JPS60166364A - Novel adhesive - Google Patents

Abstract

PURPOSE:A novel adhesive, containing a specific compound as a monomer capable of giving adhesive properties and a monomer copolymerizable therewith in respective specific amounts, capable of bonding powerfully to biological tissues and metal materials, etc., and having improved water resistance of adhesive force. CONSTITUTION:A novel adhesive obtained by incorporating (A) 1pt.wt. compound expressed by the formula [R1 and R1' are H or CH3; X1, X1', X2 and X2' are O, S, or NRalpha (Ralpha is H or 1-6C alkyl); m is an integer 1-4; n is an integer 0- 4; k and k' are 0 or 1; Ra is 8-40C (m+1)-valent organic residue; Ra' is 1-40C (n+1)-valent organic residue] with (B) 0-199pts.wt. monomer copolymerizable with the compound (A), e.g. methyl methacrylate, and if necessary a filler, e.g. a natural mineral, a polymerization inhibitor or an antioxidant. Bonding is carried out by oating or filling an adhesive surface with the above-mentioned adhesive, and polymerizing and curing the adhesive under heating, etc. USE:For fields of dental, orthopedics, general industrial uses, and domestic uses, etc.

Description

Detailed Description of the Invention (Technical Field) The present invention is capable of strongly adhering to biological hard tissues such as teeth and bones, metal materials, organic polymer materials, and ceramic materials, and has excellent adhesive strength and water resistance. Regarding superior adhesives. In the present invention, the term "adhesive" refers not only to a composition used to bond multiple adherends together, but also to a composition that has excellent adhesive properties to the surface of adherends such as metal materials and organic polymer materials. It is used to include compositions used to form a coating layer, as well as compositions used to form a filling with excellent adhesive properties when repairing biological hard tissue. In other words, organic polymer materials
It refers to all compositions which are applied to various materials such as ceramic materials and exhibit adhesive properties to these materials.

(Prior Art) Various metal materials, organic polymer materials, and ceramic materials are used as restorative materials for tooth restoration. When these materials are placed into the oral cavity, it is necessary to ensure sufficient adhesion between teeth and metal, organic polymer, or ceramic materials, and between metal and restorative materials such as metal, ceramic, or organic polymer. It is. Particularly in the dental field, since adhesives are used in the oral cavity, adhesion under moist conditions is required.

Conventionally, in the dental field, attempts have been made widely to use phosphate ester compounds as adhesives.

It has been shown to be effective as In fact, certain compositions falling within the above range have been put to practical use and are widely used as primers for coating the walls of tooth cavities before filling them.

However, when using the composition described in the above-mentioned patent, there is a problem that sufficient adhesion to the tooth cannot be obtained unless the cavity surface is acid-etched in advance. There is also a problem in that the above-mentioned composition does not have sufficient adhesion to Ni--Cr alloy, which is a metal material.

(2) Some attempts to obtain adhesives that have adhesive properties to teeth using polymerizable phosphate ester compounds are described below. However, all of these have insufficient adhesive strength and have not been put into practical use.

(1) Phosphor in USP 5aa26oo
yl mono-f 1uoride is described.

(If) Journal of Dental Re
5earch Vol153. P, 878-888 and Vol 56. P, 945-952. Chem
icalAbstract Vol 77, p, 29
0 (66175g) and JP-A-51-44152, a compound obtained by neutralizing one OH group of the two OH groups of a compound represented by CH2=CHPO(OH')2 has the general formula and the following are specifically shown (
M is an alkali metal).

CH2=CHC6H40PO(OHXOM), CH2=
CHCH20PO(OH)(OM), HO-P=0 H36M CH2=CC0C00CH2CH20CH2CHCH2
0PO(OHXO, OPO(OH)(OM) CH2=CCOO δH3 (Ethane-1,1-diphosphonic acid) is described in Japanese Patent Publication No. 57-49557 as an adhesive component of a dental adhesive.

In the case of none of the above-mentioned compounds, it is not possible to obtain high adhesive strength when wet. (Especially for metals) (3) Also refers to JP-A-57-131799 and JP-A-Sho lyloyloxy (lower) alkyl, and R2 means allyl, methacryloyloxy (lower) alkyl or aryl. The (lower) alkyl in R) and R2 may be substituted with hydroxy. Examples of lower compounds include those having 6 or less carbon atoms. ] A ruhyrophosphate ester derivative is described.

Although the compound is described as enhancing adhesion to denture enamel, nothing is said about adhesion to metals. In fact, even in additional tests conducted by the present inventors regarding the effects of the compound, no significant improvement in water resistance of metal bond strength was observed.

(4) Furthermore, attempts to use phosphate ester compounds in adhesives have been widely made in the industrial field. For example, USP5754972, USP58848
No. 64, USP 3987127, USP 400415
No. 0, USP No. 4044044, USP No. 4223115
No., JP-A-49-20238, JP-A-50-1005
No. 96, JP-A-51-125182, JP-A-53-1
No. 2995, Japanese Patent Publication No. 16-11920, Japanese Patent Application Publication No. 1987
-44658, Special Publication No. 55-4126, Special Publication No. 1983
-4790 etc. However, the phosphoric acid ester compounds described in these patent documents have problems in adhesive strength and water resistance.

(Object of the Invention) The object of the present invention is to improve the relationship between (a) biological hard tissues and (b) biological hard tissues or materials for repairing the tissues (metal materials, organic polymer materials, ceramic materials, etc.). The object of the present invention is to provide an adhesive composition having excellent adhesive properties to biological hard tissue, which is used for adhesion, and is also used to fill and repair biological hard tissue.

