JP5733946B2 - Polymerizable monomer - Google Patents

Description

  The present invention relates to a novel acidic group-containing polymerizable monomer, and more particularly to a polymerizable monomer containing a phosphate group.

  Tooth that has been damaged due to caries, accidents, or the like is repaired by adhering a crown restoration material such as a composite resin, metal, or ceramic to the tooth using a dental adhesive.

  The dental adhesive is required to firmly bond the tooth and the restoration of the crown for a long period of time in a harsh environment in the oral cavity. This is because if the adhesive strength is low or the durability is insufficient, the restoration will fall off, or a gap will be created between the tooth and the restoration, and bacteria will invade from the gap and cause secondary caries. This is because there is a risk of triggering.

  The hard tissue of a tooth consists of enamel and dentin, and it is clinically required to adhere to both. Accordingly, the development of an adhesive having high adhesion to both enamel and dentin has been promoted, and an adhesive containing an acidic group-containing polymerizable monomer has been found. Furthermore, since it has more excellent adhesiveness, it has been proposed to use a polymerizable monomer containing a phosphate group as the acidic group-containing polymerizable monomer. Specific examples of such phosphate ester polymerizable monomers include the following compounds.

  Moreover, in patent document 1, even if the organic residue to which a phosphate ester group couple | bonds has description in the description of the phosphate ester type | system | group polymerizable monomer used for the above-mentioned dental adhesives, it has a hydroxyl group. It is listed as good. However, there is no specific explanation about the bonding position of the hydroxyl group, and nothing is described about the effect of bonding of the hydroxyl group.

International Publication No. 2003/057180 Pamphlet

  In recent years, there has been a strong demand for ease of use for dental adhesives. In this regard, in normal tooth restoration, before use of a dental adhesive, pretreatment with an aqueous acid solution is performed to decalcify the tooth to enhance its adhesion. However, since such pretreatment is troublesome, such a pretreatment operation can be omitted if water can be added to the adhesive to add a decalcification function (function as an acid). is there. However, it is known that in the presence of water, the phosphoric acid ester-based polymerizable monomer undergoes hydrolysis at a portion of the phosphoric acid ester group, and phosphoric acid is gradually decomposed and released. Therefore, when the dental adhesive compounded with the phosphate ester polymerizable monomer is further mixed with water to form a one-pack form, hydrolysis of the phosphate ester group portion causes the initial adhesive strength to be that of the reagent. There was a problem of lowering during storage.

  In addition, the dental adhesive containing such a phosphate ester-based polymerizable monomer is easy to hydrolyze the phosphate ester group portion, so that even after being used for restoration of a tooth. There was a problem that the long-term durability of the adhesive strength was inferior. That is, the reason why excellent adhesiveness is shown in a dental adhesive compounded with a phosphate ester polymerizable monomer, in addition to the polymerization of the polymerizable group of the phosphate ester polymerizable monomer, It is considered that the phosphate group is three-dimensionally ion-crosslinked directly with the calcium ions of the tooth or directly with the decalcifying action. However, since the oral cavity contains a lot of moisture, the hydrolysis of the phosphate ester group portion is also caused in the polymer of the phosphate ester polymerizable monomer after the dental adhesive is used for restoration of teeth. Still occurs. Therefore, in the hardened layer of the adhesive material, decomposition and separation of the phosphate ester group gradually occur, whereby the ionic cross-linking network with the calcium ion collapses, and the initial adhesive strength cannot be sufficiently maintained over time. Met.

  From the above, in a dental adhesive containing a phosphate ester polymerizable monomer, hydrolysis of the phosphate ester group portion of the phosphate ester polymerizable monomer is a problem, and its resistance is improved. That was a big issue.

  In order to achieve the above object, the present inventor has continued intensive research. As a result, in the phosphoric acid ester-based polymerizable monomer, it was found that the above problem can be solved satisfactorily by introducing a hydroxyl group into carbon at the beta position with respect to the phosphoric acid ester group, and the present invention was completed. I came to let you.

