ADHESIVE COMPOSITION

Abstract: An adhesive composition comprises 100 parts by weight of a polymerizable monomer comprising (a) 1.5 to 50 parts by weight of a compound represented by one of Formulae I and II: where each of R₁ and R₁′ is hydrogen or methyl, R₂ is a bivalent organic residue having from 4 to 40 carbon atoms, each of X₁ and X₂ is -O-, -S- or -NH-, a is 0 or 1, and R₃ is a group of the formula having 6 to 40 carbon atoms, where each of R₄ and R₄′ is a hydrocarbon group having 1 to 29 carbon atoms optionally having as substituent(s) halogen, hydroxy, amino or car­ boxy, b is 0, 1, 2 or 3, the R₄'s, if more than one are present, being the same or different, and at least one of R₄ and R₄′ having at least three carbon atoms, and Z is - O , -COO- or - NH, and (b) 50 to 98.5 parts by weight of a vinyl monomer copolymerizable with the said compound; and 0.01 to 20 parts by weight of a curing agent. It shows a superior adhesive strength on any of the hard tissues in a living body, such as teeth and bones, as well as on metals, organic polymers and ceramics. It maintains a high adhesive strength for a long time even if it is exposed to moisture, or immersed in water. It is particularly effective for use in dentistry, though it is useful for a variety of other purposes, too.

Description: ADHESIVE COMPOSITION This invention relates to adhesive compositions for adhering strongly to hard tissues in a living body, such as teeth and bones, as well as metals, organic polymers and ceramics. The term "adhesive composition" as herein used means not only a composition used for bonding two or more adherends to one another, but also means a composition used for forming a highly adhesive coating on the surface of an adlserend such as a mctal or organic polymer, and a composition used for forming a highly adhesive filling material for repairing hard tissues in a living body. In other words, this invention covers any and all compositions that are adhesively applicable to various kinds of substances, including hard tissues in a living body, metals, organic polymers and ceramiCs. Various kinds of metals, organic polymers and ceramics are used for the restoration of teeth. When these restorative materials are moulted in the mouth, it is necessary to ensure that they are securely bonded to teeth, or to each other. Since tfiey are placed in the mouth, it is particularly necessary that satisfactor adhesion be obtained in a wet condition. A variety of attempts have hiilerto been made to explore a practically useful adhesive for dentistry as will hereinafter be set forth. Although some adhesives have been put to practical use, they are used only for a limited scope of application, since they do not work satis factorily. An adhesive that can strongly bond a metal or organic polymer, in a wet condition, exhibiting an adliesive strength not easily affected by water, would contribute greatly to improving the art of dental restoration. An adhesive tliat provides a high adhesive strength in a wet condition will also be useful for manv other applications. C.S. Patents Nos. US-A-4,259,075 and US-A-4,259,117 show that a polymerizable composition a vinyl compound having a group of the formula EMI2.1 is effective as a dental adhesive. U.S. Patent No. US-A-4,222,780 shows that a polymerizable composition containing a vinyl compound having- a group of the formula EMI2.2 is also an effective dental adhesive. In fact, some of the compositions defined by these patents are widely used as primers for application to the wall of a tooth cavity before the cavity is filled. They, however, require acid etching of the cavity wall in order to provide a satisfactory adhesive strength for the tooth. Moreover, they do not provide any satisfactory adhesive strength for a Ni-Cr alloy comprising 93% Ni and 6r Cr, which is used commonly in dentistry. There have also been proposed dental adhesives prepared from polymerizable phosphate compounds as will hereinafter be described. None of them has, however, been put to practical use because of their unsatisfactory adhesive strength. (i) U. S. Patent No. 3,882,600 describes phosphoric monofluoride. (ii) Journal of Dental Research, vol. 53, pages 878 to 888 and vol. 56, pages 943 to 952, Chemical Abstract, vol. 77, page 290 (66175 g) and Japanese Laid-Open Patent Specification No. 44152/1976 describe CH2=CH-PO(OH)2 and CH2=CHC6H4CH2PO(OH)2. (iii) Japanese Laid-Open Patent Specification No. 1138A3/ 1978 shows by a general formula the confounds obtained by neutralizing one of the two hydroxy groups in the cor-pounds of the formula EMI3.1 in which R stands for an organic residue having at least one vinyl group. 'icre specifically, it shows the following compounds. In the following formulas, X stands for an alkali metal: CH3 CH2=CHC6H4OPO(OH)(OMO), CH2=C-COOCH2CH2OPO(OH)(OM) CH2=CHCH2OPO(OH)(OM), EMI3.2 EMI3.3 EMI4.1 None of the compounds set forth at (i) to (iii) above provides a satisfactorily high adhesive strength in a wet condition. There have also been made a number of other proposals to provide adhesives which are useful for both teeth and metals, as will hereinafter be summarized. (i) U. S. Latent No. 4,148,988 shows 4-methacryloxy ethyl trimellitate as an adhesive monomer. This monomer, however, cannot maintain a strong bond between a tooth and a metal or organic polymer for a long time in the mouth in which a wet condition and repeated occlusal pressure prevail. U. S. Patent No. 3,872,047 and Japanese Laid-Open Patent Specification No. 98878/1974 disclose a polymer having both a hydrophilic group and a hydrophobic group as an adhesive constituent. They show methacryloxyethyl phosphate as a moncmer constituting the polymer. This polymer does, however, not appear to provide any satisfactory adhesive strength. (iii) It is kncwn that a polymer obtained by polymeriz- ing a vinyl monomer on the tooth surface employing a ternary curing agent composed of a peroxide, an amine and a sulfinate has an improved adhesive strength on the tooth (U. S. Patent No. 4,182,035). No satis;actory adhesive strength can, however, be obtained from any combination employing a known vinyl monomer, but it is believed necessary to explore a new adhesive vinyl monomer. It is known that if a polymerizable composition containing 2-(meth)acryloxyethyl dihyroen phosphate is cured on an iron or stainless steel surface, the cured product adheres to the metal surface, as described in the various references which will hereinafter be cited No attempt has, however, been hitherto made to obtain phosphate esters having a higher adhesive strength than 2-(meth)acryloyl- oxyethyl dihydrogen phosphate, particularly in a wet con tion. A. U. S. Patent No. 3,754,972 discloses the formation of an adhesive coating on a metal surface by applying a polymerizable composition containing a phosphate ester thereto. While it shows the applicable phosphate esters by way of a general formula, the examples set forth therein provide a specific support for the adhesive property of only the compounds of the following formula obtained by reacting hydroxy- ethyl acrylate with EMI5.1 in which m is 1 or 2, n is 1 or 2, and m + n = 3. B. U. S. Patent No. 3,884,864 discloses the manufacture of a phosphorus cured material which is useful as a fire retardant material, and save that it shows a high adhesive strength on a metal. It is, however, manufactured from phosphate esters obtained by reacting hydroxyethyl methacrylate or ss-hydroxychloropropyl methacrylate with P2O5. They are the phosphate esters represented by the general formula I which will hereinafter appear, and in which R2 has a maximum of three carbon atoms. C. U. S. Patent No. 3,987,127 discloses a radiation polymerizable coating composition containing a polymerizable phosphate ester. It shows a general formula for the applicable phosphate esters which includes those represented by the formula I when R2 stands for an alkylene group having a maximum of six carbon atoms. The compounds listed specifically therein, and employed in the examples are, however, only those obtained when R2 is a group of the formula -CH2CH2 - It does not aive any example of the compounds containing an alkylene group having three or more carbon atoms, D. U S. Patent No. 4,001,150 discloses a composition containing G polymerizable phosphate ester, and used for preparing an electroconductive resin. The applicable phosphate esters shown by way of example therein are those repre- sented by the formula I when R2 is an alkylene group having a maximum of four carbon atoms. The patent says that it is not advisable to use any compound containing an alkylene group having more than four carbon atoms. E. U. S. patent No. 4,044,044 discloses an anaerorc adhesive composition containing a polymerizable phosphate ester of the general formula: EMI6.1 in which Ra stands for H, CH3 or C2H5, Rb stands for EMI7.1 or EMI7.2 ano n is an integer of 1 to 10. It bones, however, not show any phosphate ester specifi cal ly except 2-methacryloyloxyethyl dihydrogen phosphate. F. Japanese Laid-Open Patent Specification No. 2-0238/ 1974 discloses an anaerobic adhesive containing 2 compound of the general formula EMI7.3 in which R stands for H or CH3, and Z stands for a halogen It does not show any attempt to use a phosphate ester -hav- ing 2 larger number of carbon atoms. Japanese Laid-Open Patent Specification No. 100596/ 1975 describes the usefulness of an organic compound having a P-OH group as one of the constituents of an electroconcuc- tive composition, and spe"ifically shows by way of example a compound which corresponds to that of the formula I when R2 stands for -CH2CH2- or -CH2CH2-OCH2CH2-. iT; HOWEVER; fails to show any other compound having a larger number of carbon atoms. Japanese Laid-Open Patent Specification No. 125182/ 1976 discloses a curable resin composition suitable for use in coating a metal surface, but which contains only a compound corresponding to that represented bv the formula 5 when R2 stands for -CH2CH2- or EMI7.4 Japanese Laid-Open Patent Specification No. 12995/ 1978 discloses a low temperature curable resin compo tion containing a phosphate ester which corresponds to that represented by the formula I when R2 stands for EMI8.1 Japanese Laid-Open Patent Specification No. 11920/ 1981 discloses a polymerizable composition containing an epoxy diacrylate and a phosphate ester as a diluent therefor, and having a high adhesive strength on a meal. Al- though it shows a general formula for the compounds corresponding to those represented by the formula I when R2 stands or -[CH2CH2]2-, in whicn i is from 1 to 10, it specifically snows only a compound obtained when A is 1, and 2-methacryloyloxyethyl dihydrogen phosphate is the only phosphate ester employed in the Examples set forth in the specification. It will be noted from the foregoing that, though there are a lot of prior patents and patent applications disclosing compositions containing polymerizable phosphate esters as hereinabove mentioned at A to F, it is only the compositions containing 2- (meth) acryloyloxyethyl dihydrogen phosphate corresponding to the compounds represented 5 the formula I when R2 stands or a group having two carbon atoms that have specifically been found effective as an adhesive, and that all the other similar compounds shown by ay of example therein correspond merely to those represented by the formula I when R2 stands for a group having two to four carbon atoms. Although these patents and patent applications state that the compositions containing those cor:tounos exhibit a high adhesive strength on metals, none of them speaks of the adhesiveness of the compositions in a wet condition, nor do they contemplate in the use of these compositions for dental applications. The present invention provides an adhesive composition comprising 100 parts by weight of a polymerizable monomer comprising (a) 1.5 to 50 parts by weight of a compound represented by one of formulae I and II: EMI9.1 where each of R1 and R1' is hydrogen or methyl, R2 is a bivalent organic residue having from 5 to 40 carbon atoms, each of X1 and X2 is -O-, -S- or -NH-, a is 0 or 1, and R3 is a group of the formula EMI9.2 having 6 to 40 carbon atoms, where each of and R4' is a hydrocarbon group having 1 to 29 carbon atoms optionally having as substituent(s) halogen, hydroxy, amino or carboxy, b is 0, 1, 2 or 3, the R,'s, if more than one are present, being the same or different,- and at least one or R4 and R42 having at least three carbon atoms, and Z is -o-, -COO- or -XE-, and (b) 50 - 98.5 parts by weight of a vinyl monomer copolymerizable with the said compound; and 0.01 to 20 parts by weight of a curing agent. As will appear from the experimental data below, compositions can be made in accordance with the present invention that adhere strongly to any of the hard tissues in a living body, such as teeth and bones, and to metals, organic polymers and ceramics, and that exhibits an excellent adhesive strength even in the presence of water. Such adhesive compositions can be used for bonding, witfi a high adhesive strength, a hard tissue in a living body to another tissue or to a material for tlie restoration of the tissue, such as a metal, organic polymer or ceramics, or for filling a hard tissue in a living body to restore it. In dentistry, they can be applied to the surface of a cavity in a tooth to form a strong bond between the tooth and the material with which the cavity is filled, as dental filling composition, for securing a restorative material, such as an inlay, onlay, crown, bridgework or orthodontic appliance, to a tooth tissue or abutment tooth, in every case having a high adhesion to the tooth They can also be used industrially or in the home to bond one metal to another, a metal to an organic polymer or ceramics, one ceramic to another, or ceramics to an organic polymer, or as a coating agent or paint to form a highly adhesive film on a metal or ceramic surface. Although the compositions of this invention contain a compound of the formula I or II as an adhesive monomer, a compound of formula I containing an organic residue R2 having only four carbon atoms may also be used when the compositions are for dental use. The term "organic residue" as herein used means: (i) a hydrocarbon group optionally having an OH, COOR or NE2 group or a halogen atom (C1, Br, F or I) as a substituent; or (ii) a residue consisting of 2 to 20 hydrocarbon groups of the ty-pe defined above at (i) bonded to one another by ether, thioether, ester, thioester, thiocarbonyl, amide, carbonyl, sulfonyl or urethane linkages. Furthermore, the residue may have a principal chain composed of two or more hydrocarbon groups, possibly with at least one side chain formed at least in part by hydrocarbon groups. The following formulae exemplify the applicable organic residues. In the formulae, A strands for a hydrocarbon group, B stands for a linkage EMI11.1 EMI11.2 C0NH or OCONH), [C=C] stands for a double bond, and [PO(OH)2] stands for phospliorac or phosphoric acid. [C=C] - A - [PO(OH)2] [C=C] - ABA'-[PO(OH)2] [C=C] - ABA'B'A" - [PO(OH)2] [C=C] - (AB)&alpha; - A' - [B"A")ss[PO(OH)2] (&alpha; and ss : recurring) EMI11.3 The term "hydrocarbon group" as herein used covers halogenated hydrocarbons even if not specifically mentioned. In the formula 1, R2 preferably stands for (a) a hydrocarbon group having 5 to 30 carbon atoms (or 4 to 30 carbon atoms for a composition for dental application), and optionally haing as substituent(s) halogen, hydroxy, amino or carboxy or (b) a group having 5 to 30 carbon atoms (or 4 to 30 carbon atoms for a composition for dental application), and composed of two to seven hydrocarbon groups bonded to each other by ether, thioether, ester, thioester, thiocarbonyl, amide,- urethane, carbonyl and/or sulfonyl linkage(s), each of the hydrocarbon groups having 1 to 29 carbon atoms, at least one hydrocarbon group having at least four carbon atoms (or at least three- carbon atoms for a composition for dental application), each hydrocarbon group optionally having as substituent(s) halogen7hydros-, amino or carboxy The organic residue R2 defined above at (b) is more particularly of the following formulae: (a) -R5(Y-R5')c, in which each of R5 and R5' satnds for a hydrocarbon group having 1 to 29 carbon atoms, and optionally having as substituent(s) halogenXhydroxy, amino or carboxy; Y stands for -0-, -S--, -COO-, -CO, EMI12.1 -CONE-, -OCONE-, EMI12.2 or EMI12.3 and c is an integer of from 1 to 6, and if there are two or more R 's, they are the same or different, at least one hydro 5 carbon group having at least four carbon atoms (or at least three carbon atoms for a composition for dental application); or EMI12.4 in which Y is as defined above, Y' is the same as Y, d is 0, 1, 2 or 3, and if d is 0, R6' stands for a hydrocarbon group having 4 to 27 carbon atoms (or I to 27 carbon atoms, for a composition for dental application), and optionaly having as substituent(s) halogen,hydroxy, amino or carboxy, while if d is 1, 2 or 3, each of R6 and R6' stands for a hydrocarbon group having 4 to 27 carbon atoms (or I to 27 carbon atoms for dental application and optionally having as substituent (s) halogen, hydroxy, amino or carboxy, at least one of hydrocarbon groups R4 and R61 having at least four carbon atoms (or at least one carbon atom for a composition for dental application). The compounds of the formula I in which h and X2 both stand for -O- and a is 1 are preferable for dental application from the standpoints of biological safety, storage stability and adhesive strength. In these compounds, R1 is usually a methyl group and R2 preferably stands for any of the following: EMI13.1 in which each of R7 and R7' stands for a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, optionally having halogen substituent(s); EMI13.2 in which R8 stands for hydrogen or methyl and N stands for a hydrocarbon group having 3 to 28 carbon atoms, optionally having halogen substituent(s), particularly