Another object of the present invention is to provide a method for adhering between (a) a metal material and (b) a metal material, an organic polymer material, or a ceramic material, or between a ceramic material and a ceramic material or an organic polymer material. The object of the present invention is to provide an adhesive composition for industrial and household use, or for use in coating agents, paints, etc. for forming films with excellent adhesiveness on the surfaces of metal materials and ceramic materials.

Still another object of the present invention is to provide a dental adhesive that can be applied to the wall of a tooth cavity before filling and restoring the tooth cavity to provide a strong bond between the tooth and the filling material.

Yet another object of the present invention is to provide a dental filling material that has excellent adhesion to teeth and is used for filling and restoring tooth cavities.

Furthermore, another object of the present invention is to provide tooth and dental restorative materials (
The objective is to provide a dental adhesive for bonding and fixing dental restoration materials (for example, an abutment tooth and a crown) together (inlays, anlays, abutment teeth, bridges, posts, splints, orthodontic brackets, crowns).

Yet another object of the present invention is to provide a dental adhesive for use as a Fischer sealant applied to tooth surfaces to prevent dental caries.

Furthermore, another object of the present invention is to provide a strong and stable bond between a tooth and a filling material or a restorative material, thereby making the restoration of the tooth more complete, or by coating the surface of the tooth. The aim is to provide a dental treatment method that prevents this.

This is the object of the present invention.

(a) General formula [In the above formula, R+, R;, Ra, Ra, Xl
, x? , X2, X'z, m, n, k,
k' represents the following R1, R'+: H or methyl group X1. X'+, X7. X′! : 0, S or NRα(
However, k is H or an alkyl group having 1 to 6 carbon atoms) m: 1
n: an integer from 0 to 4, ni': o or 1 Ra: (m+1)-valent organic residue having 8 to 40 carbon atoms R:
Achieved by an adhesive comprising 1 part by weight of a compound represented by an (n+1)-valent organic residue having 1 to 40 carbon atoms and (b) 0 to 199 parts by weight of a monomer copolymerizable with the compound. Ru.

(Structure and Effects of the Invention) The adhesive of the present invention is characterized in that the compound (a) is used as a monomer (sometimes referred to as an adhesive monomer) that provides adhesiveness to biological hard tissues, metals, and ceramics. has.

Incidentally, in the present invention, the term organic residue is used to include the following (1) and (11).

(1) A hydrocarbon group (11) which may have an OH group, a C0OH group, an NH2 group, or a nitrogen (C11, Br, F or E) as a substituent; a plurality (2 to 20) of the above substituents; In this case, the main chain of the organic group is composed of multiple hydrocarbon groups. It includes not only those in which a portion of the hydrocarbon group constitutes a side chain of an organic residue skeleton.

(Example) (C=C) At(P P)-A1 (C=C), (C
=C) At-CP-P)-A2(C(?)-At-B
+-A2-B2-4-CP-P) A? -B AS-B
10-A5-(C=C) In the present invention, the term "hydrocarbon group" is used in a broad sense including halogenated hydrocarbons, even if the term "hydrocarbon group" is not particularly specified.

In the above formula, pyrophosphate derivatives of (meth)acrylic acid esters in which Xl, X'*, X2, and phantom are oxygen, and k and N' are 1, have a wide range of applications as adhesives. Among them, Ra=Ra, R1=R
Compounds where <, m=n are the easiest to synthesize. From the viewpoint of adhesive strength, it is most preferable to use a compound that satisfies m"n=1. Regarding the relationship between adhesive strength and molecular structure, in formula (1), Ra represents (1) halogen, hydroxyl group,
A hydrocarbon group having 8 to 30 carbon atoms that may be substituted with an amine group or a carboxyl group, or (11) a 2 to 7 hydrocarbon group that may be substituted with a halogen, hydroxyl group, amine group, or carboxyl group. Group [The hydrocarbon group has 1 to 29 carbon atoms, and at least one hydrocarbon group therein has 3 or more carbon atoms. ] is a hydrocarbon group having 1 to 3 carbon atoms that may be substituted with an ether type, thioether type, ester type, thioester type, thiocarbonyl type, logen, hydroxyl group, amino group, or carboxyl group, or (11) halogen, 2 to 7 hydrocarbon groups that may be substituted with a hydroxyl group, an amino group, or a carboxyl group [the hydrocarbon group has 1 to 29 carbon atoms]; ] is an ether type, a thioether type, an ester type, a thioester type, a thiocarbonyl type.
1) A natural number] (++) -ca4°, 2 t or -ch prefecture □2- or 4] is 1, and Rh is a hydrocarbon group having 5 to 16 carbon atoms.

The adhesive monomers used in the present invention are illustrated below.

Satoshi Hs HOH CH3 0HOH CH3 Hg OH5 CH3 What) OC-C=CH2) s OH5 100 (however, j=2~10) OH5CHs H2C=COOC=CH2 HOH CH3 [C=CH2 -OCH2CH200C H2C=CH CH3C output HOH Hs Stomach 3 0CH2CH200C-C=CH2 CH200C(CH2)70H3 In the compound of formula (1), when the number of carbon atoms in Ra is 7 or less, the adhesive strength to materials such as teeth and metals and its water resistance are used in the present invention. It is significantly inferior to other compounds. As the number of carbon atoms in general KRa increases, the adhesive strength increases once and then decreases.
In the range of 40, preferably in the range of 8 to 50, sufficient adhesive strength can be obtained to achieve the purpose of the invention. The lower limit of Ra is high when the number of carbon atoms is small, but when the number of carbon atoms exceeds 40, R
Similar to a, there is a problem with adhesive strength.

The compound represented by the (+) formula can generally be synthesized by referring to the method for synthesizing phosphorus-containing compounds described in the following literature.

Organol) phosphorus Compound
ds (G.M. Kosolapoff, Wil
ey+ 1950), Organophosph
orus Monomers and Polymers
(Ye, written by L-Gefter + Rregamo
n Press+1962), Modern Organic Synthesis Series 5
, Organophosphorus Compounds (edited by the Organic Synthetic Chemistry Association, Gihodo, 19
71), Be1lstein (Springer-
For example, in the compound of formula (1), X+
, X< , X2, X; is oxygen, k and ′ are 1
, Ra=Ra, R+=R'i, m=n=1, that is, when the phosphoric acid ester group of the compound is synthesized by the dicyclohexylcarbodiimide method or the usual dehydration condensation method using vicryl chloride and pyridine. Ru. Also HO-R
For a-OH! l) By using K H8-Ra-8H, it is possible to synthesize a hole-shaped compound (1) in which O is replaced with S.

In the adhesive of the present invention (sometimes referred to as an adhesive composition), the compound represented by formula (1) is used in combination with a vinyl monomer copolymerizable with the compound. The viscosity, wetting properties, curing properties, mechanical properties, etc. of the adhesive can be adjusted by selecting the copolymerizable vinyl monomer. The vinyl monomer is appropriately selected depending on the purpose and use, but (meth)acrylic acid ester monomers, styrene monomers, and vinyl acetate are usually used. However, in addition to these, there are also acrylamides such as (meth)acrylamide, Nn-butoxymethyl (meth)acrylamide, and N-(hydroxymethyl)acrylamide, (meth)acrylic acid, inbutyl vinyl ether, diethyl fumarate, and diethyl maleate anhydride. Maleic acid, methyl vinyl ketone, allyl chloride, vinyl naphthalene, vinyl pyridine, etc. are used. The above-mentioned styrenic monomer compounds (divinylbenzene, P-chlorostyrene, etc.) can be mentioned. Furthermore, as the (meth)acrylic acid ester monomer, compounds commonly used in anaerobic adhesives, dental adhesives, etc. are preferably used in the present invention. (Meth represents an organic group having 1 to 5 carbon atoms, t represents an integer of 1 to 4) (see above for the definition of the organic group) is used. Such a monomer is used. The following are exemplified as the mer.

(1) Monofunctional (meth)acrylate methyl (meth)
Acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, is□-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate
Acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate (HE
(sometimes referred to as MA), 2-hydroxypropyl (
meth)acrylate, dimethylamine ethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 3-chloro-2-hydroxyglobil methacrylate), 2,3-dibromopropyl (meth)acrylate (
ii) Bifunctional (meth)acrylate toy)
z: -CH2CH2(OCH2CH2)8- or 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 , glopylene glycol di(
meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate
Propanediol di(meth)acrylate, glycerin di(meth)acrylate, 1,3-butanediol di(
meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)
acrylate, 1,6-hexanethiol di(meth)acrylate, neobentylglycol di(meth)acrylate), 1,10-decanediol di(meth)acrylate, dibromneopentylglycol dimethacrylate) U is a bisphenol A derivative Bisphenol-A di(meth)acrylate, 2.2
-bis((meth)acryloyloxyphorethoxyphenyl]propane(4-acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(3-methacryloyloxy-
2-Hydroxypropoxy)phenyl]propane (Bi
(sometimes referred to as s-GMA) Among these, in the case of Moke 1 or 2) in which U has 15 to 50 carbon atoms, 1.2-
Bis[3(meth)acryloyloxy-2-hydroxypropoxy]ethane, 1.4bis[5-(meth)acryloyloxy-2-hydroxypropoxycobutane.

*) Urethane di(meth)acrylate represented by UkaJoCONHTNHCOOJ (J is an alkylene group (usually having 2 to 10 carbon atoms) and T is an organic diisocyanate residue having 1 to 5 degrees of carbon atoms) For example, JP-A-50-687 The one listed in the number is used.

(IIQ 3-4 functional methacrylate trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, N, N' -(2,2
, 4-)limethylbenxamethylene)bis[2-(aminocarboxy)propane-1,3-diol cotetramethacrylate These copolymerizable monomers may be used alone or in combination. Among these monomers, methacrylic acid ester is preferred for use in dental adhesives.
It is desirable that it accounts for 50% by weight or more in the copolymerizable monomer. Preferred examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, HEMA, n-hexyl methacrylate, be/zyl methacrylate, lauryl methacrylate, and Bis-
GMA, bisphenol A dimethacrylate, 2.2
-Bis[(meth)acryloyloxypolyethoxyphenyl dipropane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,6-hexanesiol dimethacrylate, 1,10-decanediol dimethacrylate, neopentyl glycol These include dimethacrylate and trimethylolethane trimethacrylate.

In the adhesive of the present invention, the compound represented by (I) is 0.5% by weight or more of all polymerizable monomers, that is, (+)
0 to 1 part by weight of the above-mentioned copolymerizable monomer per 1 part by weight of the compound of formula
It is necessary to use 199 parts by weight.

