Dental adhesive composition

Abstract

Disclosed are dental adhesive compositions consisting essentially of(a) at least one urethane prepolymer containing one or more isocyanate groups, or a blend of the urethane prepolymer and an inert diluent;(b) at least one radical-polymerizable unsaturated monomer;(c) a photopolymerization initiator;and, if desired,(d) a polymerizable phosphoric ester compound having a specific structure.These dental adhesive compositions can be used to bond a restorative material to dentin without requiring any troublesome pretreatment with an etching agent such as phosphoric acid, and can exhibit bonding power sufficient for practical purposes.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to dental adhesive compositions which have excellent bonding properties and are useful in bonding living dental tissues to materials (such as metals, organic polymers and ceramics) used for the restoration thereof

2. Description of the Prior Art

In the field of dental materials, a variety of materials have conventionally been used for the purpose of restoring carious teeth (also called decayed teeth) and missing teeth. Such materials include metals such as gold, silver, platinum, alloys and amalgam; organic high polymers such as polymethyl methacrylate, polycarbonate, cured products of multifunctional vinyl resins, and composite resins; and ceramic such as porcelain and implant materials. However, these materials are inherently incapable of adhering to living tooth tissues. Accordingly, in order to achieve bonding between restorative materials and living tooth tissues, there have been proposed a number of dental adhesive compositions containing, as the adhesive component, a compound having any of various polar groups (such as a phosphate group, hydroxyl group or acid anhydride group) with the intention of improving their interaction with the principal inorganic components, such as apatite (a calcium phosphate), or principal organic components, such as collagen (a protein), constituting the tooth tissues.

When the aforesaid prior art adhesive compositions are used to bond a restorative material to living tooth tissues, they have considerable adhesivity to enamel, but completely fail to exhibit adhesivity to dentin. This is due to the physical and chemical structures of living dentin. Specifically, dentin has a structure in which a vast number of dentinal tubules are penetrated and filled with a body fluid. Moreover, dentin contains a fairly high proportion of proteins such as collagen, as compared with enamel. Thus, it may be said that, from the viewpoint of bonding, dentin is in a very adverse environment. Accordingly, the aforesaid prior art adhesive compositions require pretreatment of the principal inorganic component as apatite, with an etching agent (such as phosphoric acid) so as to produce the so-called anchoring effect which brings about a certain degree of bonding to living dentin. Nevertheless, because of the insufficiency of bond strength, a gap will be produced between the restorative material and the dentin over a long time and, in the worst case, the restorative material may even fall off. Thus, the prior art adhesive compositions cannot be said to have bonding properties adequate for practical purposes.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a novel photopolymerizable dental adhesive composition which, when used to bond a restorative material to living tooth tissues, has high adhesivity to enamel and, moreover, exhibit practically sufficient adhesivity to dentin, without requiring any troublesome pretreatment with an etching agent (such as phosphoric acid) that has been indispensable in the prior art.

According to the present invention, there is provided a dental adhesive composition consisting essentially of

(a) at least one urethane prepolymer containing one or more isocyanate groups, or a blend of the urethane prepolymer and an inert diluent; (b) at least one radical-polymerizable unsaturated monomer; and (c) a photopolymerization initiator.

According to the present invention, there is also provided another dental adhesive composition consisting essentially of

(a) at least one urethane prepolymer containing one or more isocyanate groups, or a blend of the urethane prepolymer and an inert diluent; (b) at least one radical-polymerizable unsaturated monomer; (c) a photopolymerization initiator; and (d) a polymerizable phosphoric ester compound of the general formula (1): ##STR1## where R is a group selected from the class consisting of ##STR2## in which R.sub.1 is an alkylene group, R' is an alkyl group, n is 1 or 2, m is 1 or 2, l is 0 or 1, and the sum of (n+m+l) is equal to 3.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The urethane prepolymer containing one or more isocyanate groups, which is used as component (a) in the compositions of the present invention, is a compound obtained by reacting a polyol compound with a polyisocyanate [i.e., a compound having two or more isocyanate (--NCO) groups per molecule] in such a way that part of the isocyanate groups remain unreacted.

The polyol compound used for this purpose may be selected from polyether polyols and polyester polyols. Specific examples of useful polyether polyols include compounds formed by effecting addition polymerization of an alkylene oxide (such as propylene oxide or ethylene oxide) to a low-molecular-weight compound having two or more hydroxyl groups per molecule (such as glycol, glycerol, sorbitol or sucrose). Specific examples of useful polyester polyols include compounds formed by effecting polycondensation of a dibasic acid (such as adipic acid) with a glycol (such as ethylene glycol) so as to give terminal hydroxyl groups; compounds formed by reacting a hydroxyl-containing higher fatty acid (such as ricinoleic acid) with glycerol; and compounds obtained from natural sources, such as castor oil and its derivatives.

Such polyether polyols can be prepared according to the conventional method which comprises adding an alkaline catalyst (such as potassium hydroxide or sodium hydroxide) to an active hydrogen compound (such as ethylene glycol, propylene glycol or 1,6-hexanediol) and effecting addition polymerization of an alkylene oxide (such as ethylene oxide, propylene oxide or butylene oxide) to the active hydrogen compound

In order to obtain excellent bonding properties, it is preferable to use a polyol compound having terminal hydroxyl groups.

By way of example, urethane prepolymers having one or more isocyanate groups can be obtained by reacting, in the presence of a conventional catalyst such as a tertiary amine or dibutyltin laurate, the above-defined polyol compound with an organic isocyanate (such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate or hexamethylene diisocyanate) in such an NCO/OH equivalent ratio as to provide an excess of NCO.

Among these urethane prepolymers, there may preferably be used urethane prepolymers of the following structural formulas (2), (3) and (4) which are derived from a diol obtained by using propylene glycol as an active hydrogen compound and effecting addition polymerization of ethylene oxide and propylene oxide to it. In particular, urethane prepolymers obtained by using tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate or hexamethylene diisocyanate as a terminal isocyanating agent and containing at least two free isocyanate group per molecule are preferred because of their exceptionally high adhesivity. More specifically, urethane prepolymers containing free isocyanate groups at both ends are especially preferred. ##STR3## In the above formulas, m is a whole number of 1 to 100, n is a whole number of 0 to 100, and the propylene oxide units may be randomly joined to the ethylene oxide units.

These urethane prepolymers preferably have a molecular weight of 400 to 50,000 and more preferably 400 to 20,000, chiefly for the purpose of obtaining good solubility in radical-polymerizable unsaturated monomers, as well as excellent bonding properties.

With regard to the isocyanate-containing urethane prepolymers of formulas (2) to (4) it is preferable that they be rendered hydrophilic or watersoluble by adjusting their ethylene oxide unit content to a level of 40 to 80 mole percent based on the combined amount of the propylene oxide units and ethylene oxide units constituting the prepolymer chain.

On the other hand, the dibasic acids constituting polyester polyols useful for the aforesaid purpose include adipic acid, azelaic acid, sebacic acid, maleic acid, phthalic acid, isophthalic acid or terephthalic acid. The polyols constituting such polyester polyols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol,neopentyl glycol, glycerol, trimethylolpropane or pentaerythritol.

Among others, there may preferably be used urethane prepolymers obtained by reacting a polyester polyol with a polyisocyanate, the polyester polyol being prepared, for example, from a combination of adipic acid and propylene glycol and represented by the structural formula (5): ##STR4## where a is a whole number of 1 to 5, b is a whole number of 4 to 10, and d is a whole number of 1 to 200.

Useful polyester polyols also include compounds formed by reacting a hydroxyl-containing higher fatty acid (such as ricinoleic acid) with glycerol, as well as castor oil and its derivatives. In this case, it is preferable to use tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate or hexamethylene diisocyanate as the polyisocyanate. Among others, there may preferably be used urethane prepolymers of the structural formula (6): ##STR5##

These urethane prepolymers containing one or more isocyanate groups serve to achieve bonding between a restorative material and a tooth by the reaction of the isocyanate group(s) present in the molecule, with the principal organic components constituting living tooth tissues and, in particular, dentin (especially collagen containing a large number of active hydrogen radicals in the molecule), as well as water (body fluid). Among others, urethane prepolymers containing two or more free isocyanate groups per molecule are preferred because they can exhibit excellent bonding properties.

The above-described urethane prepolymers containing one or more isocyanate groups can be used alone. However, in order to improve the workability of the composition, they may be used in combination with a diluent inert to the isocyanate group, such as acetone, methyl ethyl ketone, ethyl acetate, toluene, xylene or trichloroethane.

Basically, a dental adhesive composition comprising component (a) alone would exhibit the desired adhesivity. However, where it is intended to carry out bonding operation in the oral cavity, restrictions are often imposed on the time required to cure the adhesive layer. Thus, the radical-polymerizable unsaturated monomer used as component (b) in the compositions of the present invention is a component required to rapidly harden the adhesive layer by exposure to light in the presence of the photopolymerization initiator used as component (c). For this purpose, there may be used any radical-polymerizable unsaturated monomer that does not interfere with the adhesivity of component (a). Useful unsaturated monomers include monofunctional and multifunctional unsaturated monomers.

Specific examples of useful monofunctional unsaturated monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)-acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, vinyl acetate, styrene and acrylonitrile. Especially preferred are methyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate and benzyl methacrylate.

Useful bifunctional unsaturated monomers include, for example, polyethylene glycol di(meth)-acrylates of the general formula (7): ##STR6## where R.sup.1 is a hydrogen atom or a methyl group, and p is a whole number of 1 to 20. Specific examples thereof include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)-acrylate, tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)-acrylate, octaethylene glycol di(meth)acrylate, nonacethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, polyethylene glycol di(meth)-acrylates of the general formula (7) in which P is 14, polyethylene glycol di(meth)acrylates of the general formula (7) in which p is 17, and polyethylene glycol di(meth)acrylates of the general formula (7) in which p is 19. Especially preferred are ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylates of the general formula (7) in which p is 14. Moreover, there may also be used urethane di(meth)acrylates of the general formula (8): ##STR7## where R.sup.1 is a hydrogen atom or a methyl group, and R.sup.2 is an alkylene group of 1 to 8 carbon atoms, or ##STR8## Specific examples thereof include di(acryloxyethyl)dimethylene diurethane, di-(methacryloxyethyl)dimethylene diurethane, di(acryloxyethyl)tetramethylene diurethane, di(methacryloxyethyl)-tetramethylene diurethane, di(acryloxyethyl)-trimethylhexamethylene diurethane, and di(methcryloxyethyl)-trimethylhexanmethylene diurethane. Especially preferred is the urethane dimethacrylate of the structural formula (9): ##STR9##

Furthermore, there may also be used 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate and trimethylolpropane tri(meth)-acrylate. Especially preferred is trimethylolpropane triacrylate.