EMI13.3 in which g is an integer of 2 to 20, or 1 to 20 for a composition for dental application, or EMI13.4 EMI13.5 in which R10 stands for a hydrocarbon group having 1 to 12 carbon atoms, optionally halogen-substituted, and e is O or 1; ; EMI13.6 in which f is an integer of from 5 to 20, preferably 5 to 12, particularly 8 to 12, and may also be 4 for a composition for dental application; EMI13.7 in which h is an integer of from 1 to 5, i is 0, 1, 2 or 3, and h + i is at least 2, or at least 1 for a composition for dental application; EMI14.1 or EMI14.2 (preferably EMI14.3 EMI14.4 in which R11 stands for a hydrocarbon group having 2 to 6 carbon atoms, and optionally halogen-substituted; EMI14.5 EMI14.6 in which- R12 stands for a hydrocarbon group having 1 to 12 carbon atoms, optionally halogen-substituted, and Y preferably stands for -0- or -COO-; ; EMI14.7 in which each of R13 and R1 1 stands for a hydrocarbon group having 1 to 6 carbon atoms1 optionally halogen-substituted; preferably, EMI14.8 EMI14.9 or EMI14.10 in which q is 3 or 4; EMI14.11 in which each of R14 and stands for hydrogen or methyl, and each of k and k' is 2 or 3; (1) -CH2CH2OCH2C#CCH2OCH2CH2-; EMI15.1 in which each of r and r' is an integer from 2 to 6 (only for a composition for dental app3ication); r EMI15.2 in which R6 and R6' are as defined above, m is O or 1, and n is O, 1, 2 or 3. At least one of R6 and R6' preferably stands for an aromatic hydrocarbon. R6 may have one or two branches of the formula -(Y-R6")s in which I is as defined above, R6t is equal to R6, and s is 1 or 2. R6 and R61 may be bonded to each other by two Ys in the form of is 1. EMI15.3 when n The phosphate ester of the formula II preferably contains a group in which R4 stands for -CB2CBCH2-. The adhesive monomers suitable for use in the preparation of the adhesive composition of this invention will hereunder be shown by way of example: : EMI16.1 EMI17.1 EMI18.1 EMI19.1 EMI20.1 EMI21.1 EMI22.1 EMI23.1 EMI24.1 EMI25.1 EMI26.1 EMI27.1 EMI28.1 EMI29.1 EMI30.1 EMI31.1 EMI32.1 It is preferable to use a p)iosphatc nono- ester of the general formula: EMI33.1 in which R1 stands for hydrogen or a methyl group, and A stands for any of the following formulas 3 to 6: -(CH2)-p in which p is an integer of 5 to 12 (3) EMI33.2 EMI33.3 in which g is an integer of 2 to 4 (5) EMI33.4 in which o is an integer of 2 to 4 (6) The formulas 3 to 6 specifically represent the following compounds: Formula 3: : 5-(Meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth) acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acr,loyl- oxyoctyl dihydrogen phosphate, 9- (meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, and 12-(meth)acryloyloxydodecyl dihydrogen phosphate; Formula 4: 4-(Methacryloyloxymethyl)cyclohexylmethyl dihydrogen phosphate, and 4-(acryloyloxymethyl)cyclohexylmethyl dihydro- gen phosphate; Formula 5: : 2-[P-{2-(methacryloyloxy)ethoxy}phenoxy]ethyl dihydro gen phosphate, 3-[P-{3-(methacryloyloxy)propoxy}phenoxy]propyl dihydrogen phosphate, 4-EP- [4-(methacryloyloxy)- butoxyjphenoxy)butyl dihydrogen phosphate, 2-[P-{2- acryloyloxy) ethoxy) phenoxy) ethyl dihydrogen phosphate, 3-[P-{3-(acryloyloxy)ethoxy)ethoxy}phenoxy]ethyl phosphate, and 4-[P-{acryloyloxy)butoxy}phenoxy]butyl dihydrogen phosphate; Formula 6: : 2-[m-{2-(methacryloyloxy)propoxy)phenoxy]- $2-[m-{2-(acryloyl- $3-[m-{3dihydrogen phosphate, 3- [m- [3-(methacryloyloxy)propoxy)phenoxy]- propyl dihydrogen phosphate, 4-[m- ±4-(methacryloyloxy) - butoxy phenoxy]butyl dihydrogen phosphate, 2-[m-(2-(acryloyl- oxy) ethoxy phenoxyi ethyl dihydrogen phosphate, 3-[m-{3- (acryloxy)propoxy)phenoxy]propoxy]propyl dihydrogen phosphate, and 4-[m-(4-(acryloyloxy)butoxy}phenoxy]butyl dihydrogen phosphate The compounds of the formula I in which R2 stands for a group haviny not more than three carbon atoms are extremely inferior to the compounds employed in accordance with this invention in the adhesive strength on a tooth, metal or the like, and the water resistance of the adhesive bond. These compounds generally show an increased adhesive strength with an increase in the number of the carbon atoms which .R2 has-, and provide the highest adhesive strength when R2 has 6 to 20 carbon atoms. Their adhesive strength begins to drop if the number of the carbon atoms in R2 exceeds 30 In order to attain the objective of this invention, therefore, it is necessary to ensure that R2 have not more than 40 carbon atoms. The compounds of the formulas I and II can Ten erally be synthesized in accordance with the processes for the synthesis of phosphorus compounds as described in Organophosphorus Compounds (G.M. Kosolapoff, Wiley, 1950), Organophosphorus Monomers and Polymers (Ye. L. Gefter, Rregamon Press, 1962), Modern Organic Synthesis Series 5, Organophosphorus Compounds (The Society of Synthetic Organic Chemistry, Japan Gihodo, 1971) and Beilstein (Springer-Verlag). For example, the compounds of the for EMI35.1 form EMI35.2 reacting it with at least an eauimolar amount of phosphorus oxychloride in the presence of a tertiary amine to form a compound-of the formula EMI35.3 and hydrolyzing the P-C1 bonds therein. The compounds of the formula EMI35.4 can be obtained by synthesizing H-Xl-R2-PO3 2Na or H-X1-R2-PO (OR)2, in which R stands for a hydrocarbon group having 1 to 10 carbon atoms, and reacting it with EMI35.5 under the Shotten Baumanns reaction conditions. If R2 stands for EMI35.6 the phosphate ester for use in the preparation of the adhesive composition according to this invention may be obtained as will hereunder be described. Equimolar amounts of EMI36.1 and EMI36.2 in which R6 stands for (R6-Y')dR6', are reacted with each other in the presence of triethylbenzylammonium- chloride to form EMI36.3 Similarly, EMI36.4 and HOOC-R6" are reacted with each other to form EMI36.5 These hydroxy compounds are reacted with at least an equimolar remount of phosphorus oxychloride in the presence of a ter EMI36.6 P-C1 bonds therein. The adhesive- composition of this invention also contains a vinyl monomer which is copolymerizable with the compound of the formula I or II. The viscosity, wettability, curability and mechanical properties of the adhesive depend on the copolymerizable vinyl monomer to be employed. While various types of vinyl monomers can be used in accordance with the requirements for the adhesive to be prepared, it is usually advisable to employ a (meth)acrylate type monomer, a styrene type monomer or vinyl acetate. It is, however, possible to employ other compounds, for example, acrylamides such as (meth)acrylamide, N-n-butoxymethyl(meth)acrylamide and N-(hydroxymethyl)acrylamide, (meth)acrylic acid, isobutylvinyl ether, diethyl fumarate, methyl maleate, methyl vinyl ketone, allyl chloride, vinylnaphthalene and vinylpyridine. Suitable examples of the styrene type monomers include compounds of the formula EMI37.1 in which Q stands for a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, or more specifically, divinylbenzene and p-chlorostyrene. The (meth)acryiate type monomers often employed in the preparation of conventional anaerobic or dental adhesives can advantageously be used for preparing the adhesive composition of this invention. These monomers are repre- sented bv the formula EMI37.2 in which R1 stands for H or CH3, U stands for an organic residue (as hereinabove defined) having 1 to 50 carbon atoms, and t is an integer of 1 to 4. Specific examples of these monomers are as follows: (1) Monofunctional (meth) acrylates: Methyl (meth)acrylate, ehtyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)- acrylate, 2-hydroxyethyl (meth)acrylate (HEMA), 2-hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethyl aminoethyl (meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate, and 2,3-dibromopropyl (meth) acrylate; (2) Bifunctional (meth)acrylates: : (a) Compounds of the above formula in which Q stands for EMI38.1 in which s is an integer of 0 to 15: Ethylene glycol di(meth)acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and tripropylene glycol di(meth)- acrylate; (b) Compounds of the above formula in which Q stands for an alkylene normally having 3 to 12 carbon atoms: : Propanediol di(meth)acrylate, glycerol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1, 10-decanediol di(meth)acrylte, and 2, 3-dibromoneopene glycol dimethacrylate; (c) Compounds of the above formula in which Q contains a bisphenol A derivative residue: : Bisphenol A di (meth) acrylate, 2,2-bis[(meth)acryloyl- oxypolyethoxyphenyl]propane EMI38.2 in which t is an integer of 1 to 9 3, 2,2'-bis(4-cryloyloxypropoxy- phenyl)propane and 2,2'-bis[4-(3-methacryloyloxy-2-hydroxy propoxy)phenyl]propane (Bis-GMA), among which the compounds in which Q has 15 to 30 carbon atoms are particularly preferred; (d) Compounds of the above formula in which Q stands for EMI39.1 in which u is 1 or 2: : 1,2-Bis[3-(meth)acryloyloxy-2-hydroxypropoxy]ethyne, and 1,4-bis[3-(meth)acryloyloxy-2-hydroxypropoxy]butane, (e) Urethane di(meth)acrylates of the above formula in which 0 stands for JOCONHTNHCOOJ, in which J stands for an alkylene group normally having 2 to 10 carbon atoms, and T stands for an organic diisocyanate residue having 1 to 50 carbon atoms, as disclosed, for example, in Japanese Laid-Open Patent Specification No. 687/1975; (3) Tri functional and tetrafunctional methacrylates: Trimethylolpropane tri(meth)acrylate, trimethylol- ethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, and N,N'-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate. One or more of these copolymerizable monomers are employed. For preparing a dental adhesive composition, it is advisable to use a methacrylate or methacrylates in the quantity of at least 50% by weight of all the copolymerizable monomers employed. Preferred examples of the methacrylates include methyl methacrylate, ethyl methacrylate, HEMA, nhexyl methacrylate, benzyl methacrylate, lauryl methacrylate, Bis-GMA, bisphenol A dimethacrylate, 2,2-bis[(meth)acryloyl- oxypolyethoxyphenyli propane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,10-decanediol dimethacrylate, neopentyl glycol dimethacrylate, and trimethylolethane- trimethacrylate. For preparing the adhesive composition of this invention, it is necessary to employ the compound of the formula I or II in the quantity of 0.5 to 50%, or preferably 1.5 to 40%, by weight of all the polymerizable monomers employed. If it is less- than 0 5% by weight, no satisfactorily high adhesive strength is obtained, while the use of more than 506 by weight is likely to result in an adhesive bond of lower water resistance The water resistance of an adhesive bond is also affected by the type of the copolymerizable monomer employed¯ If a water-soluble monomer having a hydrophilic functional group, such as (meth)acrylic acid, 2hydroxyethyl (meth) acrylate or methacrylamide, is employed, therefore, it is highly advisable to ensure that it not occupy more than 50% by weight of all the polymerizable monomers employed. The adhesive composition of this invention is applied to adherend surfaces, and cured either physically by heating or irradiation with I-rays or ultraviolet or visible light,or chemically by a polymerization initiator. It is usually advisable to polymerize by irradiating light in tbe presence of a photo sensitizer, or using a polymerization initiator. The term touring agent" as herein used covers both of the polymerization initiator and the photosensitizer together. It is possible to use various curing agents, for example, organic peroxides, azo compounds, organic metal compounds, redox type initiators, and photosensitizers for ultraviolet or visible rays. More specifically, it is possible to use, for example, benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, azobisisobutyronitrile, tributylborane, organic sulfinic acids or the salts thereof, hydrogen peroxide/Fe2 salts, cumene hydroperoxide/Fe2+ slats, benzoyl peroxide/ N,N -dialkylaniline derivatives, ascorbic acid/Cu2+ salts, organic sulfinic -acid (or the salt thereof)/amine (or the salt thereof) /peroxide, -diketone/a&num; ;lylthiourea (for visible rays), benzoin methyl ether, benzoin ethyl ether, benzyl, diacetyl or diphenyl disulfide, and di--naphthyl sulfide For a dental adhesive composition, it is particularly preferable to use benzoyl peroxide, azobisisobutyronitrile, -tributylborane, organic sulfinic acids or the salts thereof, or aromatic sulfinic acid (or the salt thereof)/diacyl peroxide/ aromatic secondary or tertiary amine (or the salt thereof). Suitable examples of the aromatic sulfinic acids include benzenesulfinic acid, p-toluenesulfinic acid, W-naphthalene- sulfinic acid and styrenesulfinic acid. While alkali metal, alkali earth metal or ammonium ions may, for example, be used as. the cation to form a salt with a sulfinic acid, it is preferable to use alkali or alkali earth metal ions in order to produce a high degree of storage stability and adhesive strenght. Examples of such ions are Li+, Na+, K+, Mg2+ Ca2+ and Sr2+. Preferred examples of the aromatic amines include N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,Ndiethanolaniline, N,N-diethanol-p-toluidine, N-methylaniline, and N-methyl-p-toluidine. It, is also possible to use a salt of any such amine with an acid, e.g. hydrochloric, acetic or phosphoric acid. Preferred examples of the diacyl peroxides include benzoyl peroxide, m-toluoyl per oxide,- 2, 4-dichlorobenzoyl peroxide, octanoyl peroxide, lauroyl peroxide and succinic acid peroxide. It is particularly preferable to use benzoyl peroxide or m-toluoyl peroxide The curing agent may be used in the quantity of 0.01 to 20, or preferably 0.1 to 15, parts by weight for 100 parts by weight of the polymerizable monomer em plowed. It is sometimes preferable for the adhesive composition of this invention to contain a volatile organic solvent having a boiling point higher than 1500C at 76) Torr (101 iPa)* The addition of any such solvent is particularly useful for an adhesive composition used as a primer for the tooth cavity to be filled with a dental filling material. After the composition has been applied, air or nitrogen is blown thereagainst to volatilize the solvent to form a vinyl compound film on the adherend surface. Examples of the suitable solvents include methanol, ethanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, dichloromethane, chloroform, ethyl ether, isopropyl ether and toluene. The quantity of the solvent should not exceed 300, or preferably 100, times as much by weight as that of all the polymerizable monomers employed. The use of the solvent in any larger quantity can result, upon volatilization, in the formation of too thin a film of the polymerizable monomer on the adherend surface, or a great reduction in its adhesive strength. The adhesive composition of this invention may further contain a conventionally known filler of the inorganic, organic or composite type to form a dental cement for luting or filling, a dental composite resin or a bone cement. The adhesive composition may contain up to 1,000 parts, or preferably 20 to 500 parts, by weight of the filler for 100 parts by weight of the polymerizable monomers. The filler improves the rheological properties of the composition, and the mechanical properties, adhesive strength and water resistance of the cured composition. Examples of the applicable inorganic fillers include natural minerals such as quartz, feldspar, pottery stone, wollasto- nite, mica, clay, kaolin and marble, ceramics such as silica, alumina, silicon nitride, boron carbide, boron nitride, and glass-ceramics containing lanthanum, glass such as soda glass, barium glass, strontium glass or borosilicate glass, and water-insoluble inorganic salts such as barium sulfate and calcium carbonate. The inorganic filler is usually treated with a silane coupling agent such as r-methacryloyl- oxypropyltrimethoxysi lane, vinyltrimethoxys il ane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (2-methoxyethoxy) - silane, vinyltriacetoxysilane or Y-mercaptopropyltrimethoxy- silane. If an organic filler is preferred, it is possible to use any of various types of polymers, for example, polymethyl methacrylate, polyamide, polyester, polypeptide, polysulfone, polycarbonate, polystyrene, chloroprene rubber, nitrile rubber, styrene-butadiene rubber or polyvinyl acetate It is also possible to use a composite filler comprising a silanated inorganic filler coated with a polymer. One or more substances may be used as the filler. The filler may usually have a particle size of 1DO microns or less, and its particles may be formless, spherical, -lamellar or fibrous. If a polymer is used, it may be dissolved in the polymerizable monomer and the volatile organic solvent. The adhesive composition of this invention preferably contains an inorganic or composite filler to form a dental cement or composite resin, and an organic filler to form a bone cement In addition to the various constituents as hereinabove described, the adhesive composition of this invention may contain a polymerization inhibitor such as hydroquinone monomethyl ether (MEHQ) or an antioxidant such as 2,di-tert- butyl-p-cresol ° 1 an ultraviolet absorbing agent, a pigment or dye, phthalic acid diester or silicone oil if required to satisfy the various practical requirements for performance These additives are employed in a small quan tity up to a maximum of 10 parts, and usually up to five parts, by weight for 100 parts by weight of the polymerizable monomers. A room temperature curing redox type initiator may often be used when the adhesive composition of this invention is used for dental, orthopedic or other medical purposes. In such a case, it is necessary to ensure the storage stability of the composition, and therefore, to choose a proper package form which keeps the oxidant and the reducing agent away from each other It is, for example, possible to employ separate packages for Ca) the vinyl compound and the