If the amount is less than 0.5% by weight, the adhesive strength will be insufficient. More preferably, the compound of formula (+) is used in an amount of 1.5% by weight or more.

The adhesive of the present invention is applied or filled onto an adhesive surface, and is polymerized and cured by a physical method such as heating, irradiation with X-rays, ultraviolet rays, or visible light, or a chemical method using a polymerization initiator, and exhibits an adhesive function. . Usually, curing is carried out by adding a sensitizer and irradiating with light or adding a polymerization initiator. In the present invention, a polymerization initiator and a sensitizer are collectively referred to as a curing agent. Usable curing agents include organic peroxides,
There are various compounds such as azo compounds, organometallic compounds, redox initiators, and photosensitizers for ultraviolet or visible light.Specifically, benzoyl peroxide, di-t-
Butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, azobisisobutyronitrile, tributylborane, organic sulfinic acid (or its salt),
Hydrogen peroxide/Fe2+ salt system, cumene hydroperoxide/Fe base, benzoyl peroxide/N,N-dialkylaniline derivative system, ascorbic acid/cu2+ salt system, organic sulfinic acid (or its salt)/amine (or its salt) )/peroxide type, α-diketone/allylthiourea type (visible light type), benzoin methyl ether, benzoylethyl ether, benzyl, diacetyl, zincenyl disulfide, di-β-naphthyl sulfide, and the like. Among these, benzoyl peroxide, benzoyl peroxide, and
Azobisisobutyronitrile, tributylborane, organic sulfinic acids (or their salts), aromatic sulfinic acids (
or its salts)/diacyl peroxide/secondary aromatic
or tertiary amine (or its salt) type. Examples of aromatic sulfinic acids include benzenesulfinic acid, p-
) Luenesulfinic acid, β-naphthalenesulfinic acid,
Examples include styrene sulfinic acid. Cations that form salts with the sulfinic acid include alkali metal ions, alkaline earth metal ions, ammonium ions, etc., and alkali metal ions and alkaline earth metal ions are superior in terms of storage stability and adhesive strength. For example, Li+, Na+, K1, Mg2+, Ca2+, S
It is r2+. Preferred specific examples of aromatic amines include N
, N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-jetanolaniline, N,N-jetanol-p-toluidine, N-methylaniline, N-
Examples include methyl-p-toluidine. Further, these amines may form salts with hydrochloric acid, acetic acid, phosphoric acid, etc.

Examples of diacyl peroxide include benzoyl peroxide, m-)luoyl peroxide, 2゜4-dichlorobenzoyl peroxide, octanoyl peroxide, lauroyl peroxide, succinic acid peroxide, etc. Among these, benzoyl peroxide and m-toluoyl peroxide are particularly preferred. These curing agents usually contain 10 polymerizable monomers.
It is used in an amount of 0.01 to 20 parts by weight relative to 0 parts by weight, and a particularly preferable range is 0.1 to 15 parts by weight.

The adhesive of the present invention further has a boiling point of 1 at 760 Torr.
It may be desirable to add volatile organic solvents at temperatures below 50°C. Such an embodiment is suitable when the adhesive of the present invention is used as a primer used when filling a tooth cavity with a dental filling material. After coating, the added volatile organic solvent is evaporated by blowing air or nitrogen to form a vinyl compound film on the adhesive surface. Suitable organic solvents for this use include methanol, ethanol, acetone, methyl ethyl ketone,
Examples include methyl acetate, ethyl acetate, dichloromethane, chloroform, ethyl ether, isopropyl ether, and toluene. The ratio of these volatile solvents to all polymerizable monomers is 300 times or less (weight ratio), preferably 100 times or less. At large dilutions exceeding 500 times the volume, a significant decrease in adhesive strength is observed, probably because the film of polymerizable monomer formed on the adhesive surface after evaporation of the volatile solvent is too thin.

The adhesive of the present invention further includes conventionally known fillers (inorganic,
(organic polymers or inorganic-organic hybrids) may be added. By adding a filler, the adhesive composition of the present invention can be used as dental cement (for bonding and filling) and dental composite resin bone cement. The amount of filler added is 1000 parts by weight or less, preferably 20 to 500 parts by weight, per 100 parts by weight of the polymerizable monomer.

The addition of fillers improves the flow properties of the adhesive composition during use, its mechanical properties after curing, its adhesive strength and its water resistance. Inorganic fillers used in the present invention include:
For example, natural minerals such as quartz, feldspar, pottery stone, wollastonite, mica, clay, kaolin, marble, silicon oxide, aluminum oxide,
Glasses such as silicon nitride, boron carbide, boron nitride, soda glass, barium glass, strontium glass, borosilicate glass and ceramics such as glass ceramics containing lanthanum, water-insoluble inorganic salts such as barium sulfate, calcium carbonate, etc. can be mentioned. Inorganic fillers are typically γ-methacryloyloxyglobyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane Surface treatment with a silane coupling agent such as

In addition, organic polymer fillers include polymethyl methacrylate, polyamide, polyester, polypeptide,
Various polymers are used, such as polysulfone, polycarbonate, polystyrene, chloroprene rubber, nitrile rubber, styrene-butadiene rubber, and polyvinyl acetate.

Further, as the inorganic-organic composite filler, the above-mentioned silane-treated inorganic fin coated with the above-mentioned various polymers is used.

These fillers are used singly or in combination, but the particle size of the filler is usually 100μ or less,
The shape may be amorphous, spherical, plate-like, or fibrous, and in the case of a polymer, it may be dissolved in a polymerizable monomer or volatile organic solvent. When the adhesive of the present invention is used as a dental cement or a dental composite resin, the filler is preferably an inorganic filler or an inorganic-organic composite filler, and when it is used as a bone cement, an organic filler is preferable.