Furthermore, there may also be used (meth)-acrylate compounds having a bisphenol A skeleton and represented by the general formula (10) or (11): ##STR10## where R.sup.3 is a hydrogen atom or a methyl group, and q is a whole number of 1 to 20.

Specific examples thereof include 2,2-bis(4-methacryloxypolyethoxyphenyl)propanes, 2,2-bis [4-(3-methacryloxy-2-hydroxypropoxy)phenyl]propane, 1,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxy]ethane and 1,4-bis[3-(meth)acryloyloxy-2-hydroxypropoxy]butane.

Useful tetrafunctional unsaturated monomers include, for example, tetrafunctional urethane (meth)-acrylates having the general formula (12): ##STR11## where R.sub.1 and R.sub.2 are hydrogen atoms or methyl groups, and X is --CH.sub.2 --, --CH.sub.2 CH.sub.2 --, --(CH.sub.2).sub.3 --, --(CH.sub.2).sub.4 --, --(CH.sub.2).sub.5 --, --(CH.sub.2).sub.6 -- or Specific and preferred examples thereof include the tetrafunctional urethane (meth)acrylate of the general formula (12) in which R.sub.1 is a hydrogen atom, R.sub.2 is a methyl group, and X is --(CH.sub.2).sub.6 -- (hereinafter referred to as U-4HA) and the tetrafunctional methacrylate of the general formula (12) in which R.sub.1 and R.sub.2 are methyl groups and X is --(CH.sub.2).sub.6 -- (hereinafter referred to as U-4H).

In addition, there may preferably be used hexafunctional urethane (meth)acrylates having an isocyanuric acid skeleton and represented by the general formula (13): ##STR12## where R.sub.4 and R.sub.5 are hydrogen atoms or methyl groups, and r is a whole number of 1 to 10. Specific examples thereof include the compound of the general formula (13) in which r is 6, R.sup.4 is a hydrogen atom, and R.sup.5 is a methyl group (hereinafter referred to as U-6HA) and the compound of the general formula (13) in which r is 6 and both R.sup.4 and R.sup.5 are hydrogen atoms (hereinafter referred to as U-6H). These compounds are especially preferred hexafunctional unsaturated monomers.

The foregoing radical-polymerizable unsaturated monomers may be used either alone or in admixture.

The photopolymerization initiator used as component (c) in the composition of the present invention may be selected from conventionally known ultraviolet light polymerization initiators (such as benzophenone) and visible light polymerization initiators, according to the intended purpose of use. Where the composition of the present invention is to be used in the oral cavity, it is preferable to use a photopolymerization initiator capable of initiating the polymerization in response to visible light in the wavelength range of about 400 to 1,200 nm and free of near-ultraviolet radiation which might be harmful to the oral mucosa. Accordingly, it is preferable that the photosensitizer included in the photopolymerization initiator be one which can be excited by visible light in the wavelength range of about 400 to 1,200 nm. The compounds which can be used for this purpose are, for example, .alpha.-diketone compounds. Specific examples of useful .alpha.-diketone compounds include camphorquinone, benzil and diacetyl. Among others, camphorquinone is especially preferred because of its high polymerization activity.

In order to achieve desired excellent photopolymerizability, it is desirable to use a visible light polymerization initiator comprising a combination of a photosensitizer as described above and a reducing agent such as a tertiary amine. Specific examples of useful tertiary amines include aliphatic amines such as trimethylamine, triethylamine and tripropylamine; and aromatic amines such as isoamyl 4-(N,N-dimethylamino)-benzoate, hexyl 4-(N,N-dimethylamino)benzoate, heptyl 4-(N,N-dimethylamino)benzoate, octyl 4-(N,N-dimethylamino)benzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone and 4,4'-bis-(dibutylamino)benzophenone. Among others, aromatic tertiary amines are preferred. In particular, isoamyl 4-(N,N-dimethylamino)benzoate, 4,4'-bis(dimethylamino)-benzophenone and 4,4'-bis(diethylamino)benzophenone are most preferred because excellent visible light polymerizing activity can be obtained by using them in combination with camphorquinone.

The amounts in which these visible light polymerization initiators may be added have their respective appropriate ranges, depending on the types of photosensitizer and reducing agent used. For example, in the camphorquinone/isoamyl 4-(N,N-dimethylamino)benzoate system, camphorquinone is preferably added in an amount of 0.01 to 25% by weight, more preferably 0.05 to 15% by weight, based on the radical-polymerizable unsaturated monomer, and isoamyl 4-(N,N-dimethylamino)benzoate is preferably added in an amount of 0.05 to 30% by weight, more preferably 0.1 to 25% by weight. Similarly, in the camphorquinone4,4'-bis(dimethylamino)benzophenone system, camphorquionone is preferably added in an amount of 0.005 to 30% by weight, more preferably 0.03 to 20% by weight, based on the radical-polymerizable unsaturated monomer, and 4,4'-bis(dimethylamino)-benzophenone is preferably added in an amount of 0.01 to 25% by weight, more preferably 0.05 to 20% by weight.

In the dental adhesive compositions of the present invention, the weight ratio of component (a) to component (b) can range from 1:150 to 150:1 and more preferably from 1:100 to 100:1. In order to obtain adhesivity sufficient for practical purposes, the weight ratio most preferably ranges from 1:50 to 50:1.

Although the dental adhesive compositions of the present invention consisting essentially of the above-defined components (a), (b) and (c) exhibit adhesivity sufficient for practical purposes, further research has demonstrated that greater adhesivity can be obtained by adding thereto a polymerizable phosphoric ester compound of the general formula (1): ##STR13## where R is a group selected from the class consisting of ##STR14## in which R.sub.1 is an alkylene group having carbon atoms 2-12, R' is an alkyl or 2, m is 1 or 2, l is 0 or 1, and the sum of (n+m+l) is equal to 3.

Specific examples of the polymerizable phosphoric ester compound include ##STR15## Among these polymerizable phosphoric ester compounds, methacryloxyethyl phosphate of the formula ##STR16## and dimethacryloxyethyl phosphate of the formula are especially preferred.

The polymerizable phosphoric ester compound is usually used in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably 1.0 to 5.0 parts by weight, per 100 parts by weight of the radical-polymerizable unsaturated monomer used as component (b).

The dental adhesive compositions of the present invention consist essentially of the above-defined three or four components. If necessary, however, they may additionally contain inorganic fillers (such as silica powder, quartz powder and various glass powders), organic polymers (such as polymethyl methacrylate and polystyrene), colorants, polymerization inhibitors (such as hydroquinone and methylphenol), antioxidants, ultraviolet light absorbers, pigments and dyes.

In ordinary cases, the dental adhesive compositions of the present invention may conveniently be stored, till use, in the form of mixtures consisting of the aforesaid three or four components. Alternatively, it is also possible to separately store components (a) and a mixture of components (b), (c) and optionally (d), and mix them immediately before use.

As the light source (in particular, visible light source) for curing the dental adhesive compositions of the present invention in a short time, there may be used light emitted by a halogen lamp, xenon lamp, mercury vapor lamp or fluorescent lamp and having wavelengths in the range of 3,500 to 12,000 .degree. .ANG..

The dental adhesive compositions of the present invention can be applied to a variety of restorative materials. More specifically, they have excellent bonding properties not only to heat-curable materials commonly used as prosthetic materials in the art, including composite resins (i.e., composite materials obtained by blending a multifunctional monomer with an inorganic filler) and crown resins, but also to thermoplastic resins for use in denture bases (such as polymethyl methacrylate, polysulfone and polycarbonate), various cementing materials, amalgam, alumina, gold and alloys.

When used to bond a restorative material to living tooth tissues, especially to dentin, the dental adhesive compositions of the present invention can exhibit adhesivity sufficient for practical purposes, without requiring any troublesome pretreatment with an etching agent (such as phosphoric acid) that has been indispensable in the prior art. Moreover, owing to their photopolymerizability, the dental adhesive compositions of the present invention can be hardened in a short time by exposure to light before their inherent adhesivity is exhibited. Thus, they are easy to handle in the oral cavity.

The present invention is further illustrated by the following examples. However, these examples are not to be construed to limit the scope of the invention.

[Preparation of restorative material A (visible light curable composite resin)]

______________________________________Ingredient Amount______________________________________2,2-Bis[4-(methacryloxyethoxy)pheny]propane 8 g(hereinafter referred to as Bis-MEPP)Triethylene glycol dimethacrylate 12 g(hereinafter referred to as 3G)Silanated quartz powder (with an average 74 gparticle diameter of about 4 .mu.m)Finely powdered silicon dioxide (#R-972; 6 gtrade name; a product of Nippon Aerosil Co.)Camphorquinone 0.4 gIsoamyl 4-(N,N-dimethylamino)benzoate 2 g______________________________________

According to the above formulation, a visible light curable composite resin (i.e., a pasty mixture consisting of multifunctional monomers, inorganic fillers and a visible light polymerization initiator) was prepared in a dark room to obtain restorative material A.

[Preparation of restorative material B (visible light curable crown resin)]

______________________________________Ingredient Amount______________________________________2,2-Bis[4-(3-methacryloxy-2-hydroxy- 40 gpropoxy)phenyl]propane(hereinafter referred to as Bis-GMA)3G 60 gCamphorquinone 0.7 gIsoamyl 4-(N,N-dimethylamino)benzoate 2.8 g______________________________________

According to the above formulation, a visible light curable crown resin (i.e., a mixture consisting of multifunctional monomers and a visible light polymerization initiator) was prepared in a dark room to obtain restorative material B.

[Procedure for the evaluation of bonding properties and method for the measurement of bond strength]

(1) A freshly extracted cattle fore-tooth was cut with a precision cutter (Isomet; trade name; a product of Buhler Co.) to expose a flat dentin surface and a flat enamel surface. Then, using a piece of No. 1000 water-resistant abrasive paper, these exposed surfaces were fully polished under a stream of water. In some cases, the enamel surface was etched with a phosphoric acid etchant (manufactured by GC Dental Industries Co.) in the usual manner.

(2) A dental adhesive composition was applied to the dentin surface or the enamel surface. Any volatile components such as a solvent were scattered and evaporated by exposure to a stream of air for about 10 seconds.

(3) A cylindrical silicone ring (openable on one side) having an inner diameter of about 5 mm, a height of about 5 mm and a wall thickness of about 3 mm was placed on the surface to which the dental adhesive composition had been applied. Then, the silicone ring was filled with a liquid restorative material to a height of about 3 mm.

(4) The aperture of a visible light projector (GC Light; trade name; manufactured by GC Dental Industries Co.) was brought into contact with the upper end of the silicone ring filled with the restorative material Thus, the restorative material and the adhesive composition were cured by exposure to visible light for 60 seconds.