oxidant and (b) the vinyl compound and the reducing agent, (a) the vinyl compound and the oxidant (or reducing agent) and (b) the volatile organic solvent and the reducing agent (or oxidant), (a) the vinyl compound and the oxidant (or reducing agent) and (b) the filler and the reducing agent (or oxidant), or (a) the vinyl compound, the filler and the oxidant and (b) the vinyl compound, the filler and the reducing agent. In an organic sulfinic acid (or salt thereof)/amine (or salt thereof)/peroxide system, which is a particularly suitable redox polymerization initiator for the -adhesive composition of this invention, the ssulfinlc acid and the amine serve as a reducing agent, and the peroxide as an oxidant. In this case, it is possible to employ three separate packages by packing the sulfinic acid and the amine separately. When a photosensitizer is employed, it is necessary to keep the vinyl compound and the photosensitizer in z container shielded against light. If tributylborane or any other polymerization initiator initiating polymerization within a short time after contacting the vinyl compound is employed, it is necessary to pack the vinyl compound and the initiator separately from each other. The various constituents of the adhesive composition stored in separate packages as hereinabove described may be mixed together immediately prior to application. The adhesive composition of this invention adheres excellently to any of the following materials, and maintains a high adhesive strength for a long time even in a wet condition: (1) Hard tissues in a living body, such as teeth and bones; (2) Metals, including not only base metals such as iron, nickel, chromium, cobalt, aluminum, copper,- zinc and tin, or stainless steel, brass or other alloys thereof, but also noble metal alloys containing 50 to 90g of gold or platinum, which it has hitherto been difficult to bond by any known adhesive; (3) ceramics, such as glass, porcelain, silica and alumina; and (4) organic polymers, such as polymethyl methacryl ate, polyester, polyamide, polyurethane, poly carbonate, polyvinyl chloride and polyethylene. The adhesive composition of this invention can be used for various fields of application because of its high adhesive strength on various kinds of materials. The preferred examples of its applications will hereunder be set forth: (1) Dental Applications: The composition can be used as a composite resin adhering to a tooth, as an adhesive for application to the cavity surface prior to the placement of the composite resin in the cavity, as an adhesive for bonding an inlay, onlay, crown or the like to a cavity or abutment tooth, as an adhesive for orthodonties, as an adhesive for holding a bridgework, post or the like, or as a pit and fissure sealant. The composite resin usually comprises a polymerizable monomer, a filler and a curing agent. The composite resin and the adhesive used for the placement thereof are usually supplied together in a combination to the dentist. The specific constituents of a particular adhesive composition are selected to suit its application as hereinbefore described. If the composition is used, for example, as the adhesive to be coated on the tooth prior to the placement of the composite resin, it may contain 2 t9 40% by weight of the adhesive vinyl compound diluted with any other polymerizable monomer1 such as Bis-GMA, HEMA or an aliphatic dimethacrylate, or an organic solvent such as ethanol, and further contain a room-temperature curing agent. in accordance with the recipe shown in U. S. PatentNo. 4,259,075 vr 4,259,117. The adhesive composition which is used as a dental composite resin may comprise a customary filling material consisting of 20 to 40%by weight of Bis-GMA or -other polymerizable monomer and 60 to 80% by weight of filler, and .2 to 40% by weight of an adhesive vinyl compound based on the total weight of the polymerizable monomer in accordance with the recipe shown in the U. S. patents hereinabove cited. The composition may be applied to a tooth by a customary method. As opposed to the compositions disclosed in U. S. Patents Nos. 4,259,075 and 4,259,117, however, the composition of this invention does not call for the acid etching of the tooth surface to provide a satisfactory adhesive strength, The acid etching of the tooth should be avoided as far as possible, since it is likely to have an injurious effect on the dentin. When the composite resin is cured, it strongly adheres to the tooth, and does not require any mechanical retention -such as an undercut. The adhesive composition used for bonding an inlay, onlay, crown, or the like to a tooth cavity or abutment tooth may, for example, comprise 60. to 98 parts by weight of methyl methacrylate, 2 to 40 parts by weight of adhesive vinyl monomer, and 50 to 150 parts by weight of polymethyl methacrylate. A slight excess of the adhesive may be applied to the adherend surface, and an inlay or the like brought into intimate contact therewith, whereby it is possible to effect the bonding of any such dental restorative appliance to the tooth which no conventional luting cement has hitherto been able to achieve (2) Orthopedic Applications: : The adhesive composition of this invention can be used as a- bone cement (3) Industrial and Domestic Applications- in General: The adhesive composition of this invention is useful as an adhesive fo-r transportation machinery, electrical apparatus, building materials, cans or ceramics, or for home use, since it provides s superior adhesive strength on metals, ceramics and organic polymers. It is also useful as a paint, a primer for a paint or a coating composition. It adheres surprisingly well to an adherend surface carrying oil, or even water Its adhesive strength is markedly higher than that of any conventional polymerization curing type adhesive, such as cyanoacrylate, epoxy resin or second generation acrylic adhesives. The invention will now be described more specifically with reference to a variety of examples which are merely illustrative. They consist of the following: (1) EXAMPLES 1 to 20 - Examples of the preparation of the phosphate esters represented by formula 3, and examples of the adhesive compositions containing those compounds; (2) EXAMPLES 21 to 26 - Examples of the preparation of the phosphate esters represented by formula 4, and examples of the adhesive compositions containing those compounds; (3) EXAMPLES 27 to 36 - Examples of the preparation of the phosphate esters represented by formula 5, and examples of the adhesive compositions containing those compounds; (4) EXAMPLES 37 to 46 - Examples of the preparation of the phosphate esters represented by formula 6, and examples of the adhesive compositions containing those compounds; ; (5) EXAMPLES 47 to 53 - Examples of the adhesive composition of this invention used for dental application; and (6) EXAMPLES 54 to 61 - Adhesive -strength of the adhesive composition of this invention on metals, ceramics and organic polymers. EXAMPLE 1 A 500 cc three-neck flask was charged with 140 g (1.6 mols) of methacrylic acid, 190. g (1.6 mols) of 1,6hexanediol, 15 g of p-toluenesulfonic acid and 0.6 g of 2,2' methylene-bis (4-ethyl-6-tert-butylphenol). They were heated to 9JC at a pressure of 100to 150 mmHg (13 to 20 kPa). The reaction was continued for several hours , while oxygen was blown into the flask, until water disappeared. When water had disappeared, the reactant was cooled to ordinary room temperature, transferred into a separatory funnel, and washed with a 5% aqueous solution of sodium carbonate until the aqueous solution showed an alkaline reaction. The reactant was then washed with 300 cc of water five times. After the reactant had been dehydrated with anhydrous sodium sulfate, it was heated with 30 mg of MEHQ to 800C, whereby the remaining water was removed by distillation under Ieduod pressre and 1986 of a monoester and diester mixture were obtained. The analysis of the mixture by HLC indicated that it contained 75 mol % of monoester, and not more than 0.5% by weight of diol. A solution containing 55 g (0.36 mol) of phosphorus oxychloride in 100 cc of ethyl ether was placed in a oneliter reactor, and cooled to -40ac. A solution containing 81 g of a previously synthesized methacrylate mixture containing 0.3 mol of monoester, and 37 g (0.36 mol) of triethylamine was placed in a 300 ce dropping funnel connected to the reactor. The latter solution was dropped slowly, while the phosphorus oxychloride solution was strongly, and dry N2 gas was blown into the reactor. The reactant was kept at a temperature of -300C for three hours after the dropping of the solution from the dropping funnel had been finished, and then, its temperature was raised to 00C. 30 g of water were placed in the dropping funnel, and dropped under stirring. A solution containing 72.9 g (0.72 mol) of triethylamine in 100 cc of ethyl ether was, then, dropped The reactant was held at OOC for 10 hours thereafter under stirring. After the precipitated triethylamine hydrochloride had been separated by a glass filter, 10 mg of MEHQ were added into the filtrate, and the ethyl ether was removed by vacuum distillation at 400C, whereby a nonvolatile liquid residue was obtained. The liquid was dispersed in 200 cc of water, and while the dispersion was cooled with ice, and stirred strongly, 65 g (0.6 mol) of sodium carbonate were added little by little into the dispersion to neutralize it. When the dispersion had ceased to bubble, it was transferred into a separatory funnel, and extracted twice with 100 cc of ethyl ether and four times with 100 cc of chloroform. The aqueous solution was cooled with ice, and 6N HC1 was added thereinto to acidify it, and the separated oily matter was extracted with ethyl ether three times. All the extracts were combined, and dried with anhydrous Sodium sulfate. 10 mg of MEHQ were added, and the solvent was removed by distillation at a temperature not exceeding 40 C, whereby 67 g of a colorless, transparent liquid were obtained. The NMR of a 108 CDC1 solution of the liquid was examined at 90 MHz at ordinary room temperature. There were observed an ethylenic proton signal at @ = 6.05 and 5.5, 2 methyl proton signal at s = 1.9, a multifold hexamethylenic proton signal at @ = 3.8 to 4.2 and 1.2 to 1.8, and an acid proton signal of phosphoric acid in the vicinity of i = 9.7. The elementary analysis of the liquid indicated that it contained 44.58 C, 7.8% H, 36.5% 0 and 11.2t P, while they were theoretically 45.1%, 7.2%, 36.1% and 11.6%, respectively, and showed that it was a compound known as 6-methacryloyloxyhexyl dihyroen phosphate. The analysis of the compound by high-speed liquid chromatography (HLC) employing a Unnsil Q C18 column indicated that it had a purity of 97 to 98%. EX & 1PLE 2 A diol monoester and diester mixture was prepared by repeating the procedures of EXAMPLE 1, except for the use of 170 g (1.6 mols) of 1,5-pentanediol instead of 1,6-hexane- diol The quantity of the monoester in the mixture was determined by HLC, and that quantity of the mixture which contained 0-3- mol of monoester was subjected to phosphate esterification. The procedures of EXAMPLE 1 were repeated for the separation and purification of the reaction product to yield 6-1 g of an acidic nonvolatile liquid. The NMR of the compound thus obtained, and its elementary analysis [C: 42.6% (theoretically 42.9%), H: 7.1% (6.8%), 0: 38.5% (38.1 %), and P: 11.8t (12.3%)] indicated that it was 5-methacryloyloxypentyl dihydrogen. phosphate. The analysis of the compound. by HLC indicated that it had a- purity of 96 to 98%. EXAMPLE 3 A 500 cc flask was charged with 140 g (1,9 mols) of acrylic acid, 190- g (1.6 mols) of I,6-hexanediol, 15 g of p-toluenesulfonic acid, and 0.6 g of 2,2'-methylene- bis(4-ethyl-6-tert-butylphenol)- They were heated to 800C at a pressure of 100 to 200 mm Hg, while oxygen was being blown into the flask through a capillary, whereby water was removed by distillation. The reaction product was washed with alkaline water and water, and dehydrated to yield 175 g of an acrylic acid monoester and diester mixture. The analysis of the product by HLC indicated that it contained 68 mol % of monoester. The procedures of EXAMPLE 1 were repeated for reacting 83.6 g of the mixture with 55 g (0.36 mol) of phosphorus oxychloride, and separating phosphate monoester to yield 62 g of a colorless transparent nonvolatile liquid. The NMR of the compound thus obtained, and its elementary analysi [C: 42 7% (theoretically 42.9%), H: 7.1% (6.8%), 0: 38.3% (38.1%) and P: 11.9% (12.3%)] indicated that it was 6-acryloyloxyhexyl dihydrogen phosphate. The analysis of the compound by HLC indicated that it had a purity of 95 to 97t. EXAMPLE 4 A diol monoester and diester mixture was prepared by repeating the procedures of EXAMPLE 3, except for the use of 170 g (1.6 mols) of 1,5-pentanediol instead of 1,6hexanediol. After the monoester content of the mixture had been examined by HLC, that quantity of the mixture which contained 0.3 mol of monoester was subjected to phosphate esterification. The procedures of EXAMPLE 1 were repeated for the separation and purification -of the-reaction product to yield 48 g of an acidic nonvolatile liquid. The NMR of the compound thus obtained, and its elementary analysis 1C: 40.5% (theoretically 40.38), H: 6.58 (6.4%), 0: 40.08 (40.3t) and P: 13 08 (13.0%)) indicated that it was 5acryloyloxypentyl dihydrogen phosphate It showed a purity of 9 95 to 97% upon analysis by HLC. EXAMPLE 5 A 500 cc three-neck flask was charged with 140 -t (1.6 mols) of methacrylic acid, 230 g (1.3 mols) of 1,10decanediol, 15 g of p-toluenesulfonic acid, and 0.6 g of 2,2'-methylenebis(4-ethyl-6-tert-butylphenol). They were heated to 800C to form a uniform solution. The flask pressure was reduced to z level of 100 to 150 mn Hg, and while oxygen was being blown into the flask to stir the solution, it was subjected to phosphate esterificaion at 90 C, and water was removed by distillation. then water had ceased to appear, the reaction was discontinued, the reaction product was cooled to ordinary room temperature, and 300 cc of n-hexane were added thereinto to dilute it The solid precipitate was removed by filtration, and the filtrate was washed with an aqueous solution of sodium carbonate until The aqueous solution showed an alkaline reaction, After the reactant had been further washed with water, it was diluted with one liter of n-hexane, and left at 5 C with anhydrous sodium sulfate. After one day, the unreacted diol preci pitate was removed by filtration, 40 mg of PIEHQ were added into- the filtrate r and n-hexane was removed by vacuum dis dilation at a temperature not exceeding SO0C, whereby 268 g of a diol monoester and diester mixture were obtained. The analysis of the mixture by HLC indicated a monoester content of 65 mol e, and only a trace of unreacted diol. A solution containing 55 g (0.36 mol) of phosphorus oxychloride in 100 cc of ethyl ether was placed in a oneliter- reactor, and cooled to -400C A solution containing 123 g of a separately synthesized ester mixture containing 0.3 mol of monoester, and 37 g (0.36 mol) of triethylamine in 120 cc of ethyl ether was placed in a 300 cc dropping funnel, and the funnel was connected to the reactor. The latter solution was dropped slowly, while the phosphorus oxychloride solution was being stirred strongly, and dry N2 gas was being blown into the reactor. The reactant was held at a temperature of -30ac for three hours after the dropping of the solution from the dropping funnel, and its temperature was raised to OOC. 30 g of water were placed in the dropping funnel, and dropped under stirring. A solution containing 72.9 g (0.72 mol) of triethylamine in 100 cc of ethyl ether was, then, dropped. The reactant was held at 00C for 10 hours thereafter, while it was being stirred slowly. After the precipitated triethyl- amine hydrochloride had been removed by a glass filter, the filtrate was washed with water repeatedly, dehydrated and dried. After 20 mg of MEHO had been added, the ethyl ether was removed by vacuum distillation at 400C, whereby a liquid residue was obtained. The liquid was washed with n-hexane repeatedly for the removal of the diol and phosphate diesters by extraction, and the n-hexane was removed from the phosphate monoester phase by vacuum distillation, whereby 73 g of a liquid compound were obtained. The NMR at 90 MHz of a 10% CDC1 solution of the 3 compound was examined at ordinary room temperature. There were found an ethylenic proton signal at - = 6.05 and 5.5, a methyl proton signal -at = 1.9, a multifold decamethylenic proton signal at ; = 3.8 to 4.2 and 1.2 to 1:8, and an acidic proton signal of phosphoric acid in the vicinity of ; 9.7. The elementary analysis of the compound indicated that it contained 52.9% C, 8.7% , 29.2% 0 and 9.28 P, while they were theoretically 52.2%, 8.4%, 29.8% and 9.6%, respectively, and showed that it was 10-methacryloyloxydecyl dihydrogen phosphate. The analysis of the compound by HLC employing a Unisil O C18 column indicated a purity of 92 to 95%. EXAMPLE 6 A diol monoester and diester mixture was prepared by repeating the procedures of EXAMPLE 5, except for the use of 260 g (1.3 mols) of 1,12-dodecanediol instead of 1,10decanediol. After. the monoester content of the mixture had been. examined by HLC, that quantity of the mixture which contained 0.3 mol of monoester was subjected to phosphate esterification. The procedures of EXAMPLE 1 were repeated for the separation and purification of the reaction product to yield 75 g of 2 liquid compound. The NMR of the compound, and its elementary analysis [C: 55.3% (theoretically 54.9%), H: 9.2% (8.9%), 0: 27.0% (27.4%) and P: 8.5% (8.8%)] indicated that it was 12-methacryloyloxydodecyl dihydrogen phosphate. It showed a purity of 92 to 95% upon analysis by HLC EXAMPLE 7 A 500 cc flask was charged with 115 g (1.6 mols) of acrylic acid, 230 g (1.3 mols) of l,10-decanediol, 15 g of p-toluenesulfonic acid, and 0.6 g of 2,21-methylenebis- C4-ethyl-6-tert-butylphenol). They were heated to 80 C at a pressure of 100 to 200 mm Hg, (13 to 27 kPa) while oxygen was blowy into the flask through a capillary, and-water was removed by distillation. The procedures of EXAMPLE 5 were, then, repeated for dilution with n-hexane, filtration, washing with an alkali solution and water, dehydration, dilution with n-hexane, filtration and solvent removal by distillation to yield 223 g of a diol monoester and diester mixture. The analysis of the mixture by HLC indicated a monoester content of 66 mol t. The procedures of EXAMPLE 5 were further repeated for reacting 114 g of the mixture with 55 g (0.36 mol) of phosphorus oxychloride, and separating phosphate monoester to yield 62 g of a colorless transparent nonvolatile liquid. The NMR of the compound thus obtained, and its elemental analysis IC: 51.0% (theoretically 50.68), H: 9.4 % (8.2%), O : 30.8% (31.1%) and P: 9.0% (9.6 %)) indicated that it was 10-acryloyloxydecyl hydrogen phosphate. It showed a purity of 91 to 95% upon analysis by HLC. EXAMPLE 8 A diol monoester and diester mixture was prepared by repeating the procedures of EXAMPLE 7, except for the use of 260 g (1.3 mols) of 1,12-dodecanediol instead of 1,10-decanediol. After the monoester content of the mixture had been examined by HLC, that quantity of the mixture which contained 0.3 mol of monoester was subjected to phosphate esterification. The procedures of EXAMPLE 5 were repeated for the separation and purification of the reaction product to yield 79 g of a liquid compound. The NMR of the compound, and its elementary analysis 1C: 53.9E (theoretically 53.6%), H: 9.08 (8.