Furthermore, for adhesives of the present invention, particularly industrial and household adhesives, organic solvent-soluble polymers such as PMMA, polystyrene, polyvinyl acetate, chloroprene rubber, butadiene rubber, nitrile rubber, chlorosulfonated polyethylene, etc. For 100 parts by weight of vinyl monomer composition, 2
It is preferably dissolved in an amount of 120 parts by weight or less under 0.00 weight percent, and can be used to increase the viscosity of the adhesive and improve the mechanical properties of the cured product.

In addition to the above-mentioned components, the adhesive of the present invention may optionally contain hydroquinone monomethyl ether (abbreviation: MEH) depending on various performance requirements as a practical adhesive.
Q), polymerization inhibitors and antioxidants such as 2,6-tert-butyl-p-cresol (abbreviation: BHT), ultraviolet absorbers, various pigments and dyes, phthalic acid diesters, silicone oil, etc. are added. . These are added as a small amount additive, usually 1 part by weight per 100 parts by weight of the polymerizable monomer.
It is added in an amount of 0 parts by weight or less, usually 5 parts by weight or less.

When the adhesive of the present invention is used in medical fields such as dentistry and orthopedics, a room temperature curing redox initiator is often used as the initiator. In this case, the oxidizing agent and reducing agent must be packaged separately from the viewpoint of storage stability of the adhesive, and consideration must be given to the packaging form. Examples of packaging formats include two-part packaging for vinyl compound + reducing agent and vinyl compound + oxidizing agent, or vinyl compound + reducing agent and vinyl compound + oxidizing agent.
Two-part packaging for oxidizing agent (or reducing agent) and volatile organic solvent + reducing agent (or oxidizing agent), two-part packaging for vinyl compound oxidizing agent (or reducing agent) and filler reducing agent (or oxidizing agent)
Examples include separate packaging, two-part packaging of vinyl compound + Physi-deca oxidizing agent and vinyl compound + Physi-deca reducing agent. Among the redox polymerization initiator systems, organic sulfinic acid (or its salt)/
In the amine (but still its salt)/peroxide ternary system, the sulfinic acid and amine are the reducing agents and the peroxide is the oxidizing agent. In this case, the sulfinic acid and the amine may be packaged in five separate packages.

In addition, when using a photosensitizer as a curing agent, the vinyl compound photosensitizer must be stored in a light-shielded container. However, if an initiator is used that initiates polymerization within a short time upon contact with the vinyl compound (such as tributylborane), the vinyl compound and the polymerization initiator must be packaged separately. The separately packaged adhesive composition is mixed immediately before use.

The adhesive of the present invention has excellent adhesion to the following various materials, and has the effect of maintaining high adhesive strength over a long period of time even under wet conditions.

(1) Living body hard tissues such as teeth and bones (I+) In addition to base metals such as iron, nickel, chromium, cobalt, aluminum, copper, zinc, tin, stainless steel, and brass, it is difficult to bond with conventional adhesives. Metal materials such as noble metal alloys containing 50 to 90% gold and platinum (1 glass, ceramics, silica, ceramics such as alumina oxide (1 polymethyl methacrylate, polyester, polyamide, polyurethane, polycarbonate, polysulfone, polystyrene, etc.) The adhesive of the present invention can be applied to various materials as described above.

Since it has excellent adhesive properties, it is used in various fields, and examples of suitable uses include the following.

(1) Dental field O Tooth cavity is made of composite resin (usually polymerizable monomer,
K to be filled and repaired with (consisting of filler and polymerization initiator)
The adhesive applied to the cavity wall is usually combined with the above-mentioned composite resin and supplied to the dentist as a system.

0 A composite resin for filling a tooth cavity, in which case a filler is added to the adhesive of the present invention, and the resulting composition is used as a filling material and also provides adhesive properties to the tooth. have.

・Adhesive zero fixer for bonding inlays, onlays, abutment teeth, etc. to cavities, bridges, posts, splints, orthodontic brackets, etc. to teeth, and for bonding crowns to abutment teeth. When used in each sealant application, the specific composition of the adhesive is selected in accordance with the above description. For example, in the case of adhesives applied to teeth before filling with composite resin, USp 4259075.425911
According to the composition shown in No. 7 etc., 1.5 to 100% by weight of the above-mentioned adhesive vinyl compound is contained in the adhesive, and other polymerizable monomers (Bis-GMA, H
EMA, aliphatic dimethacrylate, etc.), diluted with an organic solvent (ethanol, etc.), and further containing a room temperature hardening agent is used. In addition, when using the adhesive composition as a composite resin, the above U
According to the composition shown in SP, 20-40% by weight of a polymerizable monomer such as Bis-GMA and 80-60% of a filler.
A conventional filling material consisting of 1.5 to 50% by weight (based on the total polymerizable monomers) of the adhesive vinyl compound described above is used. Rather than applying the adhesive thus obtained to the tooth by conventional procedures (preferably by acid etching the tooth surface and then applying the adhesive of the present invention, the adhesive of the present invention USP42
Compared to the composition disclosed in No. 59075.4259117, practical adhesive strength can be obtained without such acid etching. There are concerns about acid etching injections into tooth dentin. ), the cured composite resin strongly adheres to the tooth structure, eliminating the need for mechanical retention such as undercuts. In addition, inlays, onlays,
When bonding a crown or the like to a cavity or abutment tooth, for example, 1.5 to 50 parts by weight of an adhesive vinyl monomer, 98.5 to 50 parts by weight of a copolymerizable monomer, and 50 to 500 parts by weight of a filler.
A composition of parts by weight is used. By applying a large amount of such adhesive to the surface to be bonded and bringing it into close contact, it has become possible to bond inlays, onlays, and crowns to the tooth structure, which was impossible with conventional luting cement-e.