(5) After the lapse of about 10 minutes, the silicone ring was removed to obtain a specimen having the restorative material bonded to the surface of the tooth sample.

(6) After the entire specimen was stored in water at 37.degree. C. for a predetermined period of time, a spacer for bonding test (i.e., an acrylic rod having the same diameter as the restorative material) was joined to the top of the restorative material by means of GC Unifast Quick Self-Curing Acrylic Resine (Uni Fast; trade name; manufactured by GC Dental Industries Co.). The resulting assembly was mounted on a testing jig and subjected to a tensile test for the measurement of bond strength. The measuring conditions were as follows.

Tensile tester: Tensilon (trade name; manufactured by Toyo-Baldwin Co.). Crosshead speed (pulling speed): 0.5 mm/min. Chart speed: 10 mm/min. Full scale: 5 kgW or 20 kgW. Number of specimens: n=3.

[Synthesis of isocyanate-containing urethane prepolymers (I)]

Using propylene glycol as an active hydrogen compound, ring opening copolymerization of propylene oxide and ethylene oxide was carried out according to conventional procedure. Thus, there were obtained various polyether glycols containing ethylene oxide units (hereinafter referred to as EO) and propylene oxide units (hereinafter referred to as PO) in varying molar ratios and having different molecular weights, as shown in Table 1.

Then, according to conventional procedure, these polyether glycols were reacted with an isocyanating agent comprising tolylene diisocyanate (containing 2,4- and 2,6-isomers in a molar ratio of 80:20; hereinafter referred to as TDI), 4,4-diphenylmethane diisocyanate (hereinafter referred to as MDI) or hexamethylene diisocyanate (hereinafter referred to as HDI). In this reaction, the polyether glycol and the isocyanating agent were used in a molar ratio of 1:2. Thus, there were obtained various urethane prepolymers containing two terminal isocyanate groups and having the codes shown in Table 1.

TABLE 1__________________________________________________________________________Code for pre-polymer containing Composition of polyether glycoltwo terminal Type of Average mole- Isocyanating Propertyisocyanate groups EO/PO polymer cular weight Code agent of prepolymer__________________________________________________________________________TPT-1 0/100 -- 500 PEP-1 TDI HydrophobicTPT-2 " -- 3,000 PEP-2 " "TPT-3 " -- 18,000 PEP-3 " "TPT-4 20/80 Random 8,000 PEP-4 " "TPT-5 " " 7,000 PEP-5 " "TPT-6 " Block 1,500 PEP-6 " "TPT-7 40/60 Random 1,000 PEP-7 " HydrophilicTPT-8 " " 5,000 PEP-8 " "TPT-9 " Block 3,000 PEP-9 " " TPT-10 60/40 Random 400 PEP-10 " Water-soluble TPT-11 " " 2,000 PEP-11 " " TPT-12 " " 10,000 PEP-12 " " TPT-13 80/20 Random 600 PEP-13 " " TPT-14 " " 1,200 PEP-14 " "MPM-1 0/100 -- 500 PEP-1 MDI HydrophobicMPM-2 20/80 Random 7,000 PEP-5 " "MPM-3 40/60 Random 1,000 PEP-7 " HydrophilicMPM-4 " " 5,000 PEP-8 " "MPM-5 " Block 3,000 PEP-9 " "MPM-6 60/40 Random 2,000 PEP-11 " Water-solubleHPH-1 0/100 -- 500 PEP-1 HDI HydrophobicHPH-2 20/80 Random 7,000 PEP-5 " "HPH-3 40/60 Random 1,000 PEP-7 " HydrophilicHPH-4 " " 5,000 PEP-8 " "HPH-5 " Block 3,000 PEP-9 " "HPH-6 60/40 Random 2,000 PEP-11 " Water-soluble__________________________________________________________________________

[Synthesis of isocyanate-containing urethane prepolymers (II)]

In the same manner as described in the foregoing synthesis of urethane prepolymers (I), various polyether glycols were reacted with an isocyanating agent comprising TDI, MDI or HDI. In this case, however, the polyether glycol and the isocyanating agent were used in a molar ratio of 1:1. Thus, there were obtained various urethane prepolymers containing one terminal isocyanate group and one terminal hydroxyl group and having the codes shown in Table 2.

TABLE 2__________________________________________________________________________Code forprepolymer contg. Composition of polyether glycolone terminal Type of Average mole- Isocyanatingisocyanate group EO/PO polymer cular weight Code agent__________________________________________________________________________PT-1 0/100 -- 500 PEP-1 TDIPT-2 20/80 Random 7,000 PEP-5 "PT-3 40/60 Random 1,000 PEP-7 "PT-4 " " 5,000 PEP-8 "PT-5 " Block 3,000 PEP-9 "PT-6 60/40 Random 2,000 PEP-11 "PM-1 40/60 Random 1,000 PEP-7 MDIPM-2 " " 5,000 PEP-8 "PM-3 " Block 3,000 PEP-9 "PH-1 40/60 Random 1,000 PEP-7 HDIPH-2 " " 5,000 PEP-8 "PH-3 " Block 3,000 PEP-9 "__________________________________________________________________________

[Synthesis of isocyanate-containing urethane prepolymers (III)]

Some of the urethane prepolymers containing two terminal isocyanate groups, which had been obtained in the foregoing synthesis of urethane prepolymers (I), were reacted with a hydroxyl-containing radical-polymerizable unsaturated monomer comprising 2-hydroxyethyl methacrylate. In this reaction, the urethane prepolymer and the unsaturated monomer were used in a molar ratio of 1:1. Thus, there were obtained various urethane prepolymers containing one terminal radical-polymerizable vinyl group and one terminal isocyanate group and having the codes shown in Table 3.

TABLE 3______________________________________Code for urethane Unsaturatedprepolymer contg. monomerone terminal radical- Starting urethane used to introducepolymerizable vinyl prepolymer contg. a terminal radical-group and one terminal two terminal iso- polymerizableisocyanate group cyanate groups vinyl group______________________________________TV-1 TPT-7 2-Hydroxyethyl methacrylateTV-2 TPT-10 2-Hydroxyethyl methacrylateTV-3 TPT-13 2-Hydroxyethyl methacrylateMV-1 MPM-3 2-Hydroxyethyl methacrylateHV-1 HPH-3 2-Hydroxyethyl methacrylate______________________________________

[Synthesis of vinyl-containing urethane prepolymers (IV)]

Some of the urethane prepolymers containing two terminal isocyanate groups, which had been obtained in the foregoing synthesis of urethane prepolymers (I), were reacted with a hydroxyl-containing radical-polymerizable unsaturated monomer comprising 2-hydroxyethyl methacrylate. In this reaction, the urethane prepolymer and the unsaturated monomer were used in a molar ratio of 1:2. Thus, there were obtained various urethane prepolymers containing two terminal radical-polymerizable vinyl groups and having the codes shown in Table 4.

TABLE 4______________________________________ UnsaturatedCode for urethane monomerprepolymer contg. Starting urethane used to introducetwo terminal radical- prepolymer contg. a terminal radical-polymerizable two terminal iso- polymerizablevinyl groups cyanate groups vinyl group______________________________________DV-1 TPT-7 2-Hydroxyethyl methacrylateDV-2 MPM-3 2-Hydroxyethyl methacrylateDV-3 HPH-3 2-Hydroxyethyl methacrylate______________________________________

[Synthesis of isocyanate-containing urethane prepolymers (V)]

Adipic acid and propylene glycol were mixed in a molar ratio ranging from 1:1.1 to 1:1.5. Then, using magnesium acetate as the catalyst, polycondensation of these compounds was carried out according to conventional procedure. Thus, there were obtained various polyester glycols containing hydroxyl groups at both ends and having different molecular weights. The codes for these polyester glycols are shown in Table 5.

Then, according to conventional procedure, these polyester glycols were reacted with an isocyanating agent comprising TDI, MDI or HDI. In this reaction, the polyester glycol and the isocyanating agent were used in a molar ratio of 1:2. Thus, there were obtained various urethane prepolymers containing two terminal isocyanate groups and having the codes shown in Table 5.

TABLE 5______________________________________Code for urethaneprepolymer contg. Polyester glycoltwo terminal Average mole- Isocyanatingisocyanate groups Code cular weight agent______________________________________TS-1 SG-2 1,000 TDITS-2 SG-4 5,000 "MS-1 SG-1 500 MDIMS-2 SG-2 1,000 "MS-3 SG-3 2,000 "MS-4 SG-4 5,000 "MS-5 SG-5 10,000 "MS-6 SG-6 18,000 "HS-1 SG-2 1,000 HDIHS-2 SG-4 1,000 "______________________________________

[Synthesis of isocyanate-containing urethane prepolymers (VI)]

In the same manner as described in the foregoing synthesis of urethane prepolymers (V), various polyester glycols were reacted with an isocyanating agent comprising TDI, MDI or HDI. In this case, however, the polyester glycol and the isocyanating agent were used in a molar ratio of 1:1. Thus, there were obtained various urethane prepolymers containing one terminal isocyanate group and one terminal hydroxyl group and having the codes shown in Table 6.

TABLE 6______________________________________Code for urethaneprepolymer contg. Polyester glycolone terminal Average mole- Isocyanatingisocyanate group Code cular weight agent______________________________________TH-1 SG-2 1,000 TDITH-2 SG-4 5,000 "MH-1 SG-2 1,000 MDIMH-2 SG-3 2,000 "MH-3 SG-4 5,000 "MH-4 SG-5 10,000 "HH-1 SG-2 1,000 HDIHH-2 SG-4 1,000 "______________________________________

[Synthesis of isocyanate-containing urethane prepolymers (VII)]

According to conventional procedure, castor oil used as a polyol compound was reacted with an isocyanating agent comprising TDI, MDI or HDI. In this reaction, the polyol compound and the isocyanating agent were used in a molar ratio of 1:3. Thus, there were obtained three urethane prepolymers containing three free isocyanate groups. The molar ratio was calculated on the assumption that castor oil had the structure of ricinoleic acid triglyceride and contained no impurities.

The resulting urethane prepolymers containing three free isocyanate groups were given their respective codes according to the type of the isocyanating agent used. Specifically, the codes were CO-1 for TDI, CO-2 for MDI, and CO-3 for HDI.

[Synthesis of isocyanate-containing urethane prepolymers (VIII)]

The urethane prepolymers containing three free isocyanate groups, which had been obtained in the foregoing synthesis of urethane prepolymers (VII), were reacted with a hydroxyl-containing radical-polymerizable unsaturated monomer comprising 2-hydroxyethyl methacrylate. In this reaction, the urethane prepolymer and the unsaturated monomer were used in a molar ratio of 1:1 or 1:2. Thus, there were obtained three urethane prepolymers containing one radical-polymerizable vinyl group and two free isocyanate groups and having the codes shown in Table 7, as well as three urethane prepolymers containing two radical-polymerizable vinyl groups and one free isocyanate group and having the codes shown in Table 7.

TABLE 7______________________________________Code for the resulting Startingurethane prepolymer urethane Hydroxy-contg. one (two) prepolymer contg.radical-polymerizable contg. radical-vinyl group and three free polymerizabletwo (one) free isocyanate vinyl monomer Molarisocyanate groups groups used ratio______________________________________SV-1 CO-1 2-Hydroxyethyl 1/1 methacrylateSV-2 CO-2 2-Hydroxyethyl " methacrylateSV-3 CO-3 2-Hydroxyethyl " methacrylateVV-1 CO-1 2-Hydroxyethyl 1/2 methacrylateVV-2 CO-2 2-Hydroxyethyl " methacrylateVV-3 CO-3 2-Hydroxyethyl " methacrylate______________________________________

[Synthesis of vinyl-containing urethane prepolymers (IX)]

The urethane prepolymers containing three free isocyanate groups, which had been obtained in the foregoing synthesis of urethane prepolymers (VII), were reacted with a hydroxyl-containing radical-polymerizable unsaturated monomer comprising 2-hydroxyethyl methacrylate. In this case, the urethane prepolymer and the unsaturated monomer were used in a molar ratio of 1:3. Thus, there were obtained three urethane prepolymers containing three radical-polymerizable vinyl groups.

The resulting urethane prepolymers containing three radical-polymerizable vinyl groups were given their respective codes according to the type of the starting urethane prepolymer containing three free isocyanate groups. Specifically, the codes were PV-1 for CO-1, PV-2 for CO-2, and PV-3 for CO-3.

[Preparation of radical-polymerizable unsaturated monomer/visible light polymerization initiator mixtures]

Using a general-purpose mixer, various mixtures consisting of at least one radical-polymerizable unsaturated monomer and a visible light polymerization initiator were prepared in a dark room. The compositions of these mixtures and their respective codes are shown in Tables 8 to 10.

The code "EDMA" given in the tables as the designation of a radical-polymerizable unsaturated monomer refers to the urethane dimethacrylate of the structural formula ##STR17##

TABLE 8__________________________________________________________________________Code forradical-poly- Visible lightmerizable polymerization initiator andunsat. mono- Radical-polymerizable unsat. monomer and amount used amount used (g)mer/visible/ Tri- Nona- Trimeth- Isoamyl 4,4'-Bis-light poly- Vi- Ethylene ethylene ethylene ylol- Cam- (N,N-di- (dimeth-merization Methyl- Methyl Butyl nyl glycol glycol glycol propane phor- methyl- ylamino)-initiator acry- metha- acry- ace- dimeth- dimeth- diacry- trimeth- qui- amino)- benzo-mixture late crylate late tate acrylate acrylate late EDMA acrylate none benzoate phenone__________________________________________________________________________LC-1 -- -- -- -- 100 -- -- 0.8 1.2 --LC-2 -- -- -- -- 100 -- -- -- -- " -- 1.2LC-3 -- -- -- -- -- -- 100 -- -- " 1.2 --LC-4 -- -- -- -- -- -- 100 -- -- " -- 1.2LC-5 -- -- -- -- -- -- -- -- 100 " 1.2 --LC-6 -- -- -- -- -- -- -- -- 100 " -- 1.2LC-7 -- 55 -- -- -- -- -- 45 -- 1.2 1.6 --LC-8 -- 55 -- -- -- -- -- 45 -- " -- 1.6LC-9 55 -- -- -- -- 45 -- -- -- " 1.6 --LC-10 55 -- -- -- -- 45 -- -- -- " -- 1.6LC-11 -- -- 35 -- -- -- 65 -- -- " 1.6 --LC-12 -- -- 35 -- -- -- 65 -- -- " -- 1.6LC-13 -- -- -- 25 -- -- -- 75 -- " 1.6 --LC-14 -- -- -- 25 -- -- -- 75 -- " -- 1.6LC-15 -- 70 -- -- -- -- -- 30 -- 1.5 2.0 --LC-16 -- 70 -- -- -- -- -- 30 -- " -- 2.0LC-17 -- 85 -- -- -- -- -- 15 -- " 2.0 --LC-18 -- 85 -- -- -- -- -- 15 -- " -- 2.0LC-19 -- 30 -- -- -- -- -- -- 70 0.5 1.0 --__________________________________________________________________________ TABLE 9__________________________________________________________________________ Visible light poly. initiatorCode for radical- and amount used (g)polymerizable Radical-polymerizable unsat. monomer and amount used Isoamyl 4,4'-Bis-unsat. monomer/ Neopentyl Trimethylene Com- (N,N- (dimeth-visible light Methyl 2-Hydroxy- glycol glycol phor- dimethyl- ylamino)-poly. initiator acryl- ethyl meth- dimeth- dimeth- qui- amino)- benzo-mixture late acrylate acrylate acrylate Bis-GMA U-4HA U-6HA none benzoate phenone__________________________________________________________________________LC-20 -- -- 100 40 60 -- -- 0.8 1.2 --LC-21 -- -- 100 40 60 -- -- " -- 1.2LC-22 -- 40 -- -- -- 60 -- " 1.2 --LC-23 -- 40 -- -- -- 60 -- " -- 1.2LC-24 -- -- 40 -- -- -- 60 " 1.2 --LC-25 -- -- 40 -- -- -- 60 " -- 1.2LC-26 -- 20 30 -- 50 -- -- " 1.2 --LC-27 -- 20 30 -- 50 -- -- " -- 1.2LC-28 -- 20 -- 30 -- 50 -- 1.2 1.6 --LC-29 -- 20 -- 30 -- 50 -- " -- 1.6LC-30 20 -- 30 -- -- -- 50 " 1.6 --LC-31 20 -- 30 -- -- -- 50 1.2 -- 1.6LC-32 -- -- 20 30 -- -- 50 " 1.6 --LC-33 -- -- 20 30 -- -- 50 " -- 1.6LC-34 -- 10 20 30 40 -- -- " 1.6 --LC-35 -- 10 20 30 40 -- -- " -- 1.6__________________________________________________________________________ TABLE 10__________________________________________________________________________ Visible light poly. initiatorCode for radical- Radical-polymericable unsat. monomer and amount used and amount used (g)polymerizable Trimeth- 4,4'-Bis-unsat. monomer/ Neopentyl ylene (dimeth-visible light Methyl 2-Hydroxy glycol glycol Isoamyl ylamino)-poly. initiator acryl- ethyl dimeth- dimeth- Comphor- (N,N-dimethyl- benzo-mixture late acrylate acrylate acrylate Bis-GMA U-4HA U-6HA quinone amino)benzoate phenone__________________________________________________________________________LC-36 -- -- 40 60 -- -- -- 0.8 1.2 --LC-37 -- -- 40 60 -- -- -- " -- 1.2LC-38 20 -- 20 -- 60 -- -- " 1.2 --LC-39 20 -- 20 -- 60 -- -- " -- 1.2LC-40 -- 20 -- 20 20 40 -- 1.2 1.6 --LC-41 -- 20 -- 20 20 40 -- " -- 1.6__________________________________________________________________________

[Preparation of radical-polymerizable unsaturated monomer/polymerizable phosphoric ester compound/visible light polymerization initiator mixtures]

Using a general-purpose mixer, various mixtures consisting of at least one radical-polymerizable unsaturated monomer (hereinafter referred to as monomer X), a polymerizable phosphoric ester compound (hereinafter referred to as monomer Z), and a visible light polymerization initiator were prepared in a dark room. The compositions of these mixtures and their respective codes are shown in Table 11.

TABLE 11 Code for radical- Radical-polymerizable unsat. monomer polymerizable and amount used (g) Visible light poly. initiator unsat. monomer/ Ethylene Triethylene Trimethylol- and amount used (g) visible light Methyl Methyl Butyl Vinyl glycol glycol Nonaethylene propane Isoamyl 4- 4,4'-Bis- poly. initiator acry- methac- acry- ace- dimeth- dimeth- glycol trimeth- Camphor- (N,N-dimethyl- (dimethylamino)- mixture late rylate late tate acrylate acrylate diacrylate EDMA acrylate quinone amino)benzoate benzophenone LC-42 -- -- -- -- 100 -- -- -- -- 1.0 2.0 -- LC-43 -- -- -- -- 100 -- -- -- -- " -- 2.0 LC-44 -- -- -- -- -- -- 100 -- -- " 2.0 -- LC-45 -- -- -- -- -- -- 100 -- -- " -- -- LC-46 -- -- -- -- -- -- -- -- 100 " 2.0 -- LC-47 -- -- -- -- -- -- -- -- 100 " -- 2.0 LC-48 -- 55 -- -- -- -- -- 45 -- 0.5 1.0 -- LC-49 -- 55 -- -- -- -- -- 45 -- " -- 1.0 LC-50 55 -- -- -- -- 45 -- -- -- " 1.0 -- LC-51 55 -- -- -- -- 45 -- -- -- " -- 1.0 LC-52 -- -- 35 -- -- -- 65 -- -- " 1.0 -- LC-53 -- -- 35 -- -- -- 65 -- -- 0.5 -- 1.0 LC-54 -- -- -- 25 -- -- -- 75 -- " 1.0 -- LC-55 -- -- -- 25 -- -- -- 75 -- " -- 1.0 LC-56 -- 70 -- -- -- -- -- 30 -- 0.2 0.5 -- LC-57 -- 70 -- -- -- -- -- 30 -- " -- 0.5 LC-58 -- 70 -- -- -- -- -- -- 30 " 0.5 -- LC-59 -- 70 -- -- -- -- -- -- 30 " -- 0.5 LC-60 -- -- -- -- 30 -- -- -- 70 2.0 5.0 -- Code for monomer Monomer X, monomer Z and amounts used (g) X/monomer Z/ 2-Hydroxy- Triethylene Dimeth- Visible light poly. initiator and amount (g) visible light Benzyl ethyl glycol Methacryl- acryloxy- I soamyl 4- 4,4'-Bis- 4,4'-Bis- poly. initiator Acryloxy methac- methac- dimeth- oxyethyl ethyl Camphor- (N,N-dimethyl- (dimethylamino)- (diethylamino)- mixture pivalate rylate rylate acrylate Bis-GMA Bis-MEPP U-4HA U-6HA phosphate phosphate quinone amino)Benzoate benzophenone benzophenone LC-61 -- -- -- 40 60 -- -- -- 2.0 -- 0.8 1.2 -- -- LC-62 -- -- -- 40 60 -- -- -- -- 2.0 " " -- -- LC-63 -- 20 -- 20 -- 60 -- -- 2.0 -- " " -- -- LC-64 -- 20 -- 20 -- 60 -- -- -- 2.0 " " -- -- LC-65 -- -- 40 -- -- -- 60 -- 2.0 -- " " 1.2 -- LC-66 -- -- 40 -- -- -- 60 -- -- 2.0 " " " -- LC-67 -- -- 20 -- 20 20 -- 40 2.0 -- " " " -- LC-68 -- -- 20 -- 20 20 -- 40 -- 2.0 " " " -- LC-69 -- -- 30 10 -- 30 30 -- 2.0 -- " " " -- LC-70 -- -- 30 10 -- 30 30 -- -- 2.0 " " " -- LC-71 100 -- -- -- -- -- -- -- 2.0 -- " " " -- LC-72 100 -- -- -- -- -- -- -- -- 2.0 " " " -- Code for monomer Monomer X, monomer Z and amounts used Visible light poly. initiator and amount (g) X/monomer Z/ 2-Hydroxy- Triethylene Dimeth- Cam- visible light Benzyl ethyl glycol Methacryl- acryloxy- phor- Isoamyl 4- 4,4'-Bis- 4,4'-Bis- poly. initiator Acryloxy methac- methac- dimeth- oxyethyl ethyl qui- (N,N-dimethyl- (dimethyl amino)- (diethylamino)- mixture pivalate rylate rylate acrylate Bis-GMA 3G Bis-MEPP U-4HA U-6HA phosphate phosphate none amino)Benzoate benzophen one benzophenone LC-73 -- -- 30 10 -- -- 30 30 -- 0.2 -- 0.8 1.2 -- -- LC-74 -- -- " " -- -- " " -- -- 0.2 " " -- -- LC-75 -- -- " " -- -- " " -- 0.6 -- " " -- -- LC-76 -- -- " " -- -- " " -- -- 0.6 " " -- -- LC-77 -- -- " " -- -- " " -- 4.0 -- " " 1.2 -- LC-78 -- -- " " -- -- " " -- -- 4.0 " -- " -- LC-79 -- -- " " -- -- " " -- 7.0 -- " -- " -- LC-80 -- -- " " -- -- " " -- -- 7.0 " -- " -- LC-81 -- -- " " -- -- " " -- 20.0 -- " -- " -- LC-82 -- -- " " -- -- " " -- -- 20.0 " -- " -- LC-83 -- -- " " -- -- " " -- 2.0 -- " -- " -- LC-84 -- -- -- 40 60 -- -- -- -- -- 2.0 0.8 -- 1.2 -- LC-85 -- -- 30 10 30 -- -- 30 -- -- " " -- " -- LC-86 -- 20 -- 20 -- -- 60 -- -- 2.0 -- 1.2 -- 1.6 -- LC-87 -- -- 40 -- -- -- -- 60 -- " -- " -- " -- LC-88 -- -- 30 10 30 -- -- 30 -- -- 2.0 " -- " -- LC-89 -- -- " -- " 10 -- " -- -- " 0.8 -- -- 1.2