  That is, the present invention is a phosphoric acid ester-based polymerizable monomer represented by the following general formula (1), and further contains the polymerizable monomer, and is used for dental adhesiveness. It is a composition.

(Wherein, in the general formula (1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group, or alkylene oxyalkylene group having 3 to 7 carbon atoms, m is 1 or 2 Represents an integer.)

  The phosphate ester-based polymerizable monomer represented by the general formula (1) not only has a phosphate ester group in the molecule, but also has a hydroxyl group bonded to carbon at the beta position with respect to the phosphate ester group. Therefore, the resistance to hydrolysis at the phosphate ester group site is greatly improved. This is because by introducing a hydroxyl group into the beta-position carbon of the phosphate group that is an electron-withdrawing group, the electron density of the alpha-position carbon is that of the alpha-position of the conventionally known phosphate ester-based polymerizable monomer. It is thought that the fact that it is higher than the electron density of carbon has an influence.

  As a result, the phosphate ester group is difficult to hydrolyze, so the dental adhesive containing the phosphate ester polymerizable monomer can be stored for a long period of time, even when it is in a one-part form in which water coexists. Also, the decrease in the initial adhesive strength can be kept low. Similarly, the initial adhesive strength can be kept high over time even after being used for tooth restoration (that is, the adhesive strength is excellent in long-term durability).

In addition, the phosphate ester-based polymerizable monomer of the present invention has an acidic group (phosphate ester group) and a hydroxyl group in the same molecule. Both tooth decalcification and tooth penetration can be imparted. Further, by controlling the carbon chain length of R ₂ , the balance between hydrophilicity and hydrophobicity can be controlled within the same molecule.

  General formula (1)

In the phosphate ester polymerizable monomer represented by R ₁ , R ₁ is a hydrogen atom or a methyl group. R ₂ is an alkylene group or an alkyleneoxyalkylene group.

Examples of the alkylene group represented by R ₂ include linear or branched ones having 1 to 18 carbon atoms. Examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, Examples include hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, and the like. On the other hand, as the branched alkylene group, one or more hydrogen atoms in the linear alkylene group having 1 to 17 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n- Examples thereof include those substituted with an alkyl group such as butyl, isobutyl and t-butyl. Among these R ₂ alkylene groups, those having 1 to 10 carbon atoms are preferred, and those having 3 to 7 carbon atoms are most preferred from the viewpoint of increasing the adhesive strength.

On the other hand, the alkyleneoxyalkylene group represented by R ₂ is also preferably one having 2 to 18 carbon atoms, more preferably one having 2 to 10 carbon atoms, and most preferably one having 3 to 7 carbon atoms from the viewpoint of increasing the adhesive strength. . In particular, the alkyleneoxyalkylene group is preferably an alkyleneoxymethylene group, and specifically includes a methyleneoxymethylene group, an ethyleneoxymethylene group, a propyleneoxymethylene group, a butyleneoxymethylene group, a pentyleneoxymethylene group, and a hexylene. Examples thereof include an oxymethylene group, a heptyleneoxymethylene group, an octyleneoxymethylene group, a nonyleneoxymethylene group, and a decyleneoxymethylene group. In the case of an alkyleneoxymethylene group, the methylene side is bonded to the carbon atom substituted by the hydroxyl group in the general formula (1), and the alkylene side is bonded to the oxy group constituting the (meth) acryloyloxy group in the general formula (1). To do.

Further, the alkylene group or alkyleneoxyalkylene group of R ₂ may have a substituent such as a halogen atom such as chlorine, bromine or fluorine, or an amino group.

  Specific examples of phosphate ester polymerizable monomers that can be suitably used include:

And the like. Among these, the general formula (A), the general formula (B), the general formula (C), the general formula ( D), general formula (M), general formula (N), general formula (O), general formula (P), general formula (Q), general formula (R), general formula (S), general formula (T) The compound shown by is especially preferable.