In addition, by applying and curing a solution consisting of a polymerizable monomer containing an adhesive vinyl monomer and a polymerization curing agent to the tooth surface, a film that firmly adheres to the tooth surface is formed, thereby making it possible to prevent tooth decay. It became.

(11) Orthopedic field Used as bone cement for adhering and fixing ceramic or metal artificial joints and internal splints to bones. The adhesive composition in this case is, for example, methyl methacrylate 90 to
Preferred examples include 98.5 parts by weight of the adhesive vinyl monomer, 10 to 1.5 parts by weight of the adhesive vinyl monomer, and 50 to 150 parts by weight of polymethyl methacrylate.

(110 General industrial/household use field The adhesive of the present invention has excellent adhesion to metal materials, ceramics, and organic polymer materials.

It is useful as an adhesive in transportation equipment, electrical equipment, building materials, can manufacturing, ceramics, and household fields. It is also used as a base coat material and coating material for paints and paints. When used in such applications, the adhesive of the present invention has the surprising feature of being able to bond not only when oil is attached to the adhered surface but also when moisture is attached. ing. Moreover, the adhesive strength is significantly superior to existing polymerization-curing adhesives (cyanoacrylate, epoxy resin, 5GA).

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.Example 1 Esterification of 1 mol of methacrylic acid and 1 mol of 1.12-dodencadiol The reaction was carried out at 90°C using p-toluenesulfonic acid as a catalyst to obtain a mixture of methacrylic acid monoester and diester of 1,12-dodencadiol. The mixing ratio was analyzed by high performance liquid chromatography, and the amount of phosphorus oxychloride equivalent to the amount of monoester was
The mixture was reacted at 0°C and the remaining QP-C1 bond was then hydrolyzed at 0°C to obtain a mixture of 12-methacryloyl oxide dodecyl dino-idlodiene phosphate and 1,12-dodecanediol dimethacrylate. . The mixture was extracted with n-hexane to remove dimethacrylate and 12-methacryloyloxide dodecyl dino-
Idrosien phosphate was obtained. This phosphate 3
10.3L of dicyclohexylcarbodiimide
00 cc of ethyl acetate and stirred at room temperature for 5 hours. The crystals of the urea derivative that have precipitated are separated from each other, and B is added to the furnace liquid.
15q of HT was added and the solvent was distilled off under reduced pressure. 33 g of a non-volatile residue was obtained, which was subjected to elemental analysis, Hl and P31
- As a result of NMR analysis, it was confirmed that it was a birophosphoric acid ester compound having the following chemical structural formula.

9Hs 9J (5 Using this compound, the following two-component type primer was prepared.

1 agent Bis-GMA 5074 parts by weight HEMA 43 # Compound (4) 7N benzoyl peroxide 2I agent 2 Ethanol 100 parts by weight Sodium benzenesulfinate 31 N,N-dimethyl-p-toluidine 0.7 Human molars placed in a cylindrical holder The tooth was embedded in epoxy resin, the crown part was cut, and the dentin surface was exposed, which was used as a sample for bonding. On the other hand, a stainless steel rod of 7ffφ×25IIM was prepared. First, measure the dentin surface and the end surface of the stainless steel rod at 1100mm.
Polish with 0 abrasive paper, stick adhesive tape with a 5φ hole on the dentin surface to define the bonding area, then mix equal parts of agent 1 and agent 1, and apply adhesive tape to the dentin surface and the end surface of the stainless steel rod. was applied thinly. Air was immediately blown onto the coated surface using an air syringe to evaporate the ethanol. Knead commercially available dental composite resin (product name: "Clearfil-FJ"),
The paste was applied to the end surface of a stainless steel rod, and the paste was pressed against the dentin surface for adhesion.

50 minutes after the completion of the bonding operation, the bonded specimen was immersed in water at 37°C, and the tensile bond strength was measured one day later.
Fracture occurred at the composite resin interface, and the bond strength was 6.
It was 9/d in 6.

Comparative Example 1 Using OHOH, a known pyrophosphate ester derivative, in place of compound (4), and with the other conditions being exactly the same as in Example 1, an adhesion test to dentin of a denture was conducted, and the adhesion strength was 8 kt) /d.

Example 2 Adherents include iron, aluminum, copper, nickel, porcelain, α-alumina, glass, polymethyl methacrylate,
A polycarbonate round rod (7φ x 25g5) was prepared. The end faces of these round bars were polished with #1000 abrasive paper to serve as the adhering surface. A 5-containing ethanol solution of compound (g) was applied thinly to each adhering surface, and the ethanol was evaporated using an air syringe. Next, equal weights of a powder-cutting adhesive prepared according to the following formulation were mixed together and quickly applied to the surface to be adhered, and rods made of the same material were butt-bonded.

Part I Methyl methacrylate 100 parts by weight Benzoyl peroxide 11 Part 1 Polymethyl methacrylate powder 100 parts by weight Sodium benzene sulfinate powder 5 #N,N-jetanol p-) Luidine 11 The adhesive specimen was immersed in water 1 hour after adhesion and kept at room temperature. After storage for 10 days, the tensile adhesive strength was measured.