EXAMPLES 1 TO 124

A series of adhesive compositions were prepared by mixing various urethane prepolymers containing two terminal isocyanate groups, which had been obtained in the foregoing synthesis of urethane prepolymers (I), with the radical-polymerizable unsaturated monomer/visible light polymerization initiator mixture LC-15 in a weight ratio of 1:1.

According to the above-described procedure for the evaluation of adhesivity and the above-described method for the measurement of bond strength, each of these adhesive compositions was used to bond restorative material A to an unetched dentin surface of a cattle tooth, and the resulting bond strength was measured. The results thus obtained are shown in Table 12.

Moreover, other series of adhesive compositions were prepared from various urethane prepolymers containing two terminal isocyanate groups and the radical-polymerizable unsaturated monomer/visible light polymerization initiator mixtures LC-15, LC-16, LC-22, LC-23, LC-56 and LC-57, and evaluated in the same manner. The results thus obtained are shown in Tables 12 to 16.

TABLE 12______________________________________Adhesive components Urethane Radical- Bond strength to prepolymer polymerizable dentin (kg/cm.sup.2) contg. two unsat. monomer/ After storage terminal visible light in waterExample isocyanate poly. initiator at 37.degree. C.No. groups mixture for 1 day for 7 days______________________________________1 TPT-1 LC-15 23.0 23.32 TPT-2 " 24.5 24.53 TPT-3 " 23.8 24.04 TPT-4 " 25.2 27.55 TPT-5 " 24.8 27.06 TPT-6 " 25.0 26.27 TPT-7 " 28.7 30.08 TPT-8 " 30.6 30.99 TPT-9 " 27.0 29.310 TPT-10 " 34.1 35.611 TPT-11 " 33.5 36.012 TPT-12 " 33.0 38.213 TPT-13 " 36.3 40.014 TPT-14 " 35.1 38.815 MPM-1 " 18.7 19.716 MPM-2 " 19.0 19.017 MPM-3 " 23.0 25.118 MPM-4 " 25.0 28.819 MPM-5 " 30.2 30.520 MPM-6 " 31.5 33.021 HPH-1 " 20.0 20.022 HPH-2 " 23.6 24.123 HPH-3 " 28.1 29.024 HPH-4 " 26.8 27.025 HPH-5 " 27.0 28.626 HPH-6 " 32.1 33.0______________________________________ TABLE 13__________________________________________________________________________Adhesive components Urethane prepolymer Radical-polymerizabe Bond strength to dentin (kg/cm.sup.2)Example contg. two terminal unsat. monomer/visible light After storage in water at 37.degree. C.No. isocyanate groups poly. initiator mixture for 1 day for 7 days__________________________________________________________________________27 TPT-1 LC-16 24.1 24.528 TPT-2 " 23.3 24.029 TPT-3 " 24.0 25.330 TPT-4 " 26.6 28.131 TPT-5 " 26.8 27.332 TPT-6 " 28.0 29.033 TPT-7 " 30.4 32.234 TPT-8 " 31.5 33.035 TPT-9 " 30.2 30.536 TPT-10 " 37.0 39.037 TPT-11 " 37.1 38.538 TPT-12 " 36.9 38.039 TPT-13 " 39.6 40.040 TPT-14 " 37.0 37.041 MPM-1 " 19.0 19.042 MPM-2 " 17.2 17.543 MPM-3 " 21.1 24.044 MPM-4 " 27.0 28.545 MPM-5 " 32.1 32.146 MPM-6 " 33.7 34.047 HPH-1 " 20.2 21.048 HPH-2 " 22.4 23.549 HPH-3 " 26.3 28.050 HPH-4 " 27.5 28.051 HPH-5 " 29.1 29.152 HPH-6 " 30.3 31.5__________________________________________________________________________ TABLE 14__________________________________________________________________________Adhesive components Urethane prepolymer Radical-polymerizabe Bond strength to dentin (kg/cm.sup.2)Example contg. two terminal unsat. monomer/visible light After storage in water at 37.degree. C.No. isocyanate groups poly. initiator mixture for 1 day for 7 days__________________________________________________________________________53 TPT-1 LC-22 25.1 25.554 TPT-2 " 26.7 26.755 TPT-3 " 26.0 26.256 TPT-4 " 27.4 29.757 TPT-5 " 26.5 29.258 TPT-6 " 27.2 28.459 TPT-7 " 30.1 32.260 TPT-8 " 32.8 33.161 TPT-9 " 29.2 31.562 TPT-10 " 36.3 37.863 TPT-11 " 35.7 38.264 TPT-12 " 35.2 41.065 TPT-13 " 39.5 42.166 TPT-14 " 37.3 40.667 MPM-1 " 21.1 21.968 MPM-2 " 21.2 20.369 MPM-3 " 25.4 27.170 MPM-4 " 27.2 31.471 MPM-5 " 32.4 32.772 MPM-6 " 33.7 35.273 HPH-1 " 22.2 22.574 HPH-2 " 25.8 26.375 HPH-3 " 31.2 31.276 HPH-4 " 29.0 29.277 HPH-5 " 29.2 30.478 HPH-6 " 34.3 35.1__________________________________________________________________________ TABLE 15__________________________________________________________________________Adhesive components Urethane prepolymer Radical-polymerizabe Bond strength to dentin (kg/cm.sup.2)Example contg. two terminal unsat. monomer/visible light After storage in water at 37.degree. C.No. isocyanate groups poly. initiator mixture for 1 day for 7 days__________________________________________________________________________79 TPT-1 LC-23 22.1 26.580 TPT-2 " 21.3 26.181 TPT-3 " 22.0 25.282 TPT-4 " 24.5 29.983 TPT-5 " 26.1 31.684 TPT-6 " 27.0 38.685 TPT-7 " 28.1 37.586 TPT-8 " 30.9 40.087 TPT-9 " 30.1 37.088 TPT-10 " 36.4 30.889 TPT-11 " 21.6 33.790 TPT-12 " 28.2 18.891 TPT-13 " 27.4 24.692 TPT-14 " 23.7 30.893 MPM-1 " 18.8 29.194 MPM-2 " 27.0 24.895 MPM-3 " 22.4 26.796 MPM-4 " 33.7 25.597 MPM-5 " 33.1 29.298 MPM-6 " 31.5 33.899 HPH-1 " 22.4 26.4100 HPH-2 " 30.3 35.9101 HPH-3 " 29.1 19.8102 HPH-4 " 27.5 26.4103 HPH-5 " 24.8 26.6104 HPH-6 " 30.9 31.9__________________________________________________________________________ TABLE 16__________________________________________________________________________Adhesive components Urethane prepolymer Radical-polymerizabe Bond strength to dentin (kg/cm.sup.2)Example contg. two terminal unsat. monomer/visible light After storage in water at 37.degree. C.No. isocyanate groups poly. initiator mixture for 1 day for 7 days__________________________________________________________________________105 TS-1 LC-56 30.4 28.8106 TS-2 " 26.3 26.0107 MS-1 " 29.4 28.0108 MS-2 " 33.7 30.4109 MS-3 " 28.2 30.7110 MS-4 " 24.9 25.5111 MS-5 " 25.2 22.9112 MS-6 " 23.6 24.4113 HS-1 " 26.2 24.6114 HS-2 " 25.7 25.9115 TS-1 LC-57 29.8 30.2116 TS-2 " 27.6 28.2117 MS-1 " 27.7 26.9118 MS-2 " 32.0 29.8119 MS-3 " 28.8 29.0120 MS-4 " 27.0 26.1121 MS-5 " 25.5 26.4122 MS-6 " 25.7 23.9123 HS-1 " 26.6 27.4124 HS-2 " 25.3 24.1__________________________________________________________________________

EXAMPLES 125 TO 130

A series of adhesive compositions were prepared by mixing various urethane prepolymers containing three free isocyanate groups, which had been obtained in the foregoing synthesis of urethane prepolymers (VII), with the radical-polymerizable unsaturated monomer/visible light polymerization initiator mixture LC-56 or LC-57 in a weight ratio of 1:1.