  Next, the manufacturing method of the phosphate ester type | system | group polymerizable monomer shown by General formula (1) is demonstrated. That is, this phosphate ester polymerizable monomer has the general formula (2)

(In the formula, R ₁ and R ₂ are the same as those in the general formula (1).)
An epoxy compound represented by the general formula (3)

(In the formula, R ′ represents a primary alkyl group having 1 to 6 carbon atoms, and m represents an integer of 1 to 2).
And the resulting general formula (4)

(In the formula, R ₁ , R ₂ and m are the same as those in the general formula (1).)
It can manufacture by hydrolyzing the group shown by -OR 'about the phosphate ester compound shown by.

  In the phosphoric acid compound represented by the general formula (3), R ′ is a primary alkyl group having 1 to 6 carbon atoms, that is, a linear or branched chain having at least two hydrogen atoms at the first carbon atom. Represents an alkyl group. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Among these, an ethyl group, a propyl group, and a butyl group are particularly preferable because of easy handling. Here, when R 'is not a primary alkyl group, the hydrolysis reaction is difficult to proceed, so that it is not suitable for this reaction.

  In the phosphoric acid compound represented by the general formula (3), m is an integer of 1 or 2, and when m is 1, it is monoalkyl phosphate, and when m is 2, it is dialkyl phosphate. Examples of the phosphoric acid compound represented by the general formula (3) include monomethyl phosphate, dimethyl phosphate or a mixture thereof; monoethyl phosphate, diethyl phosphate or a mixture thereof; monopropyl phosphate, dipropyl phosphate or these. Monobutyl phosphate, dibutyl phosphate or a mixture thereof; monopentyl phosphate, dipentyl phosphate or a mixture thereof; monohexyl phosphate, dihexyl phosphate or a mixture thereof. Among these, monoethyl phosphate, diethyl phosphate or a mixture thereof; monopropyl phosphate, dipropyl phosphate or a mixture thereof; monobutyl phosphate, dibutyl phosphate or a mixture thereof has good reactivity. preferable.

  In the above method, the reaction conditions of the epoxy compound represented by the general formula (2) and the phosphoric acid compound represented by the general formula (3) are not particularly limited, but with respect to 1 mol of the epoxy compound represented by the general formula (2). The charging ratio of the phosphoric acid compound represented by the general formula (3) is preferably 0.30 to 1.50 mol, more preferably 0.40 to 1.40 mol, and 0.45 to 1 Most preferably, it is 30 moles. The reaction temperature is preferably 0 to 100 ° C, more preferably 20 to 80 ° C, and most preferably 40 to 70 ° C. This reaction may be carried out using an organic solvent, but it is preferred to carry out without a solvent from the viewpoint of the ease of reaction.

  In the phosphate ester compound represented by the general formula (4) obtained by reacting the epoxy compound represented by the general formula (2) with the phosphoric acid compound represented by the general formula (3), -OR ' Hydrolysis of the group shown may be carried out by adding water to the reaction solution. In general, the reaction rate of the hydrolysis of the OR 'group occurs rapidly and selectively. Accordingly, the target product can be easily obtained almost quantitatively by optimizing the amount of water added to the OR ′ group, the reaction temperature, and the like. Water may be added during the reaction between the epoxy compound represented by the general formula (2) and the phosphoric acid compound represented by the general formula (3). In this case, the phosphoric acid compound represented by the general formula (3) is first generated from the reactivity, and then the hydrolysis of the OR ′ group proceeds.

  The addition amount of water in the hydrolysis reaction is preferably 3 to 100 mol, more preferably 5 to 50 mol, and most preferably 7 to 20 mol with respect to 1 mol of the epoxy compound represented by the general formula (2). preferable. The hydrolysis temperature is preferably 40 ° C to 100 ° C, more preferably 60 to 90 ° C.

  When the reaction solution is allowed to stand after the hydrolysis is completed and separated into two layers, an aqueous layer and an organic layer, the aqueous layer may be separated and removed, followed by washing with water. In this case, a water-insoluble solvent may be added in order to easily separate the organic layer containing the phosphate ester polymerizable monomer from the aqueous layer. By separating and removing the aqueous layer and washing with water, it is possible to remove unreacted phosphoric acid compounds and alcohols represented by orthophosphoric acid and HOR 'produced as a by-product by hydrolysis. Thereafