains at least one ketone selected from fluorenone and diketone and at least one organic peroxide.
.DTD:
Ketones suitable for use in the composition of the present invention also show some photosensitive catalytic action on their own without the presence of organic peroxide. Such activity of the ketone is enhanced by the addition of a reducing agent as described in the German Offenlegungsschrlft 2251048. Accordingly the present ketones are selected from fluorenone and a-dlketones and their derivatives which in admixture with a similar amount of organic amine which is capable of reducing that ketone when the latter is in an exlcted state, but in the absence of organic peroxide, catalyse cure of an ethylenlcally unsaturated material. Evidence of cure may be conveniently detected by examining the change in viscosity of a mixture of the ethylenically unsaturated material containing the ketone and organic amine each at 1% by weight based on ethylenlcally unsaturated material using an oscillating rheometer, samples -- 7 -- thickness 2mm., whilst the mixture is being irradiated with light having wavelength in the range 400 to 500m. Such an examination may be carried out using the method described British Standard 5199: 1975, paragraph 6.4 provided that provision is made to allow visible light to be directed onto the mixture. Preferably the ketone has a cure time of less than 15 minutes at a radiation level of i000 w/m2 as measured at 70 m, bandwidth 8m, for example using a Macam Radiometer (Macam Photometrics Ltd., Edinburgh, Scotland).
.DTD:
Diketones have the formula:
.DTD:
A-C-C-A 0 0 in which the groups A, which may be the same or different, are hydrocarbyl or substituted hydrocarbyl groups and in which the groups A may be further linked together by a divalent link or by a divalent hydrocarbyl or substituted hydrocarbyl group or in which the groups A together may form a fused aomatic ring system. Preferably the groups A are the same.
.DTD:
The groups A may be aliphatic or aromatic. Within the scope of the term aliphatic are included cycloaliphatic groups and aliphatic groups which carry aromatic substituents, that is, aralkyl groups. Similarly within the scope of the term aromatic group are included groups which carry alkyl substituents, that is, alkaryl groups. Within the term aromatic groups are included heterocyclic groups.
.DTD:
The aromatic group may be a benzenoid aromatic group, e.g. the phenyl group, e.g. the phenyl group, or it may be a non-benzenoid cyclic group which is recognised in the art as possessing the characteristics of a benzenoid aromatic group.
.DTD:
The groups A, especially when aromatic may carry substltuent groups other than hydrocarbyl, e.g. halogen or alkoxy. Substltuents other than hydrocarbyl may result in inhibition of polymerlsation of ethylenlcally unsaturated materials, and if the -dlketone contains such substltuents it preferably is not present in the photopolymerlsable composition in such a concentration as to result in substantial inhibition of polymerlsatlon of the ethylenlcally unsaturated material in the composition.
.DTD:
The groups A may be further linked together by a direct llnk, or by a divalent group, e.g. a divalent hydrocarbyl group, that is, in addition to the link through the group, -C-C- 11 II 0 0 The groups A may be further linked so as to form a cyclic ring system. For example, where the groups A are aromatic the u-diketone may have the structure (Y)m Ph- C - C -- Ph II II 0 0 in which Ph is a phenylene group, Y is >CH2, or a derivative thereof wherein one or both of the hydrogen atoms are replaced by a hydrocarbyl group, and m is O, I or 2. Preferably the group Y is linked to the aromatic groups in positions ortho to the group system.
.DTD:
The groups A together may form a fused aromatic ring In general, u-diketones are capable of being excited by radiation in the visible region of the spectrum, that is, by light having a wavelength greater than 4OOm, e.g. in the wavelength range 400mg to 500m. For the present invention, u- diketone should have low volatility so as to mlnimlse odour and concentration variation. Suitable a-diketones include benzll in which both groups A are phenyl, a-dlketones in which both of the groups A are fused aromatic, e.g. unaphthil and -naphthil, and u- diketones in which the groups A are alkaryl groups, e.g. p-tolil. As an example of a suitable udiketone in which the groups A are non-benzenoid aromatic there may be mentioned furil, e.g. 2:2'-furil. Derivatives of the =-diketone in which the groups A carry non-hydrocarbyl groups as for example p,p'dialkoxy benzil, e.g. p,p'-dimethoxy benzil or p,p'- dihalobenzil, e.g. p,p'-dichlorobenzil, or p-nitrobenzil may be incorporated.
.DTD:
The groups A may be linked together by a direct link or by a divalent hydrocarbyl group to form a cyclic ring system. For example, where the groups A are aliphatic the =-diketone may be camphorquinone.
.DTD:
An example of an =-diketone having the structure I is phenanthraquinone in which the aromatic groups A being linked by a direct link ortho to the group -C-C- II II 0 0 Suitable derivatives include 2-bromo-, 2-nitro, 4-nitro, 3- chloro-, 2,7- dinltro, l-methyl-7-isopropyl phenanthraqulnone.
.DTD:
The =--diketone may be acenaphthene quinone in which the groups A together form a fused aromatic ring system.
.DTD:
-- I0 -- The ketone may also be fluorenone and its derivatives such as for example lower alkyl (CI-6), halo, nitro, carboxyllc acid and esters thereof, particularly in the 2- and 4-positions.
.DTD:
The ketone may for example, be present in the composition in a concentration in the range 0.01% to 2% by weight of the polymerisable material in the composition although concentrations outside this range may be used if desired. Suitably the ketone is present in a concentration of 0.1% to 1% and more preferably 0.5% to i% by weight of the ethylenlcally unsaturated material in composition. The ketone should be soluble in the polymerisable material and the above concentrations refer to solution concentration.
.DTD:
The organic peroxides suitable for use in the present composition include those having the formula R7 - 0 -- 0 -- R7 in which the groups R7 which may be the same or different, are hydrogen, alkyl, aryl, or acyl groups, no more than one of the groups R being hydrogen. The term acyl means having the formula R8 - CO - in which R8 is an alkyl, aryl, alkloxy or aryloxy group. The term alkyl and aryl have the definitions given hereinbefore for the groups A and include substituted alkyl and aryl.
.DTD:
Examples of organic peroxide suitable for use in the composition of the present invention include diacetyl peroxide, dlbenzoyl peroxide, ditertlary butyl peroxide, dilauroyl peroxide, tertiary butyl perbenzoate, ditertiary butyl cyclohexyl perdicarbonate.
.DTD:
- ii- The organic peroxide may be, for example, present in the composition in the range 0.1% to 10% by weight of the polymerlsable material in the composition although concentration outside this range may be used if desired.
.DTD:
The reactivity of a peroxide is often measured in terms of a ten hour half llfe temperature, i.e. within ten hours at that temperature half of the oxygen has been made available. The peroxides in the present compositions preferably have ten hour half life temperatures of less than 150 C, more preferably less than lOOOC.
.DTD:
The rate at which the composition of the invention cures under the influence of visible light can be increased by incorporation into the composition of reducing agent in concentration 0.1% to 10% by weight of the polymerlsable material, which is capable of reducing the ketone when the latter is in an excited state. Suitable reducing agents are described, for example, in German Offenlegungsschrlft 2251048 and include organic amines, phosphltes, sulphlnic acids.
.DTD:
In general non-baslc reducing agents are preferred because they are less likely to react with the phosphate ester.
.DTD:
Suitable non-baslc reducing agents include aldehydes and organotln compounds having the formula:- (R9)n Sn (oRIO)m in which n and m are integers having the value I, 2 or 3 and n+m=4, R9 is an alkyl or alkenyl group containing I to 18 carbon atoms and RIO is R9 or Rg.co- or having the formula ([R913Sn)20 The filler is present in amount I to 9% by weight of the composition preferably 4 to 6%. The filler in any form of silica including comminuted forms of crystalline silica including for example sand, but is preferably a colloidal form such as pyrogenic, formed or precipitate silica.
.DTD:
Mixing of the components may be effected by stirring together the polymerisable material and the filler. It may be useful to dissolve the catalyst components first in the polymerisable material| the polymerisable material may conveniently but less preferably be diluted with a suitable diluent so as to improve solution of the catalyst components. When mixing has been effected the diluent may be removed if desired, e.g. by evaporation. Desirably the present composition is substantially free of solvent because its presence may interfere with adhesion and may give rise to toxicity problems.
.DTD:
Because the photosensitive catalyst renders the polymerisable material and monomer sensitive to light in the 400m to 500m visible range, that part of the preparation of the present composition in which photosensitive catalyst is added and subsequent manipulation, e.g. filling of containers should be carried out in the substantial absence of light in that range. Most conveniently, the preparation can be carried out using light outside that range for example under that emitted by sodium vapour electric discharge lamps.
.DTD:
In accordance with a further embodiment of the present invention a curing process is provided which comprises irradiating the composition of the invention with visible radiation having wavelength between 400m. and 500m. The process may be carried out at any convenient temperature provided that the composition does not crystallize and fragment, the temperature thereby being too low, or unduly volatilic, the temperature thereby being too high. Preferably the process is carried out at ambient temperatures, i.e. between 15 C and 40 C.
.DTD:
It is envisaged that a tooth surface will be coated with the present composition and then cured under a visible light source conveniently the composition is cured from a portable light source. However it is preferred that the tooth surface is primed before being so coated a preferred primer is a bisbiguanide, polybiguanide or a long chain quaternary salt as described in British Application 8810412.
.DTD:
A dental composition according to the present invention is preferably packed in single small containers (e.g. lOg capacity) so as to facilitate handling in the surgery and reduce the risk of inadvertent curing by for example stray light.
.DTD:
For cosmetic purposes, such a dental composition may have a stained, coloured or natural tooth appearance and hece the present composition may include small quantities of pigments, opalescent agents and the like. The composition may also include small quantities of other materials such as anti- oxidants and stabilisers provided that they do not substantially affect cure.
.DTD:
The invention is illustrated with reference to the following Examples:Example I (a) Preparation of phosphate ester Phosphorus oxychloride (127.9g; 0.83 moles) was mixed with methylene chloride (600 cm3). The mixture was stirred and cooled to OOC. A mixture of hydroxypropyl methacrylate (120g 0.83 moles), pyridine (65.8g: 0.83 moles) and methylene chloride (4OOcm3) was added dropwise to the phosphorus oxychloride mixture over a period of 45 minutes whilst keeping the reaction temperature in the range O to 3 C. The mixture was stirred for a further 2 hours within that temperature range. The reaction mixture was then poured into i lltre cold water and the methylene chloride layer was separated, washed twice with water.
.DTD:
The methylene chloride solution was then mixed with water and the methylene chloride removed using a rotary evaporator to leave an aqueous phase and some water insoluble inorganic material. The aqueous layer was washed twice with methylene chloride, and then carefully acidified (hydrochloric acid 208cm3) with stirring, the aqueous phase was then extracted using ethyl acetate (i litre) and the aqueous phase was rejected. The concentration of phosphate ester was then estimated and analysed by acid base titration methods and found to contain ester impurity less than 2% by weight of 2methacryloyloxy-propyl dihydrogen phosphate. Triethylene glycol dimethacrylate (TEGDM) was then added to provide a 90:10 TEGDH:phosphate blend. Ethyl acetate was then removed using a rotary evaporator at 65 C and under a vacuum of 50mmHg.
.DTD:
(b) A number of formulations were prepared having filler concentration and composition as given in the Table i. To the monomer mixture were added the catalyst components as follows:- %w/w Camphorquinone Dibutyl tin dilaurate Topanol' 0 Aerosil' AI30 0.73 0.49 to 200 ppm on final composlt ion.
.DTD:
varying This addition and subsequent operations using the composition were carried out under sodium vapour discharge light.
.DTD:
Evaluation of adhesive strength on samples having the above formulations were carried out using the procedure described in British Dental Journal 1984, pages 93 to 95, except that the composite restorative material used in conjunction with the adhesive composition was 'Occlusin' (trade mark, Imperial Chemical Industries PLC). The surface of dentin was painted with a solution of 'Vantocil' (0.1% by weight in water), followed by drying with an air blast, before the adhesive formulation was applied. 'Vantocil' is a polybiguanide having the formula-(CH2)6--NH.C(:NH).NH.C(:NH)NH'n where n is 4 to 7. 'Vantocil' is a trade mark of Imperial Chemical Industries PLC. The samples were cured by radiation from a tungsten halogen lamp having a tuned reflector and a dichroic filter which eliminates ultra-violet radiation| the intensity was I000 Wm-2 and cure time was 30 seconds.
.DTD:
Topanol' is a trade mark of Imperial Chemical Industries PLC and 'Topanol' 0 is 2,6-ditertiarybutyl-4-methylphenol.
.DTD:
Aerosil' is a trade mark of Degussa AG; 'Aerosil' AI30 is a hydrophilic grade of fumed silica having mean particle size O.02m.
.DTD:
Table I % Bond Filler Strength (MPa) 0 7.0 13.0 7.5 Ii.0 I0 7.0 The above results are presented in the accompanying figure.
.DTD:
Example 2 .DTD:
Similar bond strength was obtained using an adhesive having the following composition:- A -- 16 - % by weight Phosphate ester (as described in Example i) 9.48 Vinyl urethane resin x 15.17 TEGDM 70.16 Camphorquinone 0.71 Dibutyl tin dilaurate 0.48 Aerosil' AI30 4.00 as described in Example i of European Patent Specification 59649.
.DTD:
The vinyl urethane resin and the phosphate ester are incorporated as solutions in TEGDM, the quantity of TEGDM so-added being included in the TEGDM total content.
.DTD:
.CLME:
Claims (1)
- CLAIMS .CLME:I. A single-component, visible light-curable liquid adhesive composition which comprises (a) 2 to 20 parts by weight of at least one substantially pure phosphate ester having the formula CH2=C(RI).c0.0.R2.0P(0)(0H)2 in which R1 is a hydrogen atom or a methyl group, and R2 is-CH2-CH2--, -CH2-CH(CH3)- or -- CH(CH3)--CH2- and (b) 98 to 80 parts by weight of at least one ethylenically unsaturated monomer copolymerisable with the phosphate ester (c) i to 9% by weight of fine inorganic filler and an effective amount of a visible light activated catalyst..CLME:2. A composition as claimed in claim I in which the phosphate ester has the formula CH2=C(CH2).CO.O.R2.0P(O)(OH)2 in which R2 is an isopropylene group..CLME:3. A composition as claimed in either claim I or claim 2 is which the concentration of the phosphate ester in 5 to 15 parts by weight..CLME:A composition as claimed in any one of claims i to 3 in which the ethylenically unsaturated monomer comprises a glycol dimethacrylate..CLME:5. A composition as claimed in claim 4 in which the monomer also includes a vinyl urethane..CLME:6. A composition as claimed in any one of claims I to 5 in which the weight of filler present is in the range 4% to 6%..CLME:7. A composition as claimed in any one of claims I to 6 in which the filler is colloidal silica..CLME:8. A composition as claimed in any one of claims I to 7 in which the visible light activated catalyst comprises camphorquiname and a reducing agent..CLME:9. A composition as claimed in claim 8 in which the reducing agent is an organotin compound having the formula (R9) ns n(0R I0) m in which n and m are integers having the value 1,2 or 3 and n+m=4, R9 is an alkyl or alkenyl group containing 1 to 18 carbon atoms and RI0 is R9 or R9C0-..CLME:i0. A composition as claimed in claim 8 in which the reducing agent is an organotin compound having the formula ([Rg]3sn)20 in which R9 is an alkyl or alkenyl group containing I to 18 carbon atoms..CLME:Published 1989 at The Patent Ofce, Stae House, 66 71 High Hcbcrn, LondonC11% 4TP.Further copies may M obtazned from The Patent Ofnce. Sales Branch. St Mary Oray, 0rplugton, rent BR5 5qD. Printed by M,altiplex techniques ltd, St Mary Cay, Kent, Con. 1/87
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB888810411A GB8810411D0 (en) | 1988-05-03 | 1988-05-03 | Adhesive compositions |
Publications (3)
Publication Number | Publication Date |
---|---|
GB8910125D0 GB8910125D0 (en) | 1989-06-21 |
GB2218104A true GB2218104A (en) | 1989-11-08 |
GB2218104B GB2218104B (en) | 1992-09-23 |
Family
ID=10636262
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB888810411A Pending GB8810411D0 (en) | 1988-05-03 | 1988-05-03 | Adhesive compositions |
GB8910125A Expired - Fee Related GB2218104B (en) | 1988-05-03 | 1989-05-03 | Adhesive compositions |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB888810411A Pending GB8810411D0 (en) | 1988-05-03 | 1988-05-03 | Adhesive compositions |
Country Status (22)
Country | Link |
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JP (1) | JPH02110178A (en) |
AT (1) | AT393355B (en) |
AU (1) | AU618805B2 (en) |
BE (1) | BE1001707A3 (en) |
CH (1) | CH678061A5 (en) |
DE (1) | DE3914687A1 (en) |
DK (1) | DK219589A (en) |
ES (1) | ES2010639A6 (en) |
FI (1) | FI892133A (en) |
FR (1) | FR2631037A1 (en) |
GB (2) | GB8810411D0 (en) |
GR (1) | GR1000398B (en) |
IE (1) | IE891446L (en) |
IL (1) | IL90147A (en) |
IT (1) | IT1230144B (en) |
LU (1) | LU87512A1 (en) |
NL (1) | NL8901112A (en) |
NO (1) | NO891824L (en) |
NZ (1) | NZ228971A (en) |
PT (1) | PT90453A (en) |
SE (1) | SE470063B (en) |
ZA (1) | ZA893292B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0449456A1 (en) * | 1990-03-16 | 1991-10-02 | Three Bond Co., Ltd. | Adhesive composition |
FR2698636A1 (en) * | 1992-11-27 | 1994-06-03 | Aerospatiale | Structural adhesive - comprises resin having functional gp(s) reactive under ionising radiation, powdered filler, elastomeric reinforcing agent, adhesion promoter and reactive diluent comprising at least one ethylenically functional monomer |
GB2299094A (en) * | 1995-03-10 | 1996-09-25 | Basf Ag | Flame-resistant aqueous polymer formulations |
WO1996031572A1 (en) * | 1995-04-03 | 1996-10-10 | Institut für Neue Materialien Gemeinnützige GmbH | Composite adhesive for optical and opto-electronic applications |
US5607985A (en) * | 1992-12-21 | 1997-03-04 | Adell Co., Ltd. | Photopolymerization initiator for visible light-polymerizing adhesive |
GB2305668A (en) * | 1995-09-30 | 1997-04-16 | Albright & Wilson | Adhesive and flame-retardant polymers |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4024192A1 (en) * | 1990-07-30 | 1992-02-06 | Uhu Gmbh | Solvent-free adhesive |
DE69222302T2 (en) * | 1992-03-05 | 1998-04-09 | Japan Inst Advanced Dentistry | PHOTOPOLYMERIZABLE ADHESIVE |
JP2021088512A (en) * | 2019-12-02 | 2021-06-10 | 株式会社トクヤマデンタル | Production method of phosphoric acid ester-based methacryl monomer for dentistry |
Citations (9)
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GB1377978A (en) * | 1970-11-25 | 1974-12-18 | Kansai Paint Co Ltd | Composition for preparing electroconductive resin |
US4044044A (en) * | 1975-04-21 | 1977-08-23 | Tsutomu Saito | Anaerobic adhesive composition containing 0.05 to 20 parts per weight of phosphate esters of hydroxyacrylates per 100 parts per weight of polymerizable acrylic ester monomer |
GB1569021A (en) * | 1976-03-17 | 1980-06-11 | Kuraray Co | Adhesive cementing agents containing partial phosphonic orphosphonic acid esters |
GB1578500A (en) * | 1977-04-27 | 1980-11-05 | Kuraray Co | Adhesive compositions comprising a phosphinic acid compound |
EP0058483A2 (en) * | 1981-02-13 | 1982-08-25 | Minnesota Mining And Manufacturing Company | Dentin and enamel adhesives |
JPS59120666A (en) * | 1982-12-27 | 1984-07-12 | Dainippon Ink & Chem Inc | Resin composition for powdered paint |
EP0115948A1 (en) * | 1983-01-31 | 1984-08-15 | Kuraray Co., Ltd. | Adhesive composition |
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GB2199330A (en) * | 1986-11-03 | 1988-07-06 | Ici Plc | Adhesive compositions |
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- 1988-05-03 GB GB888810411A patent/GB8810411D0/en active Pending
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- 1989-05-01 IL IL90147A patent/IL90147A/en unknown
- 1989-05-02 NL NL8901112A patent/NL8901112A/en not_active Application Discontinuation
- 1989-05-02 JP JP1112340A patent/JPH02110178A/en active Pending
- 1989-05-03 PT PT90453A patent/PT90453A/en not_active Application Discontinuation
- 1989-05-03 FI FI892133A patent/FI892133A/en not_active Application Discontinuation
- 1989-05-03 AU AU33969/89A patent/AU618805B2/en not_active Ceased
- 1989-05-03 DK DK219589A patent/DK219589A/en not_active Application Discontinuation
- 1989-05-03 BE BE8900483A patent/BE1001707A3/en not_active IP Right Cessation
- 1989-05-03 NO NO89891824A patent/NO891824L/en unknown
- 1989-05-03 GB GB8910125A patent/GB2218104B/en not_active Expired - Fee Related
- 1989-05-03 IT IT8920365A patent/IT1230144B/en active
- 1989-05-03 NZ NZ228971A patent/NZ228971A/en unknown
- 1989-05-03 SE SE8901595A patent/SE470063B/en not_active IP Right Cessation
- 1989-05-03 CH CH1689/89A patent/CH678061A5/de not_active IP Right Cessation
- 1989-05-03 GR GR890100293A patent/GR1000398B/en unknown
- 1989-05-03 LU LU87512A patent/LU87512A1/en unknown
- 1989-05-03 IE IE891446A patent/IE891446L/en unknown
- 1989-05-03 ES ES8901522A patent/ES2010639A6/en not_active Expired
- 1989-05-03 FR FR8905917A patent/FR2631037A1/en active Granted
- 1989-05-03 AT AT1063/89A patent/AT393355B/en not_active IP Right Cessation
- 1989-05-03 DE DE3914687A patent/DE3914687A1/en not_active Withdrawn
- 1989-05-03 ZA ZA893292A patent/ZA893292B/en unknown