According to the above-described procedure for the evaluation of adhesivity and the above-described method for the measurement of bond strength, each of these adhesive compositions was used to bond restorative material A to an unetched dentin surface and an etched enamel surface, and the resulting bond strengths were measured. The results thus obtained are shown in Table 17.

TABLE 17__________________________________________________________________________Adhesive components Bond strength to dentin (kg/cm.sup.2) Bond strength to enamel (kg/cm.sup.2) Urethane prepolymer Radical-polymeriazbe After being stored in After being stored inExample contg. three free unsat. monomer/visibe light water at 37.degree. C. water at 37.degree. C.No. isocyanate groups poly. initiator mixture for 1 day for 7 days for 1 day for 7__________________________________________________________________________ days125 CO-1 LC-56 27.8 28.3 176 152126 CO-2 " 28.6 26.2 153 168127 CO-3 " 24.5 26.9 160 133128 CO-4 LC-57 31.6 28.4 145 161129 CO-5 " 29.1 30.2 184 157130 CO-6 " 26.4 29.2 163 142__________________________________________________________________________

EXAMPLES 131 TO 203

Several series of adhesive compositions were prepared by mixing the isocyanate-containing urethane prepolymer TPT-11, MS-2 or CO-2, which had been obtained in the foregoing synthesis of urethane prepolymers (I), (V) or (VII), with various radical-polymerizable unsaturated monomer/visible light polymerization initiator mixtures in a weight ratio of 1:1.

Then, using restorative material A, the adhesivity of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Tables 18 to 21.

TABLE 18__________________________________________________________________________Adhesive components Urethane prepolymer Radical-polymerizable Bond strength to dentin (kg/cm.sup.2)Example contg. two terminal unsat. monomer/visible light After storage in water at 37.degree. C.No. isocyanate groups poly. initiator mixture for 1 day__________________________________________________________________________131 TPT-11 LC-1 13.0132 " LC-2 12.1133 " LC-3 28.6134 " LC-4 29.0135 " LC-5 20.0136 " LC-6 23.0137 " LC-7 26.6138 " LC-8 23.2139 " LC-9 20.2140 " LC-10 20.0141 " LC-11 15.7142 " LC-12 16.8143 " LC-13 19.6144 " LC-14 28.2145 " LC-17 33.0146 " LC-18 34.8147 " LC-19 37.9__________________________________________________________________________ TABLE 19__________________________________________________________________________Adhesive components Urethane prepolymer Radical-polymerizable Bond strength to dentin (kg/cm.sup.2)Example contg. two terminal unsat. monomer/visible light After storage in water at 37.degree. C.No. isocyanate groups poly. initiator mixture for 1 day__________________________________________________________________________148 TPT-11 LC-20 26.9149 " LC-21 27.8150 " LC-22 32.4151 " LC-23 33.7152 " LC-24 25.5153 " LC-25 26.1154 " LC-26 38.8155 " LC-27 38.6156 " LC-28 35.4157 " LC-29 37.1158 " LC-30 21.9159 " LC-31 24.7160 " LC-32 28.6161 " LC-33 29.3162 " LC-34 41.8163 " LC-35 43.2__________________________________________________________________________ TABLE 20__________________________________________________________________________Adhesive components Urethane prepolymer Radical-polymerizable Bond strength to dentin (kg/cm.sup.2)Example contg. two terminal unsat. monomer/visible light After storage in water at 37.degree. C.No. isocyanate groups poly. initiator mixture for 1 day__________________________________________________________________________164 MS-2 LC-36 18.2165 " LC-37 16.9166 " LC-38 26.6167 " LC-39 22.4168 " LC-40 29.8169 " LC-41 28.0170 " LC-42 30.4171 " LC-43 33.2172 " LC-44 29.1173 " LC-45 27.5174 " LC-46 25.5175 " LC-47 26.9176 " LC-48 30.1177 " LC-51 28.2178 " LC-52 34.0179 " LC-53 32.8180 " LC-54 30.4__________________________________________________________________________ TABLE 21__________________________________________________________________________Adhesive components Urethane prepolymer Radical-polymerizable Bond strength to dentin (kg/cm.sup.2)Example contg. two terminal unsat. monomer/visible light After storage in water at 37.degree. C.No. isocyanate groups poly. initiator mixture for 1 day__________________________________________________________________________181 CO-2 LC-36 18.2182 " LC-37 16.6183 " LC-38 27.4184 " LC-39 22.5185 " LC-40 33.0186 " LC-41 28.4187 " LC-42 29.3188 " LC-43 28.2189 " LC-44 24.1190 " LC-45 25.0191 " LC-46 27.8192 " LC-47 28.2193 " LC-48 26.7194 " LC-51 29.4195 " LC-52 35.4196 " LC-53 30.1197 " LC-54 34.5198 " LC-55 26.3199 " LC-56 32.5200 " LC-57 28.8201 " LC-58 27.3202 " LC-59 29.0203 " LC-60 31.6__________________________________________________________________________

EXAMPLES 204 TO 228

According to the same procedure as described in Example 1, several series of adhesive compositions were prepared by using various urethane prepolymers containing one terminal isocyanate group and one terminal hydroxyl group, which had been obtained in the foregoing synthesis of urethane prepolymers (II), (III) or (VI), and various urethane prepolymers containing one terminal radical-polymerizable vinyl group and one terminal isocyanate group, which had been obtained in the foregoing synthesis of urethane prepolymers (III). Then, the adhesivity of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Tables 22 and 23.

TABLE 22__________________________________________________________________________Adhesive components Radical-polymerizable unsat. Bond strength to dentin (kg/cm.sup.2)Example monomer/visible light poly. After storage in 37.degree. C.No. initiator mixture for 1 day__________________________________________________________________________ Urethane prepolymer contg. one terminal isocyanate group and one terminal hydroxyl group204 PT-1 LC-15 12.0205 PT-2 " 10.0206 PT-3 " 10.2207 PT-4 " 13.1208 PT-5 " 12.4209 PT-6 " 12.0210 PM-1 " 8.7211 PM-2 " 9.8212 PM-3 " 10.3213 PH-1 " 10.0214 PH-2 " 11.8215 PH-3 " 14.1 Urethane prepolymer contg. one terminal radical-polymerizable vinyl group and one terminal isocyanate group216 TV-1 LC-15 18.0217 TV-2 " 16.7218 TV-3 " 17.0219 MV-1 " 13.8220 HV-1 " 15.0__________________________________________________________________________ TABLE 23__________________________________________________________________________Adhesive components Urethane prepolymer contg. Radical-polymerizable unsat. Bond strength to dentin (kg/cm.sup.2)Example one terminal isocyanate group and monomer/visible light poly. After storage in 32.degree. C.No. one terminal hydroxyl group initiator mixture for 1 day__________________________________________________________________________221 TH-1 LC-56 10.4222 PT-2 " 8.9223 MH-1 " 13.3224 PT-2 " 10.9225 PT-3 " 11.2226 PT-4 " 8.0227 PM-1 " 10.4228 PM-2 " 7.7__________________________________________________________________________

EXAMPLES 229 TO 234

According to the same procedure as described in Example 128, a series of adhesive compositions were prepared by using various urethane prepolymers containing one radical-polymerizable vinyl group and two free isocyanate groups and various urethane prepolymers containing two radical-polymerizable vinyl groups and one free isocyanate group, which had been obtained in the foregoing synthesis of urethane prepolymers (VIII). Then, the adhesivity of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 24.

TABLE 24__________________________________________________________________________Adhesive components Urethane prepolymer contg. one Radical-polymerizable unsat. Bond strength to dentin (kg/cm.sup.2)Example (two) radical polymerizable unsat. monomer/visible light poly. After storage in 37.degree. C.No. two (one) free isocyanate groups initiator mixture for 1 day__________________________________________________________________________229 SV-1 LC-56 23.2230 SV-2 " 27.0231 SV-3 " 24.9232 VV-1 " 16.8233 VV-2 " 13.4234 VV-3 " 15.7__________________________________________________________________________

EXAMPLES 235 TO 246

According to the same procedure as described in Examples 7, 33, 59 or 85, various adhesive compositions were prepared by varying the weight ratio of the urethane prepolymer containing two terminal isocyanate groups to the radical-polymerizable unsaturated monomer/visible light polymerization initiator mixture. Then, the bonding power of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 25.

TABLE 25__________________________________________________________________________Ratio between adhesive components(parts by weight) Urethane prepolymer contg. Radical-polymerizable unsat. Bond strength to dentin (kg/cm.sup.2)Example two terminal isocyanate monomer/visible light poly. After storage in water at 37.degree. C.No. groups initiator mixture for 1 day__________________________________________________________________________235 TPT-7:10 LC-15:90 20.0236 TPT-7:30 LC-15:70 24.0237 TPT-7:80 LC-15:20 31.2238 TPT-7:10 LC-16:90 20.0239 TPT-7:30 LC-16:70 24.4240 TPT-7:80 LC-16:20 35.0241 TPT-7:10 LC-22:90 23.7242 TPT-7:30 LC-22:70 28.6243 TPT-7:80 LC-22:20 35.2244 TPT-7:10 LC-23:90 21.9245 TPT-7:30 LC-23:70 23.0246 TPT-7:80 LC-23:20 36.2__________________________________________________________________________

EXAMPLES 247 TO 249

According to the same procedure as described in Example 125, various adhesive compositions were prepared by varying the weight ratio of the urethane prepolymer containing three free isocyanate groups to the radical-polymerizable unsaturate monomer/visible light polymerization initiator mixture. Then, the adhesivity of these adhesive compositions to an unetched dentin surface was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 26.

TABLE 26__________________________________________________________________________Ratio between adhesive components(parts by weight) Urethane prepolymer contg. Radical-polymerizable unsat. Bond strength to dentin (kg/cm.sup.2)Example three free isocyanate monomer/visible light poly. After storage in water at 37.degree. C.No. groups initiator mixture for 1 day__________________________________________________________________________247 CO-1:10 LC-56:90 14.1248 CO-1:30 LC-56:70 22.4249 CO-1:80 LC-56:20 31.0__________________________________________________________________________

EXAMPLES 250 TO 265

Using the adhesive compositions obtained in Examples 10, 62, 118 and 129, their adhesivity to various restorative materials was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 27.

TABLE 27______________________________________ Bond strength to dentinExample Adhesive Type of restorative (kg/cm.sup.2)No. composition material *1______________________________________250 Example 10 Restorative material B 38.2251 " Commercially available 35.0 one-paste composite resin *2252 " Commercially available 29.6 two-paste composite resin *3253 " Polymethyl methacrylate *4 31.0254 Example 62 Restorative material B 34.7255 " Commercially available 29.4 one-paste composite resin *2256 " Commercially available 31.5 two-paste composite resin *3257 " Polymethyl methacrylate *4 30.5258 Example 117 Restorative material B 32.9259 " Commercially available 26.4 one-paste composite resin *2260 " Commercially available 28.8 two-paste composite resin *3261 " Polymethyl methacrylate *4 25.1262 Example 129 Restorative material B 30.8263 " Commercially available 24.6 one-paste composite resin *2264 " Commercially available 28.5 two-paste composite resin *3265 " Polymethyl methacrylate *4 29.0______________________________________ *1: Measured after storage in water at 37.degree. C. for 1 day. *2: Occlusin (trade name; a product of ICI Co.). *3: Microrest AP (trade name; a product of GC Dental Industries Co.). *4: Acrypet #VH (trade name; a product of Mitsubishi Rayon Co., Ltd.).

COMPARATIVE EXAMPLES 1 TO 14

According to the same procedure as described in Example 1, a series of adhesive compositions were prepared by using various polyether glycols, which had been obtained in the foregoing synthesis of urethane prepolymers (I), in place of the urethane prepolymer containing two terminal isocyanate groups. Then, the bonding power of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 28.

TABLE 28______________________________________ Bond strength to dentin Adhesive components (kg/cm.sup.2) Radical-polymer- AfterCompara- izable unsat. storagetive monomer/visible in waterExample Polyether light poly. at 37.degree. C.No. glycol initiator mixture 1 day______________________________________1 PEP-1 LC-15 0.02 PEP-2 " 0.03 PEP-3 " 0.04 PEP-4 " 0.05 PEP-5 " 0.06 PEP-6 " 0.07 PEP-7 " 0.08 PEP-8 " 0.09 PEP-9 " 0.010 PEP-10 " 0.011 PEP-11 " 0.012 PEP-12 " 0.013 PEP-13 " 0.014 PEP-14 " 0.0______________________________________

COMPARATIVE EXAMPLES 15 TO 20

According to the same procedure as described in Example 1, a series of adhesive compositions were prepared by using various polyester glycols, which had been obtained in the foregoing synthesis of urethane prepolymers (V), in place of the urethane prepolymer containing two terminal isocyanate groups. Then, the bonding power of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 29.

TABLE 29______________________________________ Bond strength to dentin Adhesive components (kg/cm.sup.2) Radical-polymer- After izable unsat. storageComp. monomer/visible in waterExample Polyether light poly. at 37.degree. C.No. glycol initiator mixture 1 day______________________________________15 SG-1 LC-57 0.016 SG-2 " 0.017 SG-3 " 0.018 SG-4 " 0.019 SG-5 " 0.020 SG-6 " 0.0______________________________________

COMPARATIVE EXAMPLE 21 TO 23

According to the same procedure as described in Example 125, a series of adhesive compositions were prepared by using various urethane prepolymers having two terminal radical-polymerizable vinyl groups, which had been obtained in the foregoing synthesis of urethane prepolymers (IX), in place of the urethane prepolymer containing two terminal isocyanate groups. Then, the adhesivity of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 30.

TABLE 30______________________________________ Bond strengthAdhesive components to dentin Urethane pre- (kg/cm.sup.2) polymer contg. Radical-polymer- After two terminal izable unsat. storageComp. radical-poly- monomer/visible in waterExample merizable vinyl light poly. at 37.degree. C.No. groups initiator mixture for 1 day______________________________________21 DV-1 LC-15 0.022 DV-2 " 0.023 DV-3 " 0.0______________________________________

COMPARATIVE EXAMPLES 24 TO 29

According to the same procedure as described in Example 125 or 128, a series of adhesive compositions were prepared by using various urethane prepolymers having three radical-polymerizable vinyl groups, which has been obtained in the foregoing synthesis of urethane prepolymers (IX), in place of the urethane prepolymer containing three free isocyanate groups. Then, the adhesivity of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 31.

TABLE 31______________________________________ Bond strength to dentinAdhesive components (kg/cm.sup.2) Urethane pre- Radical-polymer- After polymer contg. izable unsat. storageComp. three radical- monomer/visible in waterExample polymerizable light poly. at 37.degree. C.No. vinyl groups initiator mixture for 1 day______________________________________24 PV-1 LC-56 0.025 PV-2 " 0.026 PV-3 " 0.027 PV-1 LC-57 0.028 PV-2 " 0.029 PV-3 " 0.0______________________________________

EXAMPLES 266 TO 317

A series of adhesive compositions were prepared by mixing various urethane prepolymers containing two terminal isocyanate groups, which had been obtained in the foregoing synthesis of urethane prepolymers (I), with the monomer X/monomer Z/visible light polymerization initiator mixture LC-69 in a weight ratio of 1:1.

According to the above-described procedure for the evaluation of adhesivity and the above-described method for the measurement of bond strength, each of these adhesive compositions was used to bond restorative material A to an unetched dentin surface of a cattle tooth, and the resulting bond strength was measured. The results thus obtained are shown in Table 32.

Moreover, another series of adhesive compositions were prepared with LC-64 and evaluated in the same manner. The results thus obtained are also shown in Table 32.

TABLE 32__________________________________________________________________________Adhesive components Bond strength to Monomer X/monomer dentin (kg/cm.sup.2) Urethane prepolymer Z/visible light After storage in waterExample contg. two terminal poly. initiator at 37.degree. C.No. isocyanate groups mixture for 1 day for 7 days__________________________________________________________________________266 TPT-1 LC-69 37.1 37.8267 TPT-2 " 38.7 35.4268 TPT-3 " 38.0 40.9269 TPT-4 " 39.5 38.8270 TPT-5 " 37.8 37.9271 TPT-6 " 39.8 39.7272 PTP-7 " 42.2 42.0273 TPT-8 " 43.7 45.0274 TPT-9 " 41.5 41.8275 TPT-10 " 48.8 47.7276 TPT-11 " 47.4 47.6277 TPT-12 " 45.2 44.8278 TPT-13 " 50.9 47.8279 TPT-14 " 59.5 51.1280 MPM-1 " 33.0 34.2281 MPM-2 " 33.7 33.5282 MPM-3 " 37.6 39.2283 MPM-4 " 43.5 45.1284 MPM-5 " 45.5 46.4285 MPM-6 " 34.2 33.9286 HPH-1 " 37.7 35.4287 HPH-2 " 42.8 42.9288 HPH-3 " 41.0 41.7289 HPH-4 " 40.6 42.5290 HPH-5 " 41.2 40.7291 HPH-6 " 46.3 47.5292 TPT-1 LC-64 39.7 38.2293 TPT-2 " 35.2 42.5294 TPT-3 " 35.7 39.5295 TPT-4 " 37.7 36.3296 TPT-5 " 39.6 38.7297 TPT-6 " 43.6 42.6298 TPT-7 " 41.4 51.9299 TPT-8 " 45.1 45.7300 TPT-9 " 43.4 43.0301 TPT-10 " 47.7 47.9302 TPT-11 " 49.0 47.8303 TPT-12 " 51.4 50.0304 TPT-13 " 45.2 49.4305 TPT-14 " 51.4 52.5306 MPM-1 " 35.5 32.5307 MPM-2 " 35.6 30.7308 MPM-3 " 38.7 38.8309 MPM-4 " 44.2 43.2310 MPM-5 " 45.5 46.0311 MPM-6 " 47.7 47.5312 HPH-1 " 36.4 35.4313 HPH-2 " 38.7 36.4314 HPH-3 " 43.1 43.4315 HPH-4 " 39.3 38.9316 HPH-5 " 43.9 43.1317 HPH-6 " 45.5 45.5__________________________________________________________________________

EXAMPLES 318 TO 327

A series of adhesive compositions were prepared by mixing the urethane prepolymer TPT-11 containing two terminal isocyanate groups, which had been obtained in the foregoing synthesis of urethane prepolymers (I), with various monomer X/monomer Z/visible light polymerization initiator mixtures in a weight ratio of 1:1.

Then, using restorative material A, the adhesivity of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 33.

TABLE 33______________________________________ Bond strength to dentinAdhesive Components (kg/cm.sup.2) Urethane pre- After polymer contg. Monomer X/monomer storage two terminal Z/visible light in waterExample isocyanate poly. initiator at 37.degree. C.No. groups mixture for 1 day______________________________________318 TPT-11 LC-61 30.5319 " LC-62 33.7320 " LC-63 36.8321 " LC-64 38.9322 " LC-65 28.4323 " LC-66 27.5324 " LC-67 45.6325 " LC-68 48.3326 " LC-69 51.0327 " LC-70 50.1______________________________________

EXAMPLES 328 TO 344

A series of adhesive compositions were prepared by mixing the urethane prepolymer TPT-11 containing two terminal isocyanate groups, which had been obtained in the foregoing synthesis of urethane prepolymers (I), with various monomer X/monomer Z/visible light polymerization initiator mixtures (i.e, LC-73 to LC-88) in a weight ratio of 1:1.

Then, using restorative material A, the adhesivity of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 34.

TABLE 34______________________________________ Bond strength to dentinAdhesive Components (kg/cm.sup.2) Urethane pre- After polymer contg. Monomer X/monomer storage two terminal Z/visible light in waterExample isocyanate poly. initiator at 37.degree. C.No. groups mixture for 1 day______________________________________328 TPT-11 LC-73 35.4329 " LC-74 33.0330 " LC-75 43.8331 " LC-76 40.5332 " LC-77 49.7333 " LC-78 48.6334 " LC-79 37.5335 " LC-80 37.1336 " LC-81 29.9337 " LC-82 32.2338 " LC-83 36.8339 " LC-84 41.1340 " LC-85 35.2341 " LC-86 37.9342 " LC-87 47.5343 " LC-89 46.3344 " LC-89 46.8______________________________________

COMPARATIVE EXAMPLES 30 TO 43

According to the same procedure as described in Example 1, a series of adhesive compositions were prepared by using various polyether glycols, which had been obtained in the foregoing synthesis of urethane prepolymers (I), in place of the urethane prepolymer containing two terminal isocyanate groups. Then, the adhesivity of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 35.

TABLE 35______________________________________ Bond strength to dentin (kg/cm.sup.2)Adhesive components After Monomer X/monomer storageComp. Z/visible light in waterExample Polyether poly. initiator at 37.degree. C.No. glycol mixture for 1 day______________________________________30 PEP-1 LC-63 0.031 PEP-2 " 0.032 PEP-3 " 0.033 PEP-4 " 0.034 PEP-5 " 0.035 PEP-6 " 0.036 PEP-7 " 0.037 PEP-8 " 0.038 PEP-9 " 0.039 PEP-10 " 0.040 PEP-11 " 0.041 PEP-12 " 0.042 PEP-13 " 0.043 PEP-14 " 0.0______________________________________

COMPARATIVE EXAMPLES 44 TO 55

A series of adhesive compositions comprising various monomer X/monomer Z/visible light polymerization initiator mixture alone were prepared. Then, the adhesivity of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 36.

TABLE 36______________________________________ Bond strength to dentinAdhesive Components (kg/cm.sup.2) Urethane pre- After polymer contg. Monomer X/monomer storageComp. two terminal Z/visible light in waterExample isocyanate poly. initiator at 37.degree. C.No. groups mixture for 1 day______________________________________44 Not used LC-61 30.545 " LC-62 0.046 " LC-63 0.047 " LC-64 0.048 " LC-65 0.049 " LC-66 0.050 " LC-67 0.051 " LC-68 0.052 " LC-69 0.053 " LC-70 0.054 " LC-71 0.055 " LC-72 0.0______________________________________

COMPARATIVE EXAMPLES 56 TO 59

A series of adhesive compositions were prepared by mixing the urethane prepolymer TPT-11 containing two terminal isocyanate groups, which had been obtained in the foregoing synthesis of urethane prepolymers (I), with various monomer X/monomer Z/visible light polymerization initiator mixtures as shown in Table 38 (i.e., LC-77, to LC-80), in a weight ratio of 1:1.

Then, using restorative material A, the adhesivity of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 37.

TABLE 37______________________________________ Bond strength to dentinAdhesive Components (kg/cm.sup.2) Urethane pre- After polymer contg. Monomer X/monomer storageComp. two terminal Z/visible light in waterExample isocyanate poly. initiator at 37.degree. C.No. groups mixture for 1 day______________________________________56 TPT-11 LC-90 15.357 " LC-91 17.158 " LC-92 11.859 " LC-93 9.0______________________________________ TABLE 38__________________________________________________________________________Code formonomerX/monomer Monomer X, monomer Z and amounts usedZ/visible Tri- Meth- Dimeth-light Acryl- 2-Hydroxy- ethylene acryl- acryloxy-poly. oxy Benzyl ethyl glycol oxyethyl ethylinitiator piva- metha- metha- dimeth- Bis- Bis- U- U- phos- phos-mixture late crylate crylate acrylate BMA MEPP 4HA 6HA phate phate__________________________________________________________________________LC-90 -- -- 30 10 -- 30 30 -- 40.0 --LC-91 -- -- " " -- " " -- -- 40.0LC-92 -- -- " " -- " " -- 60.0 --LC-93 -- -- " " -- " " -- -- 60.0__________________________________________________________________________ Code for monomer X/monomer Z/visible light Visible light poly. initiator and amount used (g) poly. Isoamyl 4,4'-Bis- initiator Camphor- 4-(N,N-dimethyl- (dimethylamino)- mixture quinone amino) benzoate benzophenone__________________________________________________________________________ LC-90 0.8 1.2 -- LC-91 " " -- LC-92 " -- 12 LC-93 " -- "__________________________________________________________________________

EXAMPLES 345 TO 350

According to the same procedures as described in Example 1, various adhesive compositions were prepared by varying the weight ratio of the urethane prepolymer containing two terminal isocyanate groups to the monomer X/monomer Z/visible light polymerization initiator mixture. Then, the adhesivity of these adhesive compositions was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 39.

TABLE 39______________________________________ Bond strengthRatio between adhesive to dentincomponents (parts by weight) (kg/cm.sup.2) Urethane pre- After polymer contg. Monomer X/monomer storage two terminal Z/visible light in waterExample isocyanate poly. initiator at 37.degree. C.No. groups mixture for 1 day______________________________________345 TPT-7:10 LC-67:90 34.8346 .sup. :30 .sup. :70 41.6347 .sup. :80 .sup. :20 47.4348 .sup. :10 LC-68:90 30.5349 .sup. :30 .sup. :70 43.3350 .sup. :80 .sup. :20 48.4______________________________________

EXAMPLES 351 TO 354

Using the adhesive composition obtained in Example 275, its adhesivity to various restorative materials was evaluated in the same manner as described in Example 1. The results thus obtained are shown in Table 40.

TABLE 40______________________________________ Bond strengthExample to dentinNo. Restorative material (kg/cm.sup.2) *1______________________________________351 Restorative material B 40.5352 Commercially available one- 38.9 paste composite resin *2353 Commercially available two- 33.7 paste composite resin *3354 Polymethyl methacrylate *4 35.7______________________________________ *1: Measured after storage in water at 37.degree. C. for 1 day. *2: Occlusin (trade name; a product of ICI Co.). *3: Microrest AP (trade name; a product of GC Dental Industries Co.). *4: Acrypet #VH (trade name; a product of Mitsubishi Rayon Co., Ltd.).

Claims

1. A dental adhesive composition consisting essentially of

(a) at least one urethane prepolymer containing one or more isocyanate groups; or a blend of the urethane prepolymer and an inert diluent, where said urethane prepolymer contains isocyanate groups at each end;

(b) At least one radical polymerizable unsaturated monomer;

(c) a photopolymerization initiator; and

(d) a polymerizable phosphoric ester compound of the general formula (1): ##STR18## where R is a group selected from the class consisting of ##STR19## in which R.sub.1 is an alkylene group, R' is an alkyl group, n is 1 or 2, m is 1 or 2, l is 0 or 2 and the sum of (n+m+l) is equal to 3.

2. A dental adhesive composition as claimed in claim 1 wherein the urethane prepolymer containing one or more isocyanate groups is a compound of the structural formula (2): ##STR20## where m is a whole number of 1 to 100, n is a whole number of 0 to 100, and the propylene oxide units may be randomly joined to the ethylene oxide units.

3. A dental adhesive composition as claimed in claim 1 wherein the urethane prepolymer containing one or more isocyanate groups is a compound of the structural formula (3): ##STR21## where m is a whole number of 1 to 100, n is a whole number of 0 to 100, and the propylene oxide units may be randomly joined to the ethylene oxide units.

4. A dental adhesive composition as claimed in claim 1 wherein the urethane prepolymer containing one or more isocyanate groups is a compound of the structural formula (4): ##STR22## where m is a whole number of 1 to 100, n is a whole number of 0 to 100, and the propylene oxide units may be randomly joined to the ethylene oxide units.

5. A dental adhesive composition as claimed in claim 1 wherein the urethane prepolymer containing one or more isocyanate groups has an average molecular weight of 400 to 20,000.

6. A dental adhesive composition as claimed in claim 2 wherein the urethane prepolymer containing one or more isocyanate groups has been rendered hydrophilic or water-soluble by adjusting its ethylene oxide unit content to a level of 40 to 80 mole percent based on the combined amount of the propylene oxide units and ethylene oxide units constituting the prepolymer chain.

7. A dental adhesive composition as claimed in claim 1 wherein the urethane prepolymer containing one or more isocyanate groups is a compound obtained by reacting a polyester polyol with a polyisocyanate, the polyester polyol having the structural formula (5): ##STR23## where a is a whole number of 1 to 5, b is a whole number of 4 to 10, and d is a whole number of 1 to 200.

8. A dental adhesive composition as claimed in claim 1 wherein the urethane prepolymer containing one or more isocyanate groups is a compound obtained by reacting castor oil or a derivative there of with a polyisocyanate.

9. A dental adhesive composition as claimed in claim 7 wherein the polyisocyanate is one or more compound selected from the group consisting of tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and hexamethylene diisocyanate.

10. A dental adhesive composition as claimed in claim 1 wherein the radical-polymerizable unsaturated monomer is a polyethylene glycol di(meth)acrylate of the general formula (7): ##STR24## where R.sup.1 is a hydrogen atom or a methyl group, and p is a whole number of 1 to 20.

11. A dental adhesive composition as claimed in claim 1 wherein the radical-polymerizable unsaturated monomer is a urethane di(meth)acrylate of the general formula (8): ##STR25## where R.sup.1 is a hydrogen atom or a methyl group, and R.sup.2 is an alkylene group of 1 to 8 carbon atoms, or ##STR26##

12. A dental adhesive composition as claimed in claim 1 wherein the radical-polymerizable unsaturated monomer is methyl acrylate, methyl methacrylate, vinyl acetate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, nonaethylene glycol diacrylate, nonaethylene glycol dimethacrylate, tetradecaethylene glycol dimethacrylate, tetradecaethylene glycol diacrylate, trimethylolpropane trimethacrylate, or the urethane dimethacrylate of the structural formula (9): ##STR27##

13. A dental adhesive composition as claimed in claim 1 wherein the radical-polymerizable unsaturated monomer is a (meth)acrylate compound having a bisphenol A skeleton and represented by the general formula (10) or (11): ##STR28## where R.sup.3 is a hydrogen atom or a methyl group, and q is a whole number of 1 to 20.

14. A dental adhesive composition as claimed in claim 1 wherein the radical-polymerizable unsaturated monomer is a compound of the general formula (12): ##STR29## where R.sub.1 and R.sub.2 are hydrogen atoms or methyl groups. and X is --CH.sub.2 --, --CH.sub.2 CH.sub.2 --, --(CH.sub.2).sub.3 --, --(CH.sub.2).sub.4 --, --(CH.sub.2).sub.5 --, --(CH.sub.2).sub.6 -- or ##STR30##

15. A dental adhesive composition as claimed in claim 1 wherein the radical-polymerizable unsaturated monomer is a hexafunctional urethane (meth)acrylate compound having an isocyanuric acid skeleton and represented by the general formula (13): ##STR31## where R.sup.4 and R.sup.5 are hydrogen atoms or methyl groups, and r is a whole number of 1 to 10.

16. A dental adhesive composition as claimed in claim 1 wherein the photopolymerization initiator is a mixture of camphorquinone and isoamyl 4-(N,N-dimethylamino)benzoate.

17. A dental adhesive composition as claimed in claim 1 wherein the photopolymerization initiator is a mixture of camphorquinone and 4,4'-bis(dimethylamino)-benzophenone or 4,4'-bis(diethylamino)benzophenone.

18. A dental adhesive composition as claimed in claim 16 wherein the amounts of camphorquinone and isoamyl 4-(N,N-dimethylamino)benzoate used are 0.05 to 15% by weight and 0.1 to 25% by weight, respectively, based on the radical-polymerizable unsaturated monomer.

19. A dental adhesive composition as claimed in claim 1 wherein the amounts of camphorquinone and 4,4'-bis(dimethylamino)benzophenone used are 0.03 to 20% by weight and 0.05 to 20% by weight, respectively, based on the radical-polymerizable unsaturated monomer.

20. A dental adhesive composition as claimed in claim 1 wherein the weight ratio of component (a) to component (b) ranges from 1:50 to 50:1.

21. A dental adhesive composition as claimed in claim 1 wherein composition (a) and a blend of components (b) and (c) are stored separately and mixed just before use.