%), 0: 28 it (28.5%) and P: 9.0% (9.2%)) indicated that it-was 12-acryloyloxydodecyl dihydrogen phosphate. It showed a purity of -92 to 96E upon analysis by HLC. EXAMPLES 9 TO 18, ASS COMPARATIVE EXAMPLES 1 AND 2 The adhesive compositions containing the adhesive monomers obtained in EXAMPLES 1 to 8 were prepared in accordance the recipe hereinafter shown, and tested for the water resistance of their adhesive strength on metal. Components and Proportions: Package A Adhesive monomer 5 parts by weight Methyl methacrylate 95 Benzoyl peroxide (BPO) 1 part Packace B Polymethyl methacrylate (PtSSA) 100 parts by weight powder Sodium benzenesulfinate 3 ,N'diethanol-p-toluidine 1 part The package A consisted of a uniform solution, and the package'. B was a uniform dispersion of the powders of sodium benzenesulfinate and amine in the P9MA powder. A 10 mm square by 3 mm thick plate of a Ni-Cr alloy containing 92.78 of. nickel was polished with &num;1000 abrasive paper, and washed ultrasonically with water and methyl ethyl ketone. An adhesive cellophane tape having a hole with a diameter of S- mm was bonded to the plate so that the hole might be aligned with the center of the polished plate surface. An equal number of stainless steel bars having a diameter of 7 mm and a length of 35 mm were prepared, and one end surface of each bar was polished and washed as each alloy plate had been The- components in Package A were mixed with an equal weight of the components in Package B to prepare an adhesive composition The adhesive was applied by 2 brush to the alloy plate exposed through the hole of the cellophane tape, and the polished end of the bar, and the bar and the plate were bonded to each other to form a butt joint. Twenty samples, or bar and plate combinations were prepared by employing one adhesive composition, and immersed in water at 370C an hour after they had been bonded. Ten samples were removed from water after 24 hours, and the other 10 samples after 10 days. The adhesive bond on each sample was tested for tensile strength bv an Instron tensile tester. Table 1 shows an average adhesive strength obtained by each adhesive comlsosition in each lot of 10 samples. The adhesives developed cohesive failure at a tensile strength of 400 kg/cmê (39 MPa) or above, and adhesive failure mainly on the Ni-Cr alloy surface at a lower tensile strength. TABLE 1 Adhesive Strength Adhesive Monomer* 24 hours 10 days R 2 2 Example i MPa ¯¯¯¯¯ 9 5 H 423 41.5 362 35.5 10 5 CH3 443 43.5 380 37.3 11 6 ii 420 41.2 399 -39.1 12 12 6 CH3 451 44.2 425 41.7 13 8 H 456 44.7 441 43.2 14 8 5 438 43.0 449 44.0 15 10 H 430 42.2 421 41.3 16 10 CH3 465 45.6 460 45.1 17 12 H 453 44.4 441 43.2 18 12 CH3 459 45.0 465 45.6 EMI59.1 The adhesive compositions of this invention showed an adhesive strength higher than 400 kg/cmê (39 MPa) after 24 hours of immersion in water, and did not undergo any great reduction in adhesive strength after 10 days, either. For comparison purposes, similar-tests were conducted on a composition containing a conventionally known phosphate ester monomer, for example, methacryloyloxyethyl dihydrogen phosphate (Comparative Example 1), and on a composition not containing any adhesive-monomer (Comparative Example 2). The results are sbown in Table 2. Immersion in water brought about a heavy reduction in adhesive strength. TABLE 2 Adhesive Strength 24 hours 10 days Comparative Adhesive 2 2 Example Monomer kg/cmê MPa kg/cmê MPa 1 Nethacryloyloxyethyl 163 16 13 1.3 hydrogen phosphate 2 None 4 0.4 0 0 EXAMPLE 19 Nine adhesive compositions each containing a phosphate ester of the general formula EMI60.1 in which i is 2, 3, 4, 5, 6, 7, 8, 10 or 12, were prepared, and tested for adhesive strength in water. Each of these thermosetting adhesive compositions contained four parts by weight of a phosphate ester of the above formula, one part by weight of BP0, 95 parts by weight of methyl methacrylate and 100 parts by weight of PMMA powder. Two round nickel bars having a diameter of 7 mm were joined end-to-end by using each adhesive composition. The bars were heated at 800C for three hours, whereby the adhesive composition was cured. Each sample was immersed in water at 250C, and tested for adhesive strength after one day, month or year. The relationship between i and the wet adhesive strength of the composition is shown in the single figure of the drawing, which indicates that an improved adhesive strength in water was obtained vith an increase in the value of j,.particularly when it was 5 or more, and more particularly when it was 8 or more. EXAMPLA 20 AND COMPARATIVE EXAMPLE 3 Two-pack adhesive compositions were prepared in accordance with the following recipe by employing the adhesive monomers shown in TABLE 3, and tested for adhe- sive strength by bonding a commercially available dental composite resin to the dentin of a human tooth: : Package C t4- 2,2'-bis(3-methacryloyloxy-2- 40 parts by weight hydroxypropoxy)phenyl]propane Neopentyl glycol dimethacrylate 35 " " ' Adhesive monomer 25 Benzoyl peroxide 1.5 " " " 2,6-di-t-butyl-p-cresol 0.03 part by weight Package D Ethanol 100 parts by weight Sodium benzenesulfinate 4 " " " N,N-diethanol-p-toluidine 1.7 " " " Human molars were cut in the shape of a square pillar to have the dentin exposed on con adherend surface, and square ivory bars measuring 10 mm square by 30 mm long were also prepared. They were kept in cold water until immediately prior to use. Immediately prior to use, water was wiped off the adh-erend dentin surface of each mclar, and the dentin surface was etched for a minute with a 40% aqueous solution of orthophosphoric acid. The molar was washed carefully with flowing water, and after clean air or nitrogen had been blown against the molar to volatilize water, a strip of aluminum was wound about the molar. Water was also wiped off the adherend surface of each vory bar. A mixed solution prepared by mixing equal voles of the liquids C and D was coated on the molars and the ivory bars, and clean air or nitrogen was blown against them to volatilize ethanol. A commercially available dental composite resin Clearfil F (trademark of KURARAY CO., LTD., Japan) was kneaded and it was sandwiched between the adherend surfaces of the molars and the ivory bars to form test samples. They were immersed in water at 370C after 30 minutes, and examined after one day for adhesive s-trength by an Instron tensile tester at a crosshead speed of 2 mm/min. The results are shown in TABLE 3. Seven human teeth were used for testing one adhesive composition. TABLE 3 shows an average adhesive strength. TABLE 3 Adhesive Monomer Adhesive Strength 2 Comparative 2-methacryloyloxyethyl kg/cmê MPa Example 3 dihydrogen phosphate 27 2.65 Example 20 (a) 6-methacryloyloxyhexyl dihydrogen phosphate 110 10.8 (b) 10 -methacryloyloxydecyl hydrogen phosphate 172 16.9 EXAMPLE 21 A 500 cc three-neck flask was charged with 129 a (1.5 mols) of methacrylic acid, 216 g (1.5 mols) of 1,4cyclohexane dimethanol, 17 g of p-toluenesulfonic acid, and 0.7 g of 2,2'-methylenebis(4-ethyl-6-tert-butylphenol). They were dissolved in a bath of water at 700C to form a uniform solution. The bath temperature was raised to 850C, and while oxygen was being blowy into the flask at a pressure of 100 mm Hg (13.3 kPa), the water produced was removed by distillation. When water had ceased to appear, the solution was returned to normal atmospheric pressure, diluted with 500 cc of benzene and 500 cc of n-hexane, and washed with an aqueous solution of sodium carbonate, and methacrylic acid and p-toluenesulfonic acid were removed by extraction. The solution was washed with neutral water repeatedly, and after it had been ascertained that the solution was neutral, it was dried with anhydrous sodium sulfate, 100 mg of MEHO were added, and the solvent was removed by vacuum distillation at a temperature not exceeding 80"C. There was obtained a monoester and diester mixture weighing 242 g, and found to contain 72 mol z of monoester as a result of analysis by HLC. The mixture did not contain more than 0.18 of unreacted diol. A solution containing 55 g (0.36 mol) of phosphorus oxychloride in 100 cc of ethyl ether was placed in a oneliter reactor, and cooled to -400C. A solution containing 96.5 g (0.3 mol) of 2 separately synthesized methacrylate mixture, and 37 g (0.36 mol) of triethylamine i 100 cc of ethyl ether was placed in a 300 cc dropping funnel, and the funnel was connected to the reactor. The latter solution was dropped slowly1 while the phosphorus oxychloride solution was being stirred strongly, and dry N2 gas was being blown into the reactor. The reactant was held at -300C for three hours, and then, its temperature was raised to OOC. Then, 30 g of water were placed in the dropping funnel, and dropped into the reactor under stirring. A solution containing 72.9 g (0.72 mol) of triethvlamine in 100 cc of ethyl ether was, then, dropped. The reactant was held at 0 C for 10 hours thereafter under slow stirring. After the precipitated triethylamine hydrochloride had been removed by a glass filter, 10 mg of MEHQ were added into the filtrate, and ethyl ether was removed by vacuum distillation at 400C, whereupon a nonvolatile liquid was obtained as a residue. The liquid was dispersed in 200 cc of water, and while the solution was cooled with ice, and stirred. strongly, 65 g (0.6 mol) of sodium carbonate were added into the solution little by little to neutralize it. When the- solution had ceased to bubble, it was transferred into a separatory funnel, and washed four times by extraction with 100 cc of chloroform. Then, 6N HC1 was added into the solution to acidify it, while it was cooled with ice-, and the separated oily matter was extracted three times with chloroforme After all the extracts had been combined, and dried with anhydrous sodium sulfate, 10 mg of MEHQ wereadded, and the solvent was removed by distillation at a temperature not exceeding 400C., whereupon there was obtained a colorless liquid weighing 70 g. The NMR at 90 MHz of a 10% CDC13 solution of the liquid was examined at ordinary room temperature. There were found an ethylenic proton signal at # = 6.05 and 5.5 a methyl proton signal at c = 1.9, two methylenic proton signals adjacent to oxygen atoms at - = 3.6 to 4.1, methylene and methyl proton signals on the cyclohexane ring at e = 0.7 to 1.9, and an acids proton signal of phosphoric acid at # = 9.4 to 9.8. The elementary analysis of the compound indicated 48.9% C (theoretically 49.3%) , 7.6% H (7.26), 33.1% 0 (32.9%) and 10.4% P (10.6%), and showed that it was 4-(methacryloxymethyl)cyclohexylmethyl dihydrogen phosphate. phosphate. The compound showed a purity of 96 to 98t upon analysis by HLC employing a Unisil O C18 column. EXAMPLE 22 A 500 cc flask was charged with 140 g (1.9 mols) of acrylic acid, 230 g (1.6 mols) of 1,4-cyclohexanedi- methanol, 15 g of p-toluenesulfonic-acid, and 0.6 g of 2,2 '-methylenebis (4-ethyl-6-tert-butylphenol). They were heated at 800C at a pressure of 100 to 200 mm Hg (13 to 27 kPa), while oxygen was blown into the flask through a capillary, and water was removed by distillation. The procedures of EXAMPLE 21 were, then, repeated to yield 251 g of a monoester and diester mixture. The mixture showed a monoester content of 72 mol % upon analysis by HLC. The -procedures of EXAMPLE 21 were repeated for reacting 89 g of the mixture with 55 g (0.36 mol) of phosphorus oxychloride, and separating phosphate monoester to yield 59 g of a light yellow, transparent liquid. The NMR at 90 MRz of a 10% CDC13 solution of the liquid was examined. There were found three ethylenic proton signals at = = 5.7, 6.1 and 6.3, two methylenic proton signals adjacent to oxygen atoms at s = 3.6 to 4.1, methylene and methine proton signals on the cyclohexane ring at # = 0.7 to 1.9, and a phosphoric acid proton signal at i = 9.1 to 9.5. The elemental analysis of the compound indicated 47.9% C (theoretically 47.5%), 7.1% H (6.9%), 34.1% 0 (34.5%) and 11.0t P (11.1%), and shdwed that it was 4-(acryloyloxymethyl)cyclohexylmethyl dihydrogen phosphate. It showed a purity of 95 to 97% upon analysis by HLC. EXAMPLES 23 AND 24 Adhesive compositions containing the compounds obtained in EXAMPLES 21 and 22 as an adhesive monomer (EXAMPLES 23 and 24), and an adhesive composition containing - 2--methacryloyloxyethyl dihydrogen phosphate (COmPARA- TIVE EXAMPLE I) were prepared in accordance with the following recipe, and tested for adhesive strength on metal after immersion in water. Components and Proportions: Package A Adhesive monomer 5 parts by weight ethyl methacrylate 95 Benzoyl peroxide I part Package B PMMA powder 100 parts by weight Sodiums benzenesulfinate 3 N,N-diethanol-p-toluidine 1 part Package A consisted of-a uniform solution, and Package B was a uniform dispersion of the sodium benzenesulfinate and amine powders in the PMMA powder. A 10 mm square by 3 mm thick plate of a Ni-Cr alloy containing 92.7% of nickel was polished with 1000 abrasive paper, and washed ultrasonically with water and methyl ethyl ketone. An adhesive cellophane tape having a hole with z diameter of 5 mm was bonded to the plate so that the hole might be aligned with center of the polished plate surface. An equal number of stainless steel bars having a diameter of 7 mm and a length of 35 mm were prepared, and one end surface of each bar was polished and washed as the alloy plates had been. An adhesive composition was prepared by mixing equal weights of the components in Packages A and B, and applied by a brush to the alloy plate exposed through the hole in the cellophane tape, and the stainless steel bar. The alloy plate and the bar were bonded to each other to form a butt joint. Twenty samples, or bonded bar and plate combinations were prepared by employing each adhesive composition, and immersed in water at 370C after an hour. Ten samples were removed from water after 24 hours, and the remaining 10 samples after 10 days. They were examined for adhesive strength by an Instron tensile tester. TABLE 4 shows the average obtained from the test results. The adhesive compositions developed cohesive failure at a tensile strength of 400 kg/cm2 or above, and adhesive failure mainly on the Ni-Cr alloy surface at a lower tensile strength. TABLE 4 2 Adhesive strength (kg/cm Adhesive Monomer 24 hours 10 days Example 23 4-(methacryloyloxy- 413 402 methyl) cyc lohexylmethy 1 dihydrog en phosphate 24 4-(acryloyloxvmethyl)- 408 396 cyclohexylmethyl dihydrogen phosphate Comparative 2 -meth acryl oyloxyethyl 163 13 Example 1 dihydrogen phosphate As is obvious from TABLE 4, the adhesive compositions of this invention showed a very high initial adhesive strength exceeding 400 kg/cm2 (39.2 MPa), and did not undergo any appreciable reduction in adhesive strength after 10 days of immersion in water. On the other hand, the conventional adhesive composition containing 2-methacloyloxyethyl dibyarogen phosphate showed a great reduction in adhesive strength as a result of immersion in water. EXAMPLES 25 AND 26 Two-pack adhesive compositions were prepared in accordance with the following recipe by employing the adhesive monomers shown in- TABLE 5, applied for bonding a commercially available dental composite resin to the dentin of a human tooth, and tested for adhesive strength: : -Package C 2,2'-bisth-(3-methacryloyloxy-2- 40 parts by weight hydroxypropoxy) phenyl] propane Neopentyl glycol dimethacrylate 35 " Adhesive monomer 25 " " Benzoyl peroxide 1.S 2,6-di-t-butyl-p-cresol 0.03 part by weight Package D Ethanol 100 parts by weight Sodium benzenesulfinate 4 4 " N,N-diethanol-p-toluidine 1.7 " Human molars were cut in the shape of a square pillar to have an exposed adherend dentin surface and square ivory bars measuring 10 mm square by 30 mm long were also prepared. They were kept in cold water until immediately prior to use. Immediately prior to use, water was wiped off the adherend ivory surface of each molar, and the dentin surface was etched for a minute with a 40% w/w aqueous solution of orthophosphoric acid. The molar was, then, washed carefully with flowing water, and after clean air or nitrogen had been blown against the molar to volatilize water, a strip of aluminum was wound about the molar. Water was also wiped off the adherend surfaces of the ivory bars. An adhesive composition prepared by mixing equal volumes of the liquids C and D was applied to the molar and the ivory bar, and clean air or nitrogen was blown against them to dry them. A commercially available dental composite resin Clearfil F (trademark of KURARAY CO., LTD., Japan) was kneaded and it was sandwiched between the adherend surfaces of the molar and the ivory bar. The test samples thus prepared were immersed in water at 37 C after 30 minutes, and examined after one day of immersion for adhesive strength by an ,Instron tensile tester at a crosshead speed of 2 mm/min. The results are shown in TABLE 5. Seven human molars were employed for testing each adhesive composition. TABLE 5 shows the average of the results obtained. TABLE 5 Adhesive Strength Adhesive Monomer kg/cmê MPa Comparative 2-methacryloyloxyethyl 27 2.6 Example 3 dihydrogen phosphate Example 25 4-(methacrylovloxymethyl)- 148 14.3 cyclohexylmethyl dihydrogen phosphate 26 4-(acryloyloxymethyl)cvclo- 129 12.7 hexylmethyl dihydrogen phosphate EXAMPLE 27 A one-liter three-neck flask was charged with 250 g (2.9 mols) of methacryiic acid, 480 g (2.4 mols) of 1,4bis(2-hydroxyethoxy)benzene, 35 g of p-toluenesulfonic acid, and 0.6 g of MEHQ. They were heated to 800C until they were dissolved to form a uniform solution. The flask pres sure was reduced to a level of 20 to 100 mm Hg (0.27 to 1.3 kPa) by an aspirator, and while oxygen was being blown into the flask, the solution was heated at a temperature of 85 C to 900C, and water was removed by distillation. When water ceased to appear after four hours, the reaction was discontinued, and while the reactant solution was hot, it was poured' into 1.5 liters of toluene. The unreacted dial precipitate was removed by a .4- filter. The filtrate was washed twice with 500 cc of a 5% aqueous solution of Na2CO3 and three times with neutral water. After it had been dried with anhydrous sodium sulfate, 0.1 g of MEHQ was- added, and toluene was removed by vacuum distillation at a- -temperature not exceeding 800C. There was obtained a monoester and diester mixture weighing 440 g. The analysis of the mixture bv HLC indicated a monoester content of 658 by weight, and only a trace of unreacted diol. A solution containing 55.2 g (0.36 mol) of phosphorus oxychloride in 15Q cc of tetrahydrofuran was placed in a one-liter reactor, and cooled to -50 C. A solution containing 123 g of thereabove synthesized monoester and diester mixture-containing 0.3 mol of monoester, and 33.4 g (0.33 mol) of triethylamine in 150 cc of tetrahydrofuran was placed in a 500 cc dropping- funnel, and the funnel was connected to the reactor. The monoester solution was dropped slowly, while dry N2 gas was being blown to stir the phosphorus oxychloride solution strongly, and the internal temperature of the reactor was kept at a level of -45tC to -50 C. It was also kept at -450C for an hour after the dropping operation had been finished, and raised then to 0 C. A solution containing 30 ml of water and 75.9 g of triethylamine in 100 cc of tetrahydrofuran was dropped slowly. The reactant solution was then cooled with ice and stirred continuously for 15 hours, whereby the P-C1 bonds were hydrolyzed. The precipitated triethylammonium chloride was removed by a #4 glass filter. After 30 mg of MEHQ had been added to the filtrate, tetrahydrofuran was removed by vacuum distillation at a temperature not exceeding ssO C. The residue thereby obtained was poured into 400 cc of a 0.3 N aqueous solution of hydrochloric acid. The solidified residue was collected by filtration, washed with 500 cc of 0.3 N aqueous solution of hydrochloric acid, and dewatered on the filter. The residue was, then, washed with toluene several times for the removal of any matter soluble in toluene, and vacuum dried at ordinary room temperature. There was obtained a white solid crude phosphate monoester weighing 74 g. The monoester was dissolved in 300 cc of tetrahydrofuran, and after the insoluble matter had been removed by filtration, it was recrystallized with a mixed solvent containing toluene and n-hexane in a ratio by volume of 1:1 to yield 69 g of crystals. The crystals had a melting point of 108.50C to 109.50C. The NMR at 90 MRz of a d6-acetone solution of the crystals was examined at ordinary room temperature. There were found an ethylenic proton signal at > = 6.05 and 5.55, multifold signals of eight methylenic protons at d = 4.0 to 4.5, a methyl proton signal at t = 1.85, four proton signals of phenylene at # = 6.9, and a phosphoric acid proton signal at i = 8.3. The elemental analysis of the compound indicated 48.1% C (theoretically 48.68) and 9.1%- P (8,95), and showed that it was a compound of the formula: EMI72.1 EXAMPLE 28 A diol monoester and diester mixture was prepared by repeating the procedures of EXAMPLE 27, except for the use of 216 g (3.0 mols) of acrylic acid instead of methacrylic acid. After the monoester content of the mixture had been examined by RLC, that quantity of the mixture which contained 0.3 mol of monoester was subjected to phosphate esterification. The procedures of EXAMPLE 27 were repeated for separating the reaction product to yield 65 g of a white solid compound. The NMR of the compound, and its elemental analysis -1C: 46.58 (theoretically 47.0%), and P: 9.1% (9.3%)] indicated- that it was a compound of the formula: EMI72.2 It showed a purity of at least 95t upon analysis by HLC. EXAMPLES 29 TO 32 The procedures of EXAMPLES 27 and 28 were followed to synthesize four compounds as shown in TABLE 6 by employ ing methacrylic or acrylic acid, and 1,4-bis(3-hydroxypropoxy)benzene or 1,4-bis(4-hydroxybitoxy)benzene as diol. The structure of each compound was determined by NtS and elementary analysis, and its purity by HLC, As regards the results of elementary analysis, the values of C, H and P alone are shown in TABLE 6. All the compounds showed a purity of at least 95t. TABLE 6 EMI73.1 Example <SEP> Chemical <SEP> Structure <SEP> Element <SEP> Analysis <SEP> (%) <tb> <SEP> C <SEP> H <SEP> P <tb> <SEP> CH3 <SEP> O <tb> 29 <SEP> # <SEP> 51.1 <SEP> 6.4 <SEP> 8.5 <tb> <SEP> H2C=C-COO-(CH2)3--O#O-(CH2)3-O-P-(OH)2 <SEP> (51.3) <SEP> (6.2) <SEP> (8.3) <tb> <SEP> H <SEP> O <tb> 30 <SEP> # <SEP> 50.4 <SEP> 5.7 <SEP> 8.7 <tb> <SEP> H2C=C-COO-(CH2)3-O#O-(CH2)3-O-P-(OH)2 <SEP> (50.0) <SEP> (5.9) <SEP> (8.6) <tb> <SEP> H <SEP> O <tb> 31 <SEP> # <SEP> 53.4 <SEP> 6.5 <SEP> 7.7 <tb> <SEP> H2C=C-COO-(CH2)4-O#O-(CH2)4-O-P-(OH)2 <SEP> (53.7) <SEP> (6.8) <SEP> (7.7) <tb> <SEP> H <SEP> O <tb> 31 <SEP> # <SEP> 52.5 <SEP> 6.7 <SEP> 8.1 <tb> <SEP> H2C=C-COO-(CH2)4-O#O-(CH2)4-O-P-(OH)2 <SEP> (52.6) <SEP> (6.5) <SEP> (8.0) <tb> Note: ( ) calculated value EXAMPLES 33 AND 34 Three adhesive compositions containing the compounds obtained in EXAMPLES 27 and 28 (EXAMPLES 33 and 34) and 2-methacryloyloxyethyl dihydrogen phosphate (COM- PARATIVE EXAMPLE 1) as the adhesive monomer were prepared in accordance with the following recipe, and tested for adhesive strength on metal after immersion in water: Components and Proportions: Package I Adhesive monomer 3 parts by weight Methyl methacrylate 97 Benzoyl peroxide 1 part Package II Polymethyl methacrylate powder 100 parts by weight Sodium benzenesulfinate 3 n N,N-diethanol-p-toluidine 1 pert Package II was a uniform mixture of.the PM > S powder in the benzenesulfinate and amine powders. A 10 mm square by 3 mm thick plate of a Ni-Cr alloy containing 92.7% of nickel was polished with 1000 abrasive paper, and washed ultrasonically with water ane methyl ethyl ketone. An adhesive cellophane tape having a hole with a diameter of 5 mm was bonded to the plate so that the hole might be aligned with the center of the polished plate surface. An equal number of stainless steel bars having a diameter of 7 mm and a length of 35 =m were prepared, and one end surface of each bar was polished and washed as the alloy plates had been. A mixture containing equal weights of the components in Packages I and II was applied by a brush to the alloy plate exposed through the hole in the cellophane tape, and the stainless steel bar, and the plate and the bar were joined to each other by forming a butt joint. Twenty samples, or bonded plate and bar combinations were prepared by employing each adhesive composition. They were immersed in water at 370C one hour after the bar and the plate had been bonded to each other. Ten samples were removed from water after 24 hours, and the remaining 10 samples after 10 days. They were examined for adhesive strength by an Instron tensile tester. TABLE 7 shows The average of the results obtained. the adhesives developed cohesive failure at a tensile strength of 400 kg/cmê (39.2 MPa), or above, and adhesive failure mainly on the Ni-Cr alloy surface at a lower tensile strength. TABLE 7 Adhesive Strength - Adhesive Strength 24 hours 10 days Adhesive Monomer kg/cm2 MPa kg/cmê MPa Example 33 Monomer of Example 27 465 45.6 463 45.4 " 34 28 461 45.2 457 44.8 Comparative 2-methacryloyloxyethyl 163 16.0 13 1.3 Example 1 dihydrogen phosphate As is obvious from TABLE 7, the adhesive compositions of this invention showed a very high initial adhesive strength exceeding 400 kg/cm2 (59.2 MPa), and did not undergo any appreciable reduction in adhesive strength after 10 days of immersion in water. On the other hand, the adhesive composition of Comparative Example 1 showed a great reduction in adhesive strength as a result of immersion in water. EXAMPLES 35 AND 36, AND COMPARATIVE EXAMPLE 4 Two.-pa-ck adhesive compositions were prepared in accordance with the following. recipe by employing the adhesive monomers of EXAMPLES 27 and 28 and COMPARATIVE EXAMPLE 1, applied. for bonding a commercially available denta-l composite resin to acid-etched human dentin and unetched dentin, and tested for adhesive strength: : Package III 2,2-bis[4-(3-methacryloyloxy-2- 40 parts by weight hydroxypropcxy)phenyXpropane 2-hydroxyethyl methacrylate 30 " " Diethylene glycol dimethacryl- 23 ate Adhesive monomer 7 Benzoyl peroxide 1.5 " " " Package IV 9.5% ethanol 100 parts by weight Sodium benzenesulfinate 4 II N,N-diethanol-p-toluidine 1 part by weight Human-molars were cut in the shape of a square pillar to have an exposed adherend dentin surface and square ivory bars measuring 10 mm square by 30 mm long were also prepared. They were held in cold water until immediately prior to use. A half of the molars were subjected to acid etching, while the other molars were not. Ismediately prior to use, water was wiped off the adherend dentin surface of each molar. The dentin surface of each molar to be etched was etched for a minute with a 40% aqueous solution of orthophosphoric acid. The etched surface was washed carefully with flowing water, and clean air or nitrogen was blown against the dentin surface to volatilize moisture therefrom. A strip of aluminum was wound about the molar. Water was also wiped off the adherend surfaces of the ivory bars. A mixed solution containing equal volumes of the liquids III and IV was coated on the teeth and the ivory bars, and clean air or nitrogen was blown against them to.dry them. A commercially available dental composite resin Clearfil F (trademark of KURARAY CO., LTD., Japyn) was kneaded. This paste was sandwiched between the adherend surfaces of the teeth CH and the ivory bars, and bonded therewith. The test samples were immersed in water aE 37 C after 30 minutes of adhesion, and tested after one day for adhesive strength by an Instron tensile tester at a crosshead speed of 2 mm/min. The results are shown in TABLE B. Seven teeth were employed for testing each adhesive composition. . TABLE 8 shows the average of the results obtained. . TABLE 8 ,-'.. - Adhesive Strength Etched Unetched Adhesive Monomer 2 2 MPa 2 - kg/cmê MPa kg/cm MPa Example 35 Monomer of Example 27 168 16.5 74 7.3 " 36 " " " 28 160 15.7 74 7.3 Comparative n " Compara- s 32 3.1 7 0.7 Example 4 tive Example 1 ¯ -° - As is obvious from TABLE 8, the adhesive compositions of this invention showed an extremely higher adhesive strength than that of COMPARATIVE EXAMPLE 4 containing a conventional phosphate monoester monomer. The adhesive composition of this invention provides a high adhesive strength as required for clinical application in dentistry, even if no acid etching is made on the dentin. This enables the simplification of dental treatment which has never been expected from the prior art. EXAMPLE 37 A one-liter three-neck flask was charged with 250 g (2.9 mols) of methacrylic acid, 480 g (2.4 mols) of 1,3-bis (2-hydroxyethoxy) benzene, 35 g of p-toluenesulfonic acid, and 0 6 g of MEHQ- They were heated to 850C until they were dissolved to form a uniform solution. The flask pressure was reduced to a level of 20 t6 100 mm Hg (2.7 to 13 kPa) by an aspirator. While oxygen was blown into the flask, the-solution-was heated: two a temperature of 85 C to 900C, and water was- removed by distillation. When water ceased to appear after about four hours, the reaction was discon tinued. While the reactant solution was still hot, it was poured into 1.5 liters of toluene, and the precipitated unreacted diol was removed by a 4 filter. The filtrate was washed twice with a 5% aqueous solution of Na2CO3, and three times with neutral water, and dried with anhydrous sodium sulfate. After 0.1 g of MEHQ had been added, toluene was removed by vacuum distillation at a temperature not ex ceeding 800C. There was obtained a monoester and diester mixture weighing 460 g. The analysis of the mixture by HLC indicated a monoester content of 64% by weight, and only a trace of unreacted diol. A solution containing 55.2 g (0.36 mol) of phosphorus oxychloride in 150 cc of tetrahydrofuran was placed in a one-liter reactor, and cooled to -50 C. A solution contain ing 125 g of the monoester and diester mixture, which contained 0.3 mol of monoester, and 33.4 g(0.33 mol) of triethylamine in 150 cc of tetrahydrofuran was placed in a 500 cc dropping funnel, and the funnel was connected to the reactor. The monoester solution was dropped slowly, while dry N2 gas was being blown into the reactor to stir the phosphorus oxychloride solution strongly. The internal temperature of the reactor was kept at a level of -45DC to -50tC while the dropping operation was continurd, and at -450C for an hour after its termination. he temperature was, then, raised to OOC, dnd a solution contwining 30 ml of water and 75.9 g of triethylamine in 100 cc of tetrahydrofuran was dropped slowly. The reactant solution was cooled with ice, and stirred continuously for 15 hours thereafter, whereby the P-C1 bonds were hydrolyzed. The precipitated triethylammonium chloride was removed by a w4 glass filter. After 30 mg of MEHQ had been added into the filtrate, tetrahydrofuran was removed by vacuum distillation at a temperature not exceeding 30 C. A solution of the residue in 800 cc of ethyl acetate was put in a separatory funnel, and washed three times with 300 cc of a 2 N aqueous solution of hydrochloric acid, and twice with 30n cc of neutral water. After the residue bad been dehydrated overnight with anhydrous sodium sulfate, 30 mg of MEHQ were added1 and ethyl acetate was removed by vacuum distillation to yield a liquid residue. It was washed with toluene repeatedly, and any volatile matter in the residue was removed by vacuum distillation. There was obtained a -solid --crude phosphate monoester weighing 67 g. The monoester was dis solved in 150 cc of acetone, and after the insoluble matter had been removed by filtration, the phosphate monoester in the solution was recrystallized by adding a mixed solvent containing toluene and n-hexane in a ratio by volume of 1:1 to yield 58 g of crystals. The crystals had smelting point of 640C to 67 C. The NMR at 90 MHz of a d6-acetone solution of the crystals was examined at ordinary room temperature. There were found an ethylenic proton signal at 5 = 6.05 and 5.55, multifold signals of eight methylenic protons at #= 4.0 to 4.54 a methyl proton signal at A = 1.85, four proton sig nazis of phenylene.at # = 6.3 to 6.5 and 7.0 to 7.2, and a phosphoric proton signal at # = 9.2. The elemental analysis of the compound indicated 49.08 C (theoretically 48.68) and 8¯6% P (8.9%), and showed that it was a compound of the EMI80.1 EXAMPLE 38 A- diol monoester and diester mixture was prepared by repeating the procedures of EXAMPLE 37, except for the use of 216 g (3.0 mols) of acrylic acid instead of methacrylic acid¯ After the monoester content of the mixture had been examined by HLC, that quantity of the mixture which contained 0.3 mol of monoester was subjected to phosphate esterification. The procedures of EXAMPLE 37 were followed for separating the reaction product to yield a solid compound weighing 60 g. The NMR of the compound, and its elemental analysis [C: 47.5% (theoretically 47.0%) and P: 8.9% (9.3%)] indicated that it was a compound of the formula: EMI81.1 It showed a purity of at least 95% upon analysis by HLC. EXAMPLES 39 TO 42 The procedures of EXAMPLES 37 and 38 were followed for synthesizing four compounds as shown in TABLE 9 by employing methacrylic or acrylic acid, and 1,3-(bis(3 hydroxypropoxy) benzene or 1,3-bis(4-hydroxybutoxy)benzene as diol. The structure of each compound was determined by NMR and elemental analysis, and its purity by RLC. As regards the results of elemental analysis, the values of C, H and P alone are shown in TABLE 9. All the -compounds showed a purity of at least 95% TABLE 9 EMI82.1 Example <SEP> Chemical <SEP> Structure <SEP> Element <SEP> Analysis <SEP> (%) <tb> <SEP> C <SEP> H <SEP> P <tb> <SEP> CH3 <SEP> O <tb> 39 <SEP> # <SEP> 51.5 <SEP> 6.5 <SEP> 8.2 <tb> <SEP> H2C=C-COO-(CH2)3-O-#-O-(CH2)3-O-P-(OH)2 <SEP> (51.3) <SEP> (6.2) <SEP> (8.3) <tb> <SEP> H <SEP> O <tb> 40 <SEP> # <SEP> 50.3 <SEP> 5.6 <SEP> 8.8 <tb> <SEP> H2C=C-COO-(CH2)3-O-#-O-(CH2)3-O-P-(OH)2 <SEP> (50.0) <SEP> (5.9) <SEP> (8.6) <tb> <SEP> H <SEP> O <tb> 41 <SEP> # <SEP> 53.3 <SEP> 6.6 <SEP> 8.0 <tb> <SEP> H2C=C-COO-(CH2)4-O-#-O-(CH2)4-O-P-(OH)2 <SEP> (53.7) <SEP> (6.8) <SEP> (7.7) <tb> <SEP> H <SEP> O <tb> 42 <SEP> # <SEP> 53.2 <SEP> 6.8 <SEP> 7.8 <tb> <SEP> H2C=C-COO-(CH2)4-O-#-O-(CH2)4-O-P-(OH)2 <SEP> (52.6) <SEP> (6.5) <SEP> (8.0) <tb> Note: ( ) Calculated value EXAMPLES 43 AND 44 Three adhesive compositions containing the compounds of EXAMPLES 37 and 38, and 2-methacryloyloxyethyl dihydrogen phosphate as the adhesive monomer were prepared in accordance with the following recipe, and tested for adhesive strength and its durability in water: Components and Proportions: : Package I Adhesive monomer 5 parts by weight Methyl methacrylate Benzoyl peroxide 1 part Package II Polymethyl methacrylate 100 parts by weight powder Sodium benzenesulfinate 3 N,N-diethanol-p-toluidine 1 part r -.' Package II was b uniform mixture of the benzene sulfinate and amine powders in the PNMA powder. A 10 mm square by 3 mm thick plate of a Ni-Cr alloy containing 92.7% of nickel was polished with 1000 abrasive paper, and washed ultrasonically in water and methyl ethyl ketone. An adhesive cellophane tape having a hole with a diameter of 5 mm was bonded to the plate so that the hole might be aligned with the center of the polished plate surface. An equal number of stainless steel bars having a diameter of 7 mm and a length of 35 mm were prepared, and one end surface of each bar was polished and washed as the alloy plates had been. A mixture containing equal weights of the components in Packages I and II was applied by a brush to the alloy plate exposed through the hole in the cello phane- tape, and the stainless steel bar, and the plate -and the bar were joined to each other by forming a butt joint. Twenty samples, or bonded bar and plate combinations were prepared by employing each adhesive composition, and immersed in water at 370C after an hour. Ten samples were removed from water after 24 hours, and the remaining 10 samples after 10 days. They were examined for adhesive strength by an Instron tensile tester. TABLE 10 shows the average of the results obtained. Adhesive failure was entirely found on the Ni-Cr alloy surface. TABLE 10 Adhesive Strength 24 hours 10 days Adhesive Monomer kg/cm2 MPa kg/cm2 MPa Example 43 Monomer of Example 37 459 45.0 461 45.2 " 44 e " 38 450 4i.1 443 43.4 Comparative 2-metnacryloyloxyethyl 163 16.0 13 1.3 Example 1 dihydrogen phosphate As is obvious-from TABLE 10, the adhesive compositions of this invention showed a very high initial adhesive strength exceeding 400 kg/cmê (39.2 MPa), and did not undergo any appreciable reduction in adhesive strength after 10 days of immersion in water. On the other hand, the composition of Comparative Example 1 containing a conventional phosphate ester showed a great reduction in adhesive strength as a result of immersion in water. EXAMPLES 45 AND 46, AND COMPARATIVE EXAMPLE 5 Two-pack adhesive compositions were prepared in accordance with the following recipe by employing the monomers of EXAMPLES 37 and 38, and COMPARATIVE EXAMPLE 1, applied to bond a commercially available dental composite resin to acid etched human dentin and unetched dentin, and examined for adhesive strength: : Package III 2,2-bis[4-(3-methycryloyloxy-2- 40 parts by weight hydroxypropoxy)phenyXpropane 2-hydroxyethyl methacrylate 30 " Diethylene glycol dimethacryl- 23 " " ate Adhesive monomer 7 " 'H r Benzoyl peroxide 1.5 -n Package IV 95% ethanol -100 parts by weight Sodium benzenesulfinate 4 " " " N,N-diethanol-p-toluidine 1 part Human molars were cut in the shape of a square pillar to expose an adherend dentin surface and square ivory bars measuring 10 mm square by 30 mm long were also prepared. They were kept in cold water until immediately prior to use. A half of the molars were subjected to acid etching, while the other molars were not. Immediately prior to use, water was wiped off the adherend dentin surface of each molar. The dentin surface of each molar to be etched was subjected to etching for a minute with a 40% aqueous solution of orthophosphoric acid. The etched surface was washed carefully with flowing water, and clean air or nitrogen was blown against the etched surface to volatilize water therefrom. A strip of aluminum was wound about the molar. Water was wiped off the adherend surfaces of the ivory bars, too. A mixed solution containing equal volumes of the liquids III and IV was coated on the teeth and the ivory bars, and clean air or nitrogen was blown against them- to dry them A commercially available dental composite resin Clearfil F (trade- mark of KURARAY CO., LTD., Japan) was kneaded. The resulting. paste was sandwiched between the adherend surfaces of the tooth and the ivory bar, and the tooth and the ivory bar were joined to each other. The test samples were immersed in water at 37 C after 30 minutes of adhesion, and examined after one day for adhesive strength by an Instron tensile tester at a crosshead speed of- 2 mm/min. The results are shown in TABLE 11. Seven teeth were employed for testing each adhesive composition. TABLE 11 shows the average of the results obtain, TABLE 11 Adhesive Strength Etched Unetched Adhesive Monomer 2 2 kg/cm NPa k/cm MPa Examp-le 45 Monomer of Example 37 165 16.2 66 6.5 46 s n " 38 157 15.4 62 6.1 Comparative " " Comparative 32 3.1 7 0.7 Example 5 Example 1 As is obvious from TABLE 11, the adhesive compositions of this invention showed an extremely higher adhesive strength than the composition containing a zonventional phosphate ester. The adhesive composition of this invention provides a high adhesive strength as required for clinical application in dentistry, even if no acid etching is made on the dentin. This enables the simplification of dental treatment which has never been expected from the prior art. EXAMPLE 47 Two-pack adhesive compositions were prepared in accordance with the following recipe by employing the adhesive vinyl compounds shown in TABLE 12, tested for bonding a cor=mercially available dental composite resin to the dentin of a human tooth, and examined for adhesive strength: : Package I Bis-G!S 40 parts by weight Neopentyl glycol dimethacryl-35 -" ate Adhesive vinyl compound 25 " " " Benzoyl peroxide 1.5 n 2,6-di-t-butyl-p-cresol 0.03 part by weight Package II Ethanol 100 parts by weight Sodium benzenesulfinate A N,N-diethanol-p-toluidine 1.7 Human molars were cut in the shape of a square pillar to expose an adherend dentin surface and square ivory bars measuring 10 mm square by 30 mm long were also prepared. They were kept in cold water until immediately prior to use. Immediately prior to use, water was wiped off the adherend dentin surface of each molar, and the dentin surface was etched with a 40% aqueous solution of orthophosphoric acid for a minute. The etched surface was-washed carefully with flowing water, and clean air or nitrogen was blown against it to volatilize any moisture. A strip of aluminum was wound about the molar. Water was wiped off the adherend surfaces of the ivory bars, too. A mixture containing equal volumes of the liquids I and II was- coated cn the adherend surfaces of the tooth and the ivory bar. Clean air or nitrogen was blown against the adherend surfaces to volatilize ethanol. A commercially available dental. composite resin Clearfil F (trademark of KERARAY CO., LTD., Japan) was kneaded to form a paste. This paste was sandwiched between the adherend surfaces of the tooth and- the ivory bar, and bonded thereto. The test samples were immersed in water at 370C after 30 minutes of immersion and examined after one day for adhesive strength by an Instron.tensile tester at a crosshead speed of 2 mm/min. The results are shown in TABLE 12. Seven teeth were employed for testing each adhesive composition. TABLE 12 shows the average of the results obtained. TABLE 12 EMI89.1 <tb> <SEP> No. <SEP> icilesxec <SEP> vinyl <SEP> cco <SEP> Ur,a <SEP> IS"1H(SiV- <SEP> I <SEP> ;tjesivc' <tb> <SEP> -c-tren <SEP> gtir <tb> <SEP> }.IMan <SEP> tOOL; <SEP> C)n <SEP> metal <tb> <SEP> 2 <tb> <SEP> CH3 <SEP> em <SEP> ¯ <SEP> Pa¯ <SEP> U <SEP> v <SEP> cm <tb> <SEP> CH <tb> <SEP> 1 <SEP> ¸C·C3oo < CH?O(O}12) <SEP> RX <SEP> 57-7 <tb> <SEP> CH3 <tb> <SEP> 2 <SEP> 1 <SEP> H3C-CtCH,-)-oPo(oH <SEP> ) <SEP> 110 <tb> <SEP> 3 <SEP> | <SEP> h2C=C-COO4CH2)10OPO(OH2) <SEP> 172 <SEP> 16.9 <SEP> j <SEP> 465 <tb> <SEP> fi2CsC-COOfCf2CHO: <SEP> 107 <SEP> 10.5 <SEP> 423 <tb> <SEP> CN3 <tb> <SEP> 5 <SEP> 1 <SEP> 2 <SEP> C=6-COOCH <SEP> -"Th <SEP> CH <SEP> 142 <SEP> 139 <SEP> : <SEP> 4-6 <SEP> 428 <tb> <SEP> 2 <SEP> 2 <SEP> \±t <SEP> 2-OPO(OH)2 <SEP> I <SEP> I <tb> <SEP> I. <tb> <SEP> 6 <SEP> 2C-COOCH2C <SEP> z <SEP> -OCH2CH2-OPO(OH)2 <SEP> - <SEP> 151 <SEP> 14.8 <SEP> | <SEP> 446 <SEP> 43.7 <tb> . <SEP> 148 <SEP> C1}33 <tb> <SEP> 7 <SEP> -COOCH <SEP> 2 <SEP> 148 <SEP> 14.5 <SEP> 413 <SEP> 40.5 <tb> <SEP> H2C-C <SEP> 2ff\ & CH2-OPO(OH) <tb> <SEP> I <SEP> CH <SEP> CH3 <SEP> I <tb> <SEP> 8 <SEP> ' <SEP> 2CCH2CR2-OPO(OH)2 <SEP> 101 <SEP> 9.9 <SEP> L <SEP> 438 <SEP> 43.0 <tb> <SEP> 3 <SEP> .3 <tb> <SEP> 9 <SEP> t <SEP> H <SEP> C=C¯COOChWH <SEP> CH-OPOtOM) <SEP> ; <SEP> 9 <SEP> 8.8 <SEP> 1 <SEP> 387 <SEP> 38.0 <tb> <SEP> CH <SEP> Ch3 <SEP> 2CH2-3OPO(OR)2 <SEP> 9.4 <SEP> 409 <SEP> 40.1 <tb> <SEP> 1 <SEP> ; <SEP> c- & oocn--ai <SEP> 96 <tb> <SEP> C <tb> <SEP> H3 <SEP> Ch3CH2 <SEP> (32CH2CH3 <SEP> - <SEP> 411 <SEP> 2 <tb> <SEP> 2 <SEP> 2 <SEP> 2 <tb> <SEP> C:H3 <tb> <SEP> 12 <SEP> H2C=C-COOCH2CH-OPO(OH)2 <SEP> 82 <SEP> 8.0 <SEP> 08 <SEP> 0. <tb> <SEP> cH3 <tb> <SEP> 13 <SEP> H2C=C¯COO¯ <SEP> W <SEP> P ( H)2 <SEP> | <SEP> 91 <SEP> 8.9 <SEP> 390 <SEP> 38.2 <tb> <SEP> .. <SEP> ... <SEP> ¯HZC'-COD-: <SEP> 3CN <tb> <SEP> 14 <SEP> I <SEP> H2C=C-COO0C21OPO(OH)2 <SEP> 103 <SEP> 10.1 <SEP> 408 <SEP> 40.0 <tb> <SEP> CH3 <tb> <SEP> CH2R <tb> <SEP> 15 <SEP> N2C=CCh±CO3OCH2CHOPO(ON)2 <SEP> 88 <SEP> 8.6 <SEP> E20 <SEP> 41.2 <tb> <SEP> Where <SEP> CH200CSCHZr <SEP> 16CH3 <tb> <SEP> CH3 <SEP> CH2OOCCH2CH3 <SEP> 110 <SEP> 10.8 <SEP> 447 <SEP> 43.8 <tb> <SEP> H2C=C-COOCH2 <SEP> CN-OPO(OH)2 <tb> EMI90.1 <tb> <SEP> aJJu-so <SEP> vinyl <SEP> cf <SEP> s <SEP> -la <SEP> ------ <SEP> -- <SEP> hr <SEP> 1 <SEP> Adnesive <tb> <SEP> strength <SEP> on <SEP> cr.I-z-rd <SEP> 1 <SEP> F.ilcilvr <SEP> strength <tb> <SEP> human <SEP> o <SEP> tooth <SEP> on <tb> <SEP> k <SEP> cm2 <SEP> 1Pa <SEP> kg/cm <SEP> a <tb> <SEP> CH3 <SEP> ssOPO(OH) <SEP> 2 <SEP> CH3 <tb> <SEP> 1 <SEP> 1 <SEP> CH <SEP> 1 <tb> <SEP> 17 <SEP> H2C=C-COOCH2CHCH2OOCCH2CN2COOa32CH2OOC-C=CH2 <SEP> 121 <SEP> 11.9 <SEP> 435 <SEP> 42.7 <tb> <SEP> 18 <SEP> Cur3 <SEP> i <SEP> CH2CH3. <SEP> 88 <SEP> 8.6 <SEP> 410 <SEP> 40.2 <tb> <SEP> j(H2C-c-COOCH2CCH2-OPO(OH)2 <tb> <SEP> CR <SEP> COOH <tb> <SEP> 19 <SEP> IHZDC-CONhCHCH. <SEP> 93 <SEP> 93 <SEP> CH3 <SEP> 388 <SEP> 38.0 <tb> <SEP> z''\OiO <SEP> 1 <tb> <SEP> I <SEP> <tb> <SEP> 21 <SEP> 2 <SEP> H2C=CCOO*CH2 < 0OPQ(OH) <SEP> 2 <SEP> 159 <SEP> 15.6 <SEP> 430 <SEP> 42.2 <tb> <SEP> CH3 <tb> <SEP> 22 <SEP> j <SEP> H2C=C-CONH4CH2 6Nt11PO <SEP> (OH3 <SEP> 3 <SEP> 98 <SEP> 9.6 <SEP> 392 <tb> <SEP> 1 <SEP> I <SEP> H2O=C-CONHCH2*6NH-PO <SEP> (OH)2 <SEP> 98 <SEP> 9.6 <SEP> 38.4 <tb> <SEP> CH <SEP> 0 <tb> <SEP> 23 <SEP> 3 <SEP> Ii <tb> <SEP> ffa-C-CONHfCH <SEP> t,P-Off <SEP> 1U) <SEP> 11,8 <SEP> 465 <SEP> 45. <SEP> 6 <tb> <SEP> OH <tb> <SEP> 24 <SEP> H <SEP> O <SEP> 9 <SEP> 106 <SEP> 10.4 <SEP> 452 <SEP> 443 <tb> <SEP> 50sfcazt <SEP> s7P <SEP> 2. <SEP> OH <tb> <SEP> 25 <SEP> H2 <SEP> CHI3 <SEP> 9 <SEP> 89 <SEP> 8.7 <SEP> 380 <SEP> 37.3 <tb> <SEP> 25 <SEP> H2C=C <SEP> - <SEP> COOCH2CCH <SEP> O- <SEP> P-OH <tb> <SEP> CH2CH2CH3 <SEP> L <SEP> CH3 <SEP> O'H <tb> <SEP> bi <SEP> 1 <tb> <SEP> Lm <tb> <SEP> H3 <tb> <SEP> 37 <SEP> 3 <tb> <SEP> 28 <SEP> H2c--C-CooaH2o3 <SEP> 2 <SEP> 5 <SEP> H2C-C-COOCHCH2O)'m0,OCH2CH2+5OOC-C1=CH2 <SEP> 138 <SEP> 13.5 <SEP> 457 <SEP> 44.8 <tb> CH3 <SEP> 9 <tb> <SEP> 29 <SEP> H <SEP> C-C-COOCH <SEP> CH <SEP> OCR <SEP> C=CCR <SEP> oCF <SEP> CR <SEP> OP-OH <SEP> 121 <SEP> 11.9 <SEP> 401 <SEP> 39.3 <tb> <SEP> 30 <SEP> H <SEP> CCCOOCH2CH <SEP> O--OH <SEP> CH <tb> <SEP> ! <SEP> I <SEP> 'iIi,ooc <SEP> 3 <SEP> OH <tb> <SEP> 2 <SEP> CoDeCoO*CH23 <SEP> 152 <SEP> 152 <SEP> 14.9 <SEP> 438 <SEP> 43.0 <tb> EMI91.1 <tb> <SEP> ^ <SEP> szoe <SEP> nesive <tb> <SEP> C(jr..:. <SEP> 'cured <SEP> Ured <SEP> iistc-ad <SEP> of <tb> <SEP> stre;'gth <SEP> into <SEP> strength <tb> <SEP> No. <SEP> ',oGth <SEP> 1 <SEP> k <SEP> copound <SEP> tooth <tb> <SEP> No. <tb> <SEP> 1 <SEP> H2C=C-OOCH3 <SEP> 4 <SEP> 0.4 <SEP> 1 <SEP> 4 <SEP> 0.4 <tb> <SEP> H <SEP> O <tb> <SEP> 2 <SEP> 2 <SEP> 2 <SEP> 2 <SEP> OH <SEP> 25 <SEP> 2-5 <SEP> | <SEP> 128 <SEP> 25 <tb> <SEP> bH <SEP> O <tb> <SEP> CH3 <SEP> 0 <tb> <SEP> 3 <SEP> H2C=C-COOCH2CH20-P-OH <SEP> 272.6 <SEP> 163 <SEP> 16.0 <tb> <SEP> LLbH <tb> <SEP> ClH3 <SEP> O <SEP> 1 <tb> <SEP> 4 <SEP> [H,C=1;-COom,cH,o--OH <SEP> 1 <SEP> 71 <SEP> 7.0 <SEP> 96 <SEP> 9.4 <tb> <SEP> 7 <SEP> Y2C=C-COOCH2CH20-PpOCH3 <SEP> 1 <SEP> 0 <SEP> 4 <SEP> 1 <SEP> 5 <SEP> - <SEP> 5 <tb> <SEP> CH <SEP> , <SEP> O <SEP> l <SEP> s <tb> <SEP> FH? <SEP> O <SEP> I <tb> <SEP> 8 <SEP> H2C=C-LOOCH2CHP-- <SEP> - <SEP> i <SEP> 32 <SEP> 3.1, <SEP> 210 <SEP> 20.6 <tb> <SEP> 9 <SEP> H <tb> . <SEP> 2 <SEP> CH2 <SEP> C; <SEP> OH <SEP> , <SEP> I <tb> <SEP> 30 <SEP> H <SEP> C=C'-COOCHCHcP-OH <SEP> j <SEP> 2;9 <SEP> ; <SEP> 205 <SEP> 20.1 <tb> <SEP> 2 <SEP> n"ai <SEP> 6H <tb> <SEP> 3 <tb> <SEP> CH <SEP> 9 <tb> ---11 <SEP> H2C=C-COOCH2CHCH2P-OH <SEP> 25 <SEP> 25 <SEP> 2-5 <SEP> ' <SEP> 52 <SEP> 5.1 <tb> <SEP> 26H <SEP> L <tb> 6H <SEP> dH9 <SEP> f <SEP> 21 <SEP> 2.1 <SEP> 30 <SEP> 2.9 <tb> <SEP> IOH <tb> 13 <SEP> z13 <SEP> |[H2C=CCOOCH2ç2CHOPOH <SEP> 52 <SEP> - <SEP> 5.1 <SEP> - <SEP> 185 <SEP> 18.1 <tb> <SEP> OH <tb> <SEP> CH3 <SEP> 1 <SEP> + <SEP> 50 <SEP> 4.9 <SEP> 32 <tb> <SEP> 14 <SEP> JH2C=C-COOCH2CH2-,CHO-% <SEP> Na <SEP> -'. <SEP> 3.1 <tb> <SEP> OH <tb> <SEP> CH3 <SEP> 0 <SEP> 1 <tb> <SEP> 15 <SEP> H2C=CCoOCH2CH20 <SEP> 75 <SEP> 7.4 <SEP> 120 <SEP> 11.8 <tb> <SEP> OH <tb> I <SEP> CR3 <tb> <SEP> 16 <SEP> H2C=C- <SEP> 2 <SEP> H2C- <SEP> 70 <SEP> 6.9 <SEP> 91 <SEP> 8.9 <tb> 1 <tb> <SEP> 17 <SEP> &verbar; <SEP> H2C=CH&commat;CH2POH <SEP> - <SEP> I <SEP> 28 <SEP> 2.7 <SEP> 101 <SEP> 9.9 <tb> <SEP> 18 <SEP> | <SEP> H2C=CHCH2-9 <tb> <SEP> OH <tb> <SEP> 19 <SEP> 19 <SEP> | <SEP> H2C=CHPOH <SEP> 20 <SEP> 2.0 <SEP> 11 <SEP> 1.1 <tb> COMPARATIVE EYkE'PLE 6 Adhesive compositions were prepared by employing the adhesive vinyl compounds shown in TABLE 13, and repeating the procedures of EXAMPLE 47 in all the other respects The results are shown in TABLE 13. EXAMPLE 48 Powder-liquid type adhesive compositions were prepared in accordance with the following recipe by employing the adhesive vinyl compounds employed in EXAMPLE 47, and tested for adhesive strength on metal: Package III Adhesive vinyl compound 5 parts by weight Methyl methacrylate 95 " Xi Benzoyl peroxide 1 part Package IV Polymethyl methacrylate 100 parts by weight Sodium benzenesulfinate 3 " " " N,N-diethanol-p-toluidine 1 part A cast plate of a dental Ni-Cr alloy Now Chrom (I) (product of TOWA GIKEN K.K., Japan, containing 92.7% Ni, and 6.0% Cr) was ground to provide a smooth surface, polished with 1000 abrasive paper, washed ultrasonically, and dried. As adhesive cellophane tape having a hole with a diameter of 5 mm was bonded to the polished plate surface. A stainless steel (SUS 304) bar having a diameter of 7 mm and a length of 35 mm was likewise polished with &num;1000 abrasive paper, washed ultrasonically, and dried. Equal weights of the components in Packages III and IV were placed in a Dappen dish, and mixed together for 10 to 20 seconds. The resultant viscous mixture was coated on the 2chc-ren surfaces of the alloy plate and the stainless steel bar. They were joined to each other by forming a butt joint. The bonded plate and bar combination was immersed in water at 370C after one hour, and tested after 72 hours for adhesive strength by an Instron tensile tester at a crosshead speed of 2 mm/min. The results are shown in the right column of TABLE 12. COMPARATIVE EXAMPLE 7 Adhesive compositions were prepared by employing the 19 vinyl compounds shown in TABLE 13 instead of the adhesive vinyl compounds in Package III employed in tYS PLE 48, and otherwise repeating the procedures of EXAMPLE 48. They were tested for adhesive strength on the Ni-Cr alloy. The test results are shown in the right column of TABLE 13. EXAMPLE 9 AND COMPARATIVE EXAMPLE 8 The procedures of EXAMPLE 48 were followed for bonding a Ni-Cr alloy by employing the -six adhesive vinyl compounds shown in TABLE 14. The test samples were immersed in water at 370C after one hour of adhesion, and tested after 10 days for adhesive strength. The results are shown in TABLE 14. As is obvious from TABLE 1, the dental adhesive composition of this invention showed a high adhesive strength on not only the dentin, but on the metal as well. It is surprising to note that the adhesive composition of this invention shows a by far higher adhesive strength than the methacryloyloxy dihydrogen phosphate (COMPARATIVE EXAMPLE) which is known for its high adhesive strength on metals. TABLE 14 EMI94.1 <tb> <SEP> Adhesive <tb> <SEP> No. <SEP> Adhesive <SEP> Vinyl <SEP> Compound <SEP> o <SEP> strength <tb> <SEP> fts <SEP> 10 <SEP> days <tb> k <SEP> cm <SEP> HPa <tb> Exnple <SEP> 48 <SEP> CH3 <tb> <SEP> (1) <SEP> 1 <tb> <SEP> B2C=C-Coo4CHz&num;O-PO(OH)2 <SEP> 321 <SEP> 31.5 <tb> <SEP> Example <SEP> 48 <SEP> CH3 <tb> <SEP> (2) <SEP> H2C=C-COO4CR2*O-pO(OH)2 <SEP> 460 <SEP> 45.1 <tb> <SEP> Example <SEP> 48 <SEP> 1 <SEP> 3 <SEP> CR3 <tb> <SEP> H2C' <SEP> H <SEP> -CHZ-OPO(OH)2 <SEP> 402 <SEP> 39.4 <tb> <SEP> omparative <SEP> CH <tb> <SEP> Example <SEP> 8 <SEP> j <SEP> 3 <tb> <SEP> (1) <SEP> H2C=C-COOCH2CR2-OPO(OR)2 <SEP> 13 <SEP> 1.3 <tb> <SEP> ro3sayac, <SEP> ve <SEP> I <tb> <SEP> (2) <SEP> -(12)-Cn2PO <SEP> (OH)2 <SEP> - <SEP> 6 <SEP> &commat; <SEP> CH2PO(OH)2 <SEP> 6 <SEP> o.6 <tb> <SEP> gCm'=:eathvet <SEP> CH3 <SEP> 0 <tb> (3) <SEP> | <SEP> H,C'C-CooCH2CH2-o-P-ol/ <SEP> O) <SEP> 11 <SEP> 1.1 <tb> <SEP> OH <tb> EXAMPLE 4 9A AND COMPARATIVE -XA"'JPLE 9 Two-pack adhesive compositions