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GB1377978A (en) * | 1970-11-25 | 1974-12-18 | Kansai Paint Co Ltd | Composition for preparing electroconductive resin |
US4044044A (en) * | 1975-04-21 | 1977-08-23 | Tsutomu Saito | Anaerobic adhesive composition containing 0.05 to 20 parts per weight of phosphate esters of hydroxyacrylates per 100 parts per weight of polymerizable acrylic ester monomer |
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GB1569021A (en) * | 1976-03-17 | 1980-06-11 | Kuraray Co | Adhesive cementing agents containing partial phosphonic orphosphonic acid esters |
GB1578500A (en) * | 1977-04-27 | 1980-11-05 | Kuraray Co | Adhesive compositions comprising a phosphinic acid compound |
EP0058483A2 (en) * | 1981-02-13 | 1982-08-25 | Minnesota Mining And Manufacturing Company | Dentin and enamel adhesives |
JPS59120666A (en) * | 1982-12-27 | 1984-07-12 | Dainippon Ink & Chem Inc | Resin composition for powdered paint |
EP0115948A1 (en) * | 1983-01-31 | 1984-08-15 | Kuraray Co., Ltd. | Adhesive composition |
EP0132318A1 (en) * | 1983-06-28 | 1985-01-30 | Minnesota Mining And Manufacturing Company | Light-curable dentin and enamel adhesive |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0449456A1 (en) * | 1990-03-16 | 1991-10-02 | Three Bond Co., Ltd. | Adhesive composition |
FR2698636A1 (en) * | 1992-11-27 | 1994-06-03 | Aerospatiale | Structural adhesive - comprises resin having functional gp(s) reactive under ionising radiation, powdered filler, elastomeric reinforcing agent, adhesion promoter and reactive diluent comprising at least one ethylenically functional monomer |
US5607985A (en) * | 1992-12-21 | 1997-03-04 | Adell Co., Ltd. | Photopolymerization initiator for visible light-polymerizing adhesive |
GB2299094A (en) * | 1995-03-10 | 1996-09-25 | Basf Ag | Flame-resistant aqueous polymer formulations |
WO1996031572A1 (en) * | 1995-04-03 | 1996-10-10 | Institut für Neue Materialien Gemeinnützige GmbH | Composite adhesive for optical and opto-electronic applications |
GB2305668A (en) * | 1995-09-30 | 1997-04-16 | Albright & Wilson | Adhesive and flame-retardant polymers |
Also Published As
Publication number | Publication date |
---|---|
ES2010639A6 (en) | 1989-11-16 |
CH678061A5 (en) | 1991-07-31 |
AT393355B (en) | 1991-10-10 |
FR2631037A1 (en) | 1989-11-10 |
GR1000398B (en) | 1992-06-30 |
FI892133A0 (en) | 1989-05-03 |
AU3396989A (en) | 1989-11-09 |
IL90147A (en) | 1993-02-21 |
PT90453A (en) | 1989-11-30 |
JPH02110178A (en) | 1990-04-23 |
LU87512A1 (en) | 1990-06-12 |
NL8901112A (en) | 1989-12-01 |
DE3914687A1 (en) | 1989-11-16 |
IE891446L (en) | 1989-11-03 |
ZA893292B (en) | 1990-01-31 |
IT8920365A0 (en) | 1989-05-03 |
NO891824L (en) | 1989-11-06 |
SE470063B (en) | 1993-11-01 |
BE1001707A3 (en) | 1990-02-13 |
NO891824D0 (en) | 1989-05-03 |
DK219589D0 (en) | 1989-05-03 |
GB8810411D0 (en) | 1988-06-08 |
IT1230144B (en) | 1991-10-14 |
GB8910125D0 (en) | 1989-06-21 |
FR2631037B1 (en) | 1994-08-19 |
GR890100293A (en) | 1990-03-12 |
SE8901595L (en) | 1989-11-04 |
IL90147A0 (en) | 1989-12-15 |
ATA106389A (en) | 1991-03-15 |
SE8901595D0 (en) | 1989-05-03 |
FI892133A (en) | 1989-11-04 |
AU618805B2 (en) | 1992-01-09 |
GB2218104B (en) | 1992-09-23 |
NZ228971A (en) | 1991-09-25 |
DK219589A (en) | 1989-11-04 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19960503 |