The results were as follows. Iron: 351#/14, Aluminum laminated 2qa#/d, Copper: 266 to 9/d, Nickel: 355 kg/ci, Porcelain: 187 min/d, α
-Alumina = 172kg/cd, Glass: 81#/d,
Polymethyl methacrylate): 153 #/d, Polycarbonate: 1 o8 #/d Comparative Example 2 An adhesion test was carried out in exactly the same manner as in Example 2, using the compound () instead of the compound. iron, aluminum,
Copper, nickel, porcelain, α-alumina.

The adhesive strength of the glass was 50#/d or less in all cases.

Example 3 A powder-cutting adhesive having the following composition was prepared using compound (4).

V agent Bis -GMA 40 overlapping parts HEMA 30 s Neopentyl glycol dimethacrylate 20 〃Compound (5) 10 J Benzoyl peroxide 2I MEHQ Trace amount ■ Agent Silanized quartz powder ioo Weight parts Separate parts Sodium Zensulfinate powder o, s pN,N
- Disentanol - 1) -) Luizine Q, 4 g The crown of an anterior tooth was embedded in a cylindrical holder with epoxy resin to prepare a specimen for bonding. At that time, this surface was exposed and fixed to the holder so that it could be bonded to the labial enamel. After polishing the labial enamel with #1000 abrasive paper,
Acid etching was performed for 1 minute with a 40% orthophosphoric acid aqueous solution. After washing away the acid with water, the etched tooth surface was dried with an air syringe and used as an adhesion surface. One end face is tNO
A 7φ x 25H stainless steel round bar polished with OO abrasive paper was prepared. A paste-like adhesive was made by thoroughly mixing 0.1 g of agent V and 0.3 g of agent (■), and this was applied to the end face of a stainless steel round rod, and this surface was pressed against the acid-etched tooth surface for bonding. . After 1 hour of adhesion, the specimen was immersed in 37°C water, and 1 day later, the tensile adhesive strength was measured.The fracture occurred at the enamel-adhesive interface, and the strength was 205.
kg/d.

Examples 4 to 9 Adhesives were prepared according to the method of Example 1 using the compounds in Table 1, and the adhesive strength to dentin of dentures was examined. Furthermore, Compound (4) of Agent V in Example 3 was replaced with the compound in Table 1,
A powder-pattern adhesive was prepared and its adhesive strength to an Nj-Cr alloy was examined in the following manner.

Dental Ni-Cr alloy [Narachrome (1), Towa Giken ■] was cast into a square plate shape of 4 x 10 x 10 m.
After polishing the fl surface with #1000 abrasive paper,
Adhesive tape with mφ holes was pasted on it.

On the other hand, prepare a stainless steel round bar of 7nφ×25M11,
This end face was sandblasted at a pressure of 3.5 and 9/d using alumina abrasive grains with an average grain size of 53 μm. Adhesive powder 0
．． A paste obtained by mixing 69 and 0.1 g of a liquid agent was applied to the end face of a stainless steel round bar, and the paste was pressed against a cast plate of Nt-Cr alloy for adhesion.

One hour after bonding, the sample was immersed in 37°C water, and one day later, the bond strength was measured using an Instron universal test at a crosshead speed of 2 fights/min. The results are shown in the third and fourth columns of Table 1.

J'/Lower Margin Comparative Example 3 Chemical structural formula: Adhesives were prepared according to the methods of Examples 4 to 9 using the compound represented by, and adhesives were prepared on denture dentin and Ni-Cr alloy [Narachrome (I), Towa Giken]. The adhesion strength was examined and found to be 11 #/cd and 53 #/d, respectively. Comparing this with the values of the compounds in Table 1, it is clear that the values are significantly inferior.

Example 10 A cylindrical cavity with a diameter of 4fl and a depth of 4H was formed on the lingual side of an intercuspid molar using a diamond bur, and the inside of the cavity was dried using a hunting gun. Next, the isostatic mixture of Agents I and I used in Example 1 was applied to the entire cavity wall, and after evaporating the ethanol with a hunting gun, a commercially available dental composite resin (trade name: Clearfill-FJ) was illegally applied. Filled according to the following. After storing this tooth in 37°C water for one day, it was dyed at 4°C and ISO'.
The tooth was immersed in water bath C 100 times for 1 minute at a time, and then cut with a cutter to examine whether or not the dye had penetrated into the bonding interface between the tooth and the filling. No dye had penetrated at all. .

Example 11 A conical cavity with a diameter of 6 mm and a depth of 4 mm was formed on the occlusal surface of a large molar, and an inlay matching the size of the cavity was cast using Type I gold alloy. 1 of Agent V and Agent ■ of Example 3
:3. The mixture was kneaded in a weight ratio of O and applied to the conical surface of the inlay, pressed into the cavity, and bonded. Thirty minutes after adhesion, it was immersed in water at 37°C, and one day later, it was subjected to a heat cycle test in which it was immersed alternately in water baths at 4°C and 60'C 100 times. Even after the heat cycle test, the inlay remained firmly attached to the tooth, and although I tried to tear it off with the edge of a knife, I was unable to do so.