were prepared in accordance with the recipe of EXAMPLE 47 by employing the phosphate esters shown in TABLE 15, though methacrylic acid was employed in COMPARATIVE EXAMPLE 9(3). The procedures of EXAMPLE 47 were followed for adhesive strength tests on the unetched dentin of the human molar. The dentin surface was cut by a diamond point in a stream of water being poured to provide an adherend surface The test results are shown in TABLE 15. The compounds employed in accordance with this invention were extremely superior in adhesive property to the conventional phosphate esters employee in COMPARATIVE EXAMPLES 9(1) and (2). According to this invention, a clinically significant adhesive strength was obtained without the acid cleaning of the dentin surface. TABLE 15 EMI95.1 <tb> <SEP> Phosphate <SEP> Ester <SEP> .Adhesive <SEP> Strength <tb> <SEP> 2 <tb> Example <SEP> o <SEP> CH3 <SEP> W <SEP> kg/cm <SEP> MPa <tb> I <SEP> Ii <tb> <SEP> (1) <SEP> H2C=C-COO+CH2yl00-P-OH <SEP> 73 <SEP> 7.2 <tb> <SEP> CH3 <SEP> OH <SEP> 0 <tb> <SEP> (2) <SEP> H2C=C-COOCH2CH2 <SEP> O0; ;OCH2CH2OPOH <SEP> 71 <SEP> 7.0 <tb> <SEP> OH <tb> <SEP> Comparative <SEP> CH3 <SEP> 0 <tb> <SEP> Example <SEP> 9(1) <SEP> H2C=C-COOCH2CH2-D-P-OH <SEP> 10 <SEP> 1.0 <tb> <SEP> CH3 <SEP> oOH <tb> <SEP> II <tb> <SEP> (2) <SEP> H2C=C-COOCH2CH20-P-0 <SEP> 25 <SEP> 2.5 <tb> <SEP> CR <SEP> 6H <tb> <SEP> 0 <SEP> 0 <tb> <SEP> (3) <SEP> H2C=C-COOH <tb> EXAMPLE 50 A dental restoration system comprising thr adhesive composition of EXAMPLE 49A(1) and z commercially available composite resin of the following recipe was tested for dental treatment: Two-Pack Composite resin: : Package I Quartz powder 75 parts by weight Triethylene glycol dimeth- 8 " " " acrylate 2,2'-bis[p-(&gamma;-methaxryloxy- 15 " &num;-hydroxypropoxy)phenylapro- pane (Bis-GMA) Colloidal silica 2 " Dibenzoyl peroxide 0.5 part by weight Hocroauinone monomethyl ether 0.01 2,6-di-t-butylp-resol 0.01 " " 2-Hydroxy-4-methoxybenzo- 0.01 " " phenone Package II Quartz powder 75 parts by weight Triethylene glycol dimeth- 8 " " acrylate 2,2'-bis[p-(&gamma; ;-methacryloxy- 15 ss-hydroxypropoxy)phenyl]pro pane (Bis-GMA) Colloidal silica 2 N,N-diethanol-p-toluidine 0.2 part by weight Hydroquinone monomethyl ether 0.01 " 2-Hydroxy-4-methoxybenzo- 0.01 phenone 2,6-di-t-butyl-p-cresol 0.01 Two cylindrical cavities having a cian,eter of 3.5 mm, and a depth of 3 mm were formed in an extracted human molar by a diamond point in a stream of water being poured. The cavities were treated with a 40% aqueous solution of phosphoric acid for a minute, washed with water, and dried fully by an air syringe. Two liquids forming the adhesive composition of EXAMPLE 49(1) were dropped into a Dappen dish, and mixed together. The resultant mixture was coated on the inner surfaces of the cavities, and air was blown thereagainst by an air syringe for several seconds to volatilize ethanol. The components of the twopack composite resin were mixed, and the resultant mixture was filled in the cavities under pressure. The molar was immersed in water at 370C overnight, and on the following day, the excess of the composite resin was removed to expose the margins of the cavities. The remaining portion of the tooth was sealed with an acrylic resin. The test samples were immersed alternately in two aqueous solutions of fuchsine having a temperature of 40C and 60"C, respectively, 100 times for a minute each time for examination as to the penetration of the dye into the cavity margins (percolation test). After the percolation tests had been finished, the tooth was split, and did not indicate any penetration of fuchsine into the margins. EXAMPLE 51 A powder-liquid type adhesive composition was prepared by employing adhesive monomer No. 3 of EXAMPLE 47, and tested for adhesive strength on the dentin of human teeth, the enamel of bovine teeth, and a Ni-Cr alloy Nowchrom (I) (product of TOWS GIKEN K.K., Japan) (1) Components of the Adhesive Composition: : Package V (Liquid) Bis-GMA 40 parts by weight 1,10-Decanediol dimethacrylate 3Q " HEMA 20 -Adhesive monomer No. 3 of 10 " " EXAMPLE 47 Benzoyl peroxide 1 part Hydroguinone monomethyl ether 0.05 " " " Package VI (Powder) Silanated quartz powder 100 parts by weight Sodium benzenesulfinate 0.6 part N,N-Diethanol-p-toluidine 0.6 " The powder VI was prepared by spraying a solution of sodium benzenesulfinateand N,N-diethanol-p toluidine in 10 parts by weight of methanol uni formly on quartz powder, and volatilizing methanol. (2) Adhesion on Human Dentin: The crown of a human molar was cut off to expose the dentin, while water was being poured on the tooth. The dentin surface was etched with a 40% aqueous solution of orthophosphoric acid for a minute, and after it had been washed with water, the water on the dentin surface was blown away by an air syringe. A double coated adhesive tape was bonded to the dentin surface. The tape had a hole with a diameter of 5 mm. The tooth was supported so that it might have a horizontal cross section. Aplastics ring having an inside diameter of 6 mm and a thickness of 5 mm was placed on the tape so that the ring might be aligned with the center of the hole in the tape. The liquid V dnd the powder VI were mixed in a ratio by weight of 1:2, and kneaded for about one minute to form a paste. This paste was filled in the ring, and a hook for a tensile test was anchored in the paste and left at rest for 30 minutes. This test sample was immersed in water at 370C. ' Five teeth were employed for testing each adhesive composition. (3) Adhesion on Bovine Tooth Enamel: The labial surface of a bovine incisor was ground in a stream of water to provide a smooth surface. The procedures described at (2) above were followed for the acid etching of the labial surface, and the preparation of a test sample. (4) Adhesion on Ni-Cr Alloy: A 10 mm square by 3 mm thick plate and a round bar having a diameter of 7 mm and a length of 20 mm were cast from a Ni-Cr alloy Nowchrom (I) containing 928 Ni (product of TOWA GIKEN K.K., Japan). The plate and the bar were polished with =1000 abrasive paper, washed ultrasonically with water, and dried by an air syringe. An adhesive backed tape Transpore (trademark) having a hole with R diameter of 5 mm was bonded to the alloy plate. The liquid V and the powder VI were mixed in a ratio by weight of 1:2, and kneaded for about one minute to form a paste. A thick layer of the paste was applied onto one end of the bar, and pressed against the plate to bond the bar to the plate. The test sample thus prepared was left at rest for 30 minutes, and immersed in water at 370C. Six samples were prepared by employing each adhesive composition. (5) Adhesive Strength Test: After one week of immersion in water at 370C, each sample was examined for adhesive strength by an Instron tensile tester at a crosshead speed of 2 mm/min. TABLE 16 shows the average of the results obtained on the several samples in each case. TABLE 16 EMI100.1 <SEP> 1 <SEP> 2 <tb> <SEP> Adhesive <SEP> Strength <SEP> MPa <tb> <SEP> MPa <tb> <SEP> Adhesive <SEP> Monomer <SEP> Human <SEP> dentin <SEP> Bovine <SEP> enamel <SEP> Ni-Cr <SEP> alloy <tb> <SEP> CE3 <SEP> - <SEP> '. <SEP> O <SEP> ° <tb> <SEP> 1 <SEP> <tb> H2C=C-COO+CH20 <SEP> 0-P-OH <SEP> 120 <SEP> 162 <SEP> 438 <tb> <SEP> OH <SEP> 11.8 <SEP> .9 <SEP> 43.0 <tb> EXAMPLE 52 A cylindrical cavity having a diameter of 4 mm and 2 depth of 3 mm was formed in the occlusal surface of an extracted human molar by a diamond point while water was being poured on the molar. An inlay fitting the cavity was cast from a 14-carat gold alloy, and its adherend surface was sandblasted. with alumina particles having a particle size of 30 microns. The cavity was not etched with an acid, but was only washed with water, and dried fully by an air syringe. The liquid and the powder for the powder-liquid type adhesive composition (resin cement) employed in EXAMPLE 51 were mixed in a ratio of 0.1 to 0.4 g, and kneaded for a minute to form a soft paste. This paste was coated on the cavity surface, and the inlay was immediately fitted in the cavity. The bonded molar and inlay assembly was immersed in water at 370C after 10 minutes, and subjected to a percola tion test after 24 hours in accordance with the method employed in EXAMPLE 50. The test results indicated that the penetration of fuchsine had stopped in the enamel in the cavity, and that there was no penetration of fuchsine in the dentin. EXAMPLE 53 A visible light curing dental composite resin was prepared from 15 parts by weight of Bis-GER, 4 parts by weight of 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 4 parts by weight of neopentyl glycol dimethacrylate, 3 parts by weight of 10-methacryloyloxydecyl dihydrogen phosphate, 0.1 part by weight of camphorquinone, 0.3 part by weight of allylthiourea, 73 parts by weight of silanated quartz powder, and 1.5 parts by weight of colloidal silica. A cavity having a diameter of 3 mm and a depth of 2 mm was formed in the labial surface of an extracted human incisor by a diamond point. The cavity was etched, washed with water, and dried in accordance with the procedures of EXAMPLE 50. The cavity was filled with the composite resin, and the resin was exposed for three minutes to the light of a 500 W tungsten-halogen lamp. The tooth was, then, immersed in water at 37 C. After it had been removed from water, it was cut, and the adhesion of the resin to the cavity wall was examined through a microsccpe. This examination indicated complete adhesion of the resin to the cavity wall, and did not reveal any clearance therebetween. EXAMPLE 54 AND COMPARATIVE EXAMPLE 10 Powder-liquid type adhesive compositions were prepared in accordance with the following recipe by employing the phosphate esters shown in TABLE 17, tested for adhesion on nickel and a cold alloy, and examined for the durability of their adhesive strength in water. (1) Recipe: Package I (Liquid) Adhesive vinyl compound 5 parts by weight Methyl methacrylate 95 us benzoyl peroxide 1 part " " Package II (Powder) PMMA powder 100 parts by weight Sodium benzenesulfinate 3 5' 1s N,N-Diethanol-p-toluidine 1 part " " The powder II was prepare by grinding sodium benezenesulfinate and N,N-diethanol-p-toluidine into fine particles, and dispersing them in the PMMA powder. (2) Adhesion on Nickel: One end surface of a round nickel bar having a diameter of 7 mum and a length of 30 mm was polished with &num;1000 silicon carbide abrasive paper, washed ultrasonically in water for 10 minutes, and dried. Equal weights of the liquid I and the powder II were mixed to form a viscous mixture The viscous mixture was coated on the end surfaces of a pair of nickel bars forming one test sample, and the bars were joined together by forming a butt joint. Fourteen samples were prepared for testing each adhesive composition. The samples were left at rest in a temperature controlled bath having a constant temperature of 30 C for 24 hours, and seven samples were immediately removed from the bath and examined for adhesive strength by a tensile tester. The other seven samples were tested for adhesive strength after they had been immersed in water at 30"C for five days. (3) Adhesion on Gold Alloy: An 8 mm square by 1.5 mm thick plate of a gold alloy containing 555 Au, 29% Ag and 8.98 Pd, and one end of a round stainless steel (SUS 304) bar having a diameter of 5 mm and a length of 30 mm were polished and washed, as the nickel bars had been. A Transpore (trademark) surgical tape having a hole with a diameter of 4 mm was bonded to the gold alloy plate to serve as a spacer. The adhesive composition was applied in a somewhat thick layer to the gold alloy plate exposed through the hole in the tape. The polished end of the stainless steel bar was pressed against the adhesive layer, and bonded to the gold alloy plate. The test samples thus prepared were kept and examined for adhesive strength in accordance with the procedures described at (2) above for the nickel samples. The results are shown in TABLE 17. TABLE 17 EMI104.1 No. <SEP> Nickel <SEP> Gold <SEP> Alloy <tb> <SEP> Phosphate <SEP> Ester <SEP> Initial <SEP> After <SEP> immersion <SEP> Initial <SEP> After <SEP> immersion <tb> <SEP> in <SEP> water <SEP> in <SEP> water+ <tb> <SEP> CH3 <SEP> O <tb> <SEP> # <tb> Example <SEP> 54(1) <SEP> H2C=C-COO-(CH2)6-O-P-OH <SEP> 451 <SEP> 44.2 <SEP> 450 <SEP> 44.1 <SEP> 203 <SEP> 19.9 <SEP> 178 <SEP> 17.5 <tb> <SEP> OH <tb> <SEP> CH3 <SEP> O <tb> <SEP> # <tb> <SEP> " <SEP> 54(2) <SEP> H2C=C-COO-(CH2)4-OOC-#-P-OH <SEP> 426 <SEP> 41.8 <SEP> 409 <SEP> 40.1 <SEP> 176 <SEP> 17.3 <SEP> 155 <SEP> 15.2 <tb> <SEP> OH <tb> <SEP> CH3 <SEP> O <tb> <SEP> # <tb> <SEP> " <SEP> 54(3) <SEP> H2C=C-COO-(CH2)2O-#-(CH2)2-O-P-OH <SEP> 448 <SEP> 43.9 <SEP> 456 <SEP> 44.7 <SEP> 179 <SEP> 17.6 <SEP> 162 <SEP> 15.9 <tb> <SEP> OH <tb> Compara- <SEP> CH3 <SEP> O <tb> tive <SEP> # <tb> Example <SEP> 10(1) <SEP> H2C=C-COOCH2CH2OP-OH <SEP> 361 <SEP> 35.4 <SEP> 53 <SEP> 5.2 <SEP> 105 <SEP> 10.3 <SEP> 0 <SEP> 0 <tb> <SEP> OH <tb> <SEP> CH3 <SEP> O <tb> <SEP> # <tb> <SEP> " <SEP> 10(2) <SEP> [H2C=C-COOCH2CH2O]2-P-OH <SEP> 234 <SEP> 22.9 <SEP> 0 <SEP> 0 <SEP> 61 <SEP> 6.0 <SEP> 0 <SEP> 0 <SEP> OH <tb> <SEP> CH3 <SEP> O <tb> <SEP> # <tb> <SEP> " <SEP> 10(3) <SEP> H2C=C-COO-(CH2CH2O)3-P-OH <SEP> 287 <SEP> 28.1 <SEP> 0 <SEP> 0 <SEP> 73 <SEP> 7.2 <SEP> 0 <SEP> 0 <tb> <SEP> OH <tb> EXAMPLE 55 The procedures of EXAMPLE 54 were followed for preparing test samples each consisting of a pair of round bars having a diameter of 7 mm and a length of 30 mm, and joined end to end by employing the adhesive composition containing the phosphate ester shown at EXAMPLE 54(1) in TABLE 17. The samples were prepared from bars of stainless steel (SUS 304), ordinary steel, aluminum, hard glass, PMA and polycarbonate. They were left at rest in a dry temperature controlled bath having a constant temperature of 30 C for 24 hours, and examined for adhesive strength by a tensile tester. The results were as follows: Adhesive Strength Sample 2 kg/cmê MPa Stainless steel 463 45.4 Ordinary steel 470 46.1 Aluminum 251 24.6 Hard glass 233 ' 22.8 PMMA 320 31.4 Polycarbonate 265 26.0 EXAMPLE 56 AND COMPARATIVE EXAMPLE 11 Powder-liquid adhesive compositions were prepared in accordance with the following recipe by employing the phosphate esters shown in TABLE 18: : Package III (liquid) Bi s-GMA 50 parts by weight 1,4-Butanediol dimethacrylate 40 Phosphate ester compound 10 Benzoyl peroxide 1 part 'µ 2 ,6-Di-t-butyl-p-cresol Trace Package IV (Powder) Silica powder 100 parts by weight Sodium benzenesulfinate 0.5 part N,N-Diethanol-p-toluidine 0.5 Test samles were prepared from stainless steel (SUS304) bars having a diameter of 7 mm and a length of 30 mm. One end surf ace o.f each bar was polished with silicon carbide abrasive paper. The bars were immersed in water at 250C. The liquid III and the powder IV were mixed in a ratio by weight of 1:4, and kneaded by a spatula for a minute to form an adhesive paste. A pair of bars were joined to each other by the paste while they were in water. The samples were left at rest in water at 25 C., and examined after one day for adhesive strength by a tensile tester. Five samples were prepared for testing each adhesive composition. TABLE 18 shows the average of the results obtained on those samples. TABLE 18 EMI106.1 <tb> <SEP> Phosphate <SEP> Ester <SEP> Adhesive <SEP> Strength <tb> Example <SEP> 56 <SEP> CR3 <SEP> -O <SEP> - <SEP> MPa <tb> <SEP> I <SEP> II <SEP> 2 <SEP> MPa <tb> <SEP> H <SEP> 2C=C-COO+CR210O-P-OR <SEP> 384 <SEP> 37-7 <tb> <SEP> OR <tb> <SEP> CH <SEP> CR <SEP> Cl <SEP> 0 <tb> Comparative <SEP> 3 <SEP> I <tb> Example <SEP> 11 <SEP> C=C-COO <SEP> CH <SEP> ZM-O-P-OH <SEP> -26 <SEP> 2.5 <tb> <SEP> OH <tb> EXAMPLE 57 AND COMPARATIVE EXAMPLE 12 Light curable paint compositions were prepared in accordance with the following recipe by employing the phosphate esters shown in TABLE 19: : Recipe Phosphate ester 3 parts by weight Methyl methacrylate 20 n-Butyl acrylate 20 " " " Styrene 10 " n ." Benzoinisopropyl ether 3 " " Oil-free alkyd resin modified 100 with a urethane compound A film of each paint composition having a thickness of 40 microns was formed on a steel plate polished with &num;800 ab'rasive paper. The composition was cured by exposure for 20 seconds to the light of a 2 kW high-pressure mercury lamp positioned at a distance of 30 cm from the plate. The plate was, -then, immersed in water at 700C for 20 days, and the coated film was examined. The results are shown in TABLE 19. TABLE 19 EMI107.1 <tb> <SEP> Phosphate <SEP> Ester <SEP> Change <SEP> in <SEP> Coated <SEP> Film <tb> Example <SEP> 57 <SEP> H <SEP> o <tb> <SEP> H2 <SEP> C <SEP> C O+CE2+2 <SEP> o0+cH2i2 <SEP> 0-P-OH <SEP> None. <tb> <SEP> OH <tb> <SEP> H <SEP> O <tb> Comparative <SEP> I <SEP> !! <tb> Example <SEP> 12(1) <SEP> H2C=C-COOCH2CH2-0-D-OH <SEP> Blisters <SEP> all <SEP> over. <tb> <SEP> OH <tb> <SEP> OR <tb> <SEP> H. <SEP> CH3 <SEP> o <tb> Comparative <SEP> í <SEP> . <SEP> i <SEP> 3 <tb> Example <SEP> 12(2) <SEP> H2C=C-COOCH2CH-C-:-OH <SEP> t <SEP> 0C <tb> <SEP> i <tb> <SEP> OH <tb> EXAMPLE 58 AND COMPARATIVE EXAMPLE 13 Powder-liquid type adhesive compositions were prepared in accordance with the following recipe by employing the phosphate esters shown in TABLE 20, tested for adhesion on nickel and a gold alloy. (1) Recipe: Package I (Liquid) Phosphate ester compound 5 parts by weight Methyl methacrylate 95 n Benzoy peroxide 1 part Package II (Powder) - PMA- powder 100- parts' by weight Sodium benzenesulfinate 3 N ,N-Diethanol-p-toluidine I part The powder was prepared by grinding sodium benzene sulfinate and N,N-diethanol-p-toluidine into fine particles, and dispersing them uniformly in the SMA powder. (2) Adhesion on Nickel: Round nickel bars having a diameter of 7 mm and a length of 30 mm had one end surface polished with 1000 silicon carbide abrasive paper, and were washed ultrasonically in water for 10 minutes, and dried. Equal weights of the liquid I and the powder II were mixed to form a viscous mixture. It was coated on the polished ends of the bars, and each pair of bars were joined end to end. Fourteen test samples were prepared for testing each adhesive composition. They were left at rest in a temperature controlled bath having a constant temperature of 30 C for 24 hours. Seven of them were, then, removed from the bath immediately, and examined for adhesive strength by a tensile tester. The other seven samples were earinec for adhesive strength after they had been immersed in water at 300C for five days. (3) Adhesion on Gold Alloy: An 8 mm square by 1.5 mm thick plate of a gold alloy containing 55% Au, 296 Ag and 8.98 Pd, and one end surface of a round stainless steel (SUS 304) bar having a diameter of 5 mm and a length of 30 mm were polished and washed as the nickel bars had been. A Transpore (trademark) surgical tape having a hole with a diameter of 4 mm was bonded to the gold alloy plate to serve as a spacer. The adhesive composition was applied in a somewhat thick layer to the gold alloy plate exposed through the hole in the tape. The polished end of the stainless steel bar was pressed against the adhesive layer, and bonded to the gold alloy plate. The test samples were kept and examined for-adhesive strength in accordance with the procedures as hereinbefore described with reference to the nickel samples. The results are shown in TABLE 20. TABLE 20 EMI110.1 No. <SEP> Nickel <SEP> Gold <SEP> Alloy <tb> <SEP> Phosphate <SEP> Ester <SEP> Initial <SEP> After <SEP> immersion <SEP> Initial <SEP> After <SEP> immersion <tb> <SEP> in <SEP> water <SEP> in <SEP> water <tb> <SEP> CH3 <tb> Example <SEP> 58(1) <SEP> H2C=C-COOCH2CHCH2O-# <SEP> 433 <SEP> 42.5 <SEP> 430 <SEP> 42.2 <SEP> 162 <SEP> 15.9 <SEP> 147 <SEP> 14.4 <tb> <SEP> OPO3H2 <tb> <SEP> CH3 <tb> <SEP> " <SEP> 58(2) <SEP> H2C=C-COOCH2CHCH2OOC-(CH2)6-CH3 <SEP> 415 <SEP> 40.7 <SEP> 408 <SEP> 40.0 <SEP> 157 <SEP> 15.4 <SEP> 144 <SEP> 14.1 <tb> <SEP> OPO3H2 <tb> <SEP> CH3 <tb> <SEP> " <SEP> 58(3) <SEP> H2C=C-COOCH2CHOOC-#-OCH3 <SEP> 427 <SEP> 41.9 <SEP> 424 <SEP> 41.6 <SEP> 168 <SEP> 16.5 <SEP> 156 <SEP> 15.3 <tb> <SEP> PO3H2 <tb> Compara- <SEP> CH3 <SEP> O <tb> tive <SEP> # <tb> Example <SEP> 13(1) <SEP> H2C=C-COOCH2CH2O-P-OH <SEP> 361 <SEP> 35.4 <SEP> 53 <SEP> 5.2 <SEP> 105 <SEP> 10.3 <SEP> 0 <SEP> 0 <tb> <SEP> OH <tb> <SEP> CH3 <SEP> O <tb> <SEP> # <tb> <SEP> " <SEP> 13(2) <SEP> [H2C=C-COOCH2CH2O]2-O-P-OH <SEP> 234 <SEP> 22.9 <SEP> 0 <SEP> 0 <SEP> 61 <SEP> 6.0 <SEP> 0 <SEP> 0 <SEP> OH <tb> <SEP> CH3 <SEP> O <tb> <SEP> # <tb> <SEP> " <SEP> 13(3) <SEP> H2C=C-COO-(CH2CH2O)3-P-OH <SEP> 287 <SEP> 28.1 <SEP> 0 <SEP> 0 <SEP> 73 <SEP> 7.2 <SEP> 0 <SEP> 0 <tb> <SEP> OH <tb> EXAMPLE 59 The procedures of EXAMPLE 58 were followed for preparing test samples each consisting of a pair of round bars having a diameter of 7 mm and a length of 30 mm, and joined end to end by employing the adhesive composition containing the phosphate ester shown at EXAMPLE 58(1) in TABLE 20. The samples were prepared from bars of stainless steel (SUS 304), ordinary steel, aluminum, hard glass, PNMA and polycarbonate. They were left at rest in 2 dry temperature controlled bath having a constant temperature of 30 C for 24 hours, and examined for adhesive strength by a tensile tester. The results. were as follows: Adhesive Strength Sample 2 kg/c MPa Stainless steel 447 43.8 Ordinary steel 452 44.3 Aluminum 266 26.1 Hard glass 209 20.5 PMMA 289 28.3 Pol ycarbonate 263 25.8 EXAMPLE 60 AND COMPARATIVE EXAMPLE 14 Powder-liquid type adhesive compositions were prepared in accordance with the following recipe r5 employing the phosphate esters shown in TABLE 21: : Package III (Liquid) Bis-GMA 50 parts by weight 1,4-BUtanediol dimethacrylate 40 " Phosphate ester compound 10 " " Benzoyl peroxide 1 part " 2,6-Di-t-butyl-p-cresol Trace Package IV (Pcwder) Silica powder 100 parts by weight Sodium benzenesulfinate 0.5 part N,N-Diethanol-p-toluidine 0.5 " Test samples were prepared from stainless steel (SUS 304) bars having a diameter of 7 num and 2 length of 30 mm. One end surface of each bar was polished with silicon carbide abrasive paper. The bars were immersed in ater at Z5 C. The liquid III and the powder IV were mixed in a ratio by weight of 1:4, and kneaded by a spatula for a minute to form an adhesive paste. A pair of bars were joined to each other by the paste while they were in water. The samples were left at rest in water at 250C, and examined after one day for adhesive strength by a tensile tester. Five samples were prepared for testing each adhesive composition. TABLE 21 shows the average of the results obtained on those samples. TABLE 21 EMI112.1 <tb> <SEP> Phosphate <SEP> Ester <SEP> Adhesive <SEP> Strength <tb> Example <SEP> 60 <SEP> CH, <SEP> O <SEP> k/cm2 <SEP> ¯¯¯ <tb> <SEP> Example <SEP> 34.4 <tb> <SEP> H2C=C-COOCH2CHOOC.-O <SEP> 2 <SEP> 351 <SEP> 34.4 <tb> <SEP> 1OPO <SEP> 3R2 <tb> Comparative <tb> Example <SEP> 14 <tb> <SEP> CH3 <SEP> CH2C10 <tb> <SEP> I <SEP> II <tb> <SEP> H2C=C-COOCH2CH-O-P-O26 <SEP> 2.5 <tb> <SEP> OH <tb> EXAMPLE 61 AND COMPARATIVE EXAMPLE 15 Light curable paint compositions were prepared in accordance with the following recipe by employing the phos plate esters shown in TABLE 22: : Recipe Phosphate ester 3 parts by weight Methyl methacrylate 20 n-Butyl acrylate 20 " " " Styrene 10 Benzoinisopropyl ether 3 Oil-free alkyd resin modified 100 " " " with a urethane compound A film of each paint composition having a thickness of 40 pm was formed on a steel plate polished with '800 abrasive paper. The composition was cured by exposure for 20 seconds to the light of a 2 kW high-pressure mercury lamp positioned at a distance of 30 cm from the plate. The plate was, then, immersed in water at 700C for 20 days, and the coated film was examined. The results are shown in TABLE 22. TABLE 22 EMI113.1 <tb> <SEP> Phosphate <SEP> Ester <SEP> Chance <SEP> in <SEP> Coated <SEP> Film <tb> example <SEP> 61 <SEP> H <tb> <SEP> H2C=C-COOCH2C\-CH2-O <SEP> None. <tb> <SEP> w <tb> <SEP> OPO <SEP> }4 <tb> <SEP> 3 <SEP> 2 <tb> Comparative <SEP> H <tb> Example <SEP> 15(1) <SEP> H <tb> <SEP> H2C=C-COOCH2CH2-0-P-OH <SEP> Blisters <SEP> all <SEP> over <SEP> the <tb> <SEP> film. <tb> <SEP> OH <tb> <SEP> OH <tb> Comparative <SEP> H <SEP> CH3 <SEP> 0 <tb> Example <SEP> 15(2) <SEP> | <tb> <SEP> H2C=C-COOCH2 <SEP> CH-O-P-OH <SEP> Blisters <SEP> all <SEP> over <SEP> the <tb> <SEP> zilm <SEP> . <SEP> film. <tb> <SEP> OH <tb>

Claims: CLAIMS 1. An adhesive composition comprising 100 parts by weight of a polymerizable monomer comprising (a) 1.5 to 50 parts by weight of a compound represented by one of formulae I and II: EMI114.1 where each of RI and ' is hydrogen or methyl, R2 is a bivalent organic residue having from 5 to 40 carbon atoms, each of X1 and X2 is -0-, -S- or -NH-, a is O or 1, and R3 is a group of the formula EMI114.2 having 6 to 40 carbon atoms, where each of R4 and R4t is a hydrocarbon group having 1 to 29 carbon atoms optionally having as substituent(s) halogen, hydroxy, amino or carboxy, b is 0, 1, 2 or 3, the 's, if more than one are present, being the same or different, and at least one of R4 and R4' having at least three carbon atoms, and Z is -O-, -CO- or -NH-, and (b) 50 to 9805 parts by weight of a vinyl monomer copolymerizable zth the said compound; and 0.01 to 20 parts by weight of a curing agent. 2. A composition as claimed in Claim 1, in which the said compound is of formula I. 3. A composition as claimed in Claim 2 in which k2 is (a) a hydrocarbon group having 5 to 30 carbon atoms optionally having halogen, hydroxy, amino and/or carboxy substituent(s), or (b) a group having 5 to 30 carbon atoms composed of two to seven hydrocarbon rcsidues bonded to one another by one or more ether, thioether, ester, thioester, thiocarbonyl, amide, urethane, carbonyl and/or sulfonyl linkages, each of the hydrocarbon residues having 1 to 29 carbon atoms and at least one of them having four or more carbon atoms, and optionally having halogen, hydroxy, amino or carbon substituents. 4. A composition as claimed in Claim 3, in which R2 is represented by the formula EMI115.1 where each of R5 and R5' is a hydrocarbon group having 1 to 29 carbon atoms, optionally having halogen, hydroxy, amino and/or carboxy substituent(s), at least one of R5 and R5 having at least four carbon atoms, Y is -O-, -S, -COO-, -COS-, EMI115.2 -CONH-, -OCONH-, EMI115.3 or EMI115.4 and c is an integer of 1 to 6, the R5ts, when two or more are present, being the same or different. 5. A composition as claimed in Claim 3, in which R2 is represented by the formula EMI115.5 where each of Y and Y', which are the same or different, are as defined for Y in Claim 4, d is 0, 1, 2 or 3, and each of R6 and R6' is a hydrocarbon group haring 4 to 27 carbon atoms, and 'optionally having halogen, hydro, amino and/or carboxy substituent(s), at least one of R6 and R6' having at least four carbon atoms. 6. A composition as claimed in Claim 3, in which h and both stand for -e and a is 1. 7. A composition as claimed in Claim 4, in which h and X2 both stand for -0- and a is 1. 8. A composition as claimed in Claim 5, in which h and X2 both stand for -O- and a is 1. 9. A composition as claimed in Claim 6, in which R9 is represented by the formula EMI116.1 where each of R7 and is a hydrogen atom or hydrocarbon or halogenated hydrocarbon group having 1 to 4 carbon atoms. 10. A composition as claimed in Claim 6, in which R2 is represented by the formula EMI116.2 where N stands for hydrogen or methyl and Rg stands for a hydrocarbon or halogenated hydrocarbon group having 3 to 28 carbon atoms. 11. A composition as claimed in Claim 6, in which R2 is represented by the formula EMI116.3 where R10 stands for a hydrocarbon or halogenated hydrocarbon group haring 1 to 12 carbon atoms and e is O or 1. 12. A composition as claimed in Claim 6, in which R9 is represented by the formula EMI116.4 where f is an integer of from 5 to 20. 13. A composition as claimed in Claim 6, in which R2 is represented by the formula EMI117.1 where his an integer of 1 to 5, and i isO, 1, 2 or 3, the sum of h and i being at least 2. 14. A composition as claimed in Claim 6, in which R2 is represented by the formula EMI117.2 EMI117.3 15. A composition as claimed in Claim 6, in which R2 is represented by the formula EMI117.4 where Rll is a hydrocarbon or halogenated hydrocarbon group having 2 to 6 carbon atoms. 16. A composition as claimed in Claim 6, in which R2 is represented by the formula EMI117.5 17. A composition as claimed in Claim 10, in which R2 is represented by the formula EMI117.6 where g is an integer of 2 to 20, or by the formula EMI117.7 18. A composition as claimed in Claim 12, in which R2 is represented by the formula EMI118.1 where i is an integer of 5 to 12. 19. A composition as claimed in Claim 14, in which R2 is represented by the formula EMI118.2 20. A composition as claimed in any one of Claims 9 to 19, in which R1 is a methyl group. 21. A composition as claimed in Claim 7, in which R2 is represented by the formula EMI118.3 where R12 is a hydrocarbon or -halogenated hydrocarbon group having 1 to 12 carbon atoms. 22. A composition as claimed in Claim 21, in which Y stands for -O- or -COO-. 23. A composition as claimed in Claim 7, in which R2 is represented by the formula EMI118.4 where each ofR13 and h 3', which are the same or different, is a hydrocarbon or halogenated hydrocarbon group having 1 to 6 carbon atoms. 24. A composition as claimed in Claim 7, in which R2 is represented by the formula EMI118.5 where each of r14 , and ' is hydrogen or methyl, and each of k and k' is 2 or 3. 25. A composition as claimed in Claim 7, in which R2 is represented by the formula -CH2CH2OCH2C=CCE2 0Cn2 CH2 26. A composition as claimed in Claim 23, in which R2 is represented by the formula EMI119.1 27. A composition as claimed in Claim 23, in which R2 is represented by the formula EMI119.2 28. A composition as claimed in Claim 23, in which R2 is represented by the formula EMI119.3 where q is 3 or 4. 29. A composition as claimed in any one of Claims 21 to 28, in which RI stands for a methyl group. 30. A composition as claimed in Claim 8, in which R2 is represented by the formula EMI119.4 where R6 and R6' are as defined in Claim 5, m is 0 or , and n is 0, 1, 2 or 3. 31. A composition as claimed in Claim 30, in which at least one of R6 and R6' is an aromatic hydrocarbon group. 32. A composition as claimed in Claim 30 or 31, in which RI is a methyl group. 33. A composition as claimed in Claim 1, in which the said compound is a compound represented by formula II. 34. A composition as claimed in Claim 33, in which h is represented by the formula EMI120.1 35. A composition as claimed- in any one of Claims 1 to 34 in which the vinyl monomer is a (meth)acrylate monomer, styrene monomer or vinyl acetate. 36. A composition as claimed in Claim 35, in which the monomer is a mono- to tetra-functional (meth)acrylate having 1 to 66 carbon atoms. 37. A composition as claimed- in Claim 35, in which the monomer is represented by the formula EMI120.2 where Q stands for a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms. 38. A composition as claimed in any one of Claims 1 to 37 further comprising a volatile organic solvent having a boiling point up to 1500C at 760 Torr (10.1 kPa), the amount of solvent by weight being not more than 300 times that of the polymerizable monomer. 39. A composition as claimed in any one of Claims 1 to 38, in which the curing agent is an agent of the redox type. 40. A composition as claimed in Claim 39, in which the curing agent is a ternary agent composed of (a) a salt of an organic sulfinic acid, (b) an amine or amine salt, and (c) a peroxide. 41. A composition as claimed in any one of Claims 1 to 40, further comprising 20 to 500 parts by weight of a filler. 42. A composition as claimed in Claim 41, in which tlie filler is a silanated inorganic filler or an organic-inorganic composite filler. 43. For use in applying to the wall of a tooth cavity before filling the cavity with a dental composite resin, a dental adhesive composition comprising: 100 parts by weight of a polymerizable monomer comprising (a) 1.5 to 50 parts by weight of a compound represented by general formula I or 11 set forth in Claim 1, where R1, Rl', R2, X1, X2 and R3 are as defined in Claim 1, and R2 can additionally be a C4 bivalent organic.residue and (b) 50 to 98.5 parts by weight of a vinyl monomer copolymerizable with the said compound; and 0.01 to 20 parts by weight of a curing agent. 44. For use in applying to the wall of a tooth cavity before filling the cavity with a dental composite resin, a composition as set forth in Claim 43, in which the compound is of formula I and R2 stands for (a) a hydrocarbon group haring 4 to 30 carbon atoms optionally having halogen, hydroxy, amino or carboxy substituent(s), or (b) a group having 4 to 30 carbon atoms and composed of two to seven hydrocarbon residues bonded to one another by one or more ether, thioether, ester, thioester, thiocarbonyl, amjde, urethane, carbonyl and/or sulfonyl linkages, each of the said hydrocarbon residues having 1 to 29 carbon atoms and at least one of them having three or more carbon atoms, and optionally having halogen, hydroxy, amino and/or carbon substituent(s). 45. For use in applying to the wall of a tooth cavity before filling the cavity with a dental composite resin, a composition as set forth in Claim 44, in which R2 is represented by the formula -R5-(Y-R5')-c where each of R5 and R5'is a hydrocarbon group having 1 to 29 carbon atoms, optionally having halogen, hydro, amino and/or carbox4t substituent(s), at least one of R5 and R5' having at least three carbon atoms, and Y and c are as defined in Claim 4, the R5ts, when two or more are present, being the same or different. 46. For use in applying to the wall of a tooth cavity before filling the cavity with a dental composite resin, a composition as set forth in Claim- 44-, in which R2 is represented by the formula EMI122.1 where d, Y and Y' are as in Claim 5 and each of R6 and R61 is a hydrocarbon group having 1 to 27 carbon atoms, optionally having halogen, hydroxy, amino or carbon substituent(s). 47. For use in applying to the wall of a tooth cavity before filling the cavity with a dental composite resin, a composition as set forth in Claim 44, 45 or 46, in which h and X2 both stand for -e and a is 1. 48 For use in applying to the wall of a tooth cavity before filling the cavity with a dental composite resin, a composition as set forth in Claim 47, in which R2 is represented by the formula -(CH2)-f where f is an integer of 4 to 20. 49. For use in applying to the wall of a o tooth cavity before filling the cavity with a dental composite resin, a composition as set forth in Claim 47, in which R2 is represented by the formula EMI122.2 where g is an integer of 1 to 20, or the formula EMI122.3 50. For use in applying to the wall of a tooth cavity before filling the cavity with a dental composite resin, a composition as claimed in any of Claims 7 to 11, 13 to 16 and 18 to 40. 51. For use in filling a tooth cavity, a dental filling material comprising a dental adhesive composition as set forth in any one of Claims 45 to 50 and, per 300 parts by weight of the said polymerizable monomer, 20 to 500 arts by weight of a filler. 52. For use in filling a tooth cavity, a dental filling material as set forth in Claim 51, in which the filler is a silanated inorganic filler, or an organic-inorganic composite filler. 53. A phosphate monoester of the general formula EMI123.1 where RL stands for hydrogen, or a methyl group, and A stands for one of formulae 3 to 6 : EMI123.2 where p is ah integer of 5 to 12; EMI123.3 where q is an integer of 2 to 4; EMI123.4 where q is an integer of 2 to 4.

Inventors: NAGASE, YOSHINORI, OMURA, IKUO, UEMURA, FUMIKO, YAMAUCHI, JUNICHI
Applicants: KURARAY CO., LTD.
Application year: 1982
Main classification: C09J3
IPC codes: C09J4, C07F9, A61K6