Example 12 A plate-shaped cast body with a thickness of 1 m that fits the lingual side of an anterior tooth was made of Ni.
-Cr alloy (Ni near 6%, Cr: 12%, MO=3%
, Others: 9%). The surface of the cast body in contact with the teeth was sandblasted with 33 μm alumina abrasive grains, while the lingual surface of the anterior denture was etched with a 40-thiphosphoric acid aqueous solution for 1 minute. Agent V and agent (■) of Example 6 were mixed in a ratio of 1:3.
The mixture was kneaded at a weight ratio of 0, applied to the surface of the cast body, overlapped with the lingual side surface of the denture, and bonded. 10 minutes after gluing 7
When the tensile adhesive strength was measured after 1 day after being immersed in °C water, a value of 183 kg/d was obtained, indicating interfacial failure on the denture side.

Example 13 A Fischer sealant having the following composition was prepared to perform Fischer filling of molar teeth.

■Agent 2.2-bis(methacryloyloxybolyene 60 parts by weight, toxyphenyl)propane neopentyl glycol dimethacrylate 20 #Compound (4) 10 〃 HEMA 10 N Benzoyl peroxide 2I ■Agent Bin -GMA 40 parts by weight HEMA 40 g Neopentyl glycol dimethacrylate 20 I Sodium benzene sulfinate 2 #N,N-jetanol p-) luidine 2 Clean the fissure of the interdigital molar with a probe, wash with water, dry, and apply etching to sealant. (equal-situation compound of ■ agent and ■ agent) was packed into Fisher. After 10 minutes of curing, this tooth was
It was immersed in water at 7°C. After being stored under these conditions for 1 day, the dye was placed in a water bath at 4°C and 60°C for a total of 1 minute each.
When this sample was immersed 00 times and cut with a cutter to examine whether or not the dye had penetrated into the bonding interface between the tooth and the filling, almost no dye had penetrated.

Example 14 A cylindrical cavity with a diameter of 4M and 4 depths was formed on the buccal side of a human molar using a diamond bur, and the cavity wall was filled with a 40% phosphoric acid aqueous solution.
After acid etching for 1 minute, it was washed with water and dried. Next, the base material obtained by mixing agent V and agent (2) of Example 5 in a weight ratio of 1:3.0 was filled into the cavity of the patient. hardening 10
After 1 minute, the sample was immersed in 37°C water, and 1 day later, a thermal cycle test was performed according to method 1j of Example 16 to examine the degree of penetration of the dye into the adhesive interface.
I was so angry.

Patent applicant RiRashi Co., Ltd. Agent: Patent Attorney Ken Honda

Claims (1)

[Claims] (1) (a) General formula [In the above formula, R1, R; , Ra, Ra, X
i, Xz, Xz %Xyu, scolding n, ni%ni' represents the following R1, R? :H or methyl group Xl, X'+, Xz, Xl2:0, S or N'Rct
(However, - is H but is an alkyl group having 1 to 6 carbon atoms) m
: An integer from 1 to 4t n: An integer from 0 to 4, ni': 0 or 1 Ra: (m+1) valent organic residue having 8 to 40 carbon atoms Ra:
An adhesive comprising 1 part by weight of a compound represented by an (n+1)-valent organic residue having 1 to 4 carbon atoms and (b) 0 to 199 parts by weight of a monomer copolymerizable with the compound. (2) Xl, X:, Xz and oblique are oxygen, and
The adhesive according to claim 1, wherein k and ni' are 1. (3) Ra is equal to Ra, R1 is equal to R1, and n
The adhesive according to claim 1 M2, wherein is equal to m. (4) The adhesive according to claim 3, wherein m and n are 1. (5) Ra has (υ8 to 5 carbon atoms which may be substituted with halogen, hydroxyl group, amino group or carboxyl group)
0 hydrocarbon group or (11) may be substituted with halogen, hydroxyl group, amino group or carboxyl group 2
~7 hydrocarbon groups [the hydrocarbon group has 1 to 29 carbon atoms, at least one of which has 5 carbon atoms]
It has the above. ] is ether type, thioether type, ester type, thioester type, thiocarbonyl type, amide type, carbonyl type, sulfonyl type, ureta (1) carbon number 1 which may be substituted with halogen, hydroxyl group, amine group or carboxyl group ~60 hydrocarbon groups (2 to 7 hydrocarbon groups having 1 to 29 carbon atoms, each of which may be substituted with a halogen, hydroxyl, amine or carboxyl group) is an ether type, a thioether type, an ester type, a thioester type, a thiocarbonyl type, an amide type, a carbonyl type, or an adhesive according to claim 1. (6) - is +CH2) I L dashi is natural number from 8 to 20] according to claim 4. (7) & is -CHr-@L oH2- or -CH2℃
The adhesive according to claim 4, which is represented by ``'CH2-; or 4]. 0.01 to 20 parts by weight of the curing agent per 0 parts by weight of the polymerizable monomers C(a)+(b)) (11) A volatile organic solvent having a boiling point of 150°C or less at 760 Torr is added to the polymerizable monomer ((a) + (b)
)) The adhesive according to claim 1, wherein the adhesive is added in an amount of 300 times or less (weight ratio). θ→filacy the polymerizable monomer ((a)+(b))
The adhesive according to claim 1, which contains 20 to 500 parts by weight per 100 parts by weight. θ→ The adhesive according to claim 1, wherein the vinyl monomer (b) is a (meth)acrylic acid ester monomer, a styrene monomer, or vinyl acetate. (14. The adhesive according to claim 10, wherein the curing agent is a redox polymerization initiator. The adhesive according to claim 14, which is packaged in at least two parts. 11. The adhesive according to claim 10, wherein the curing agent is a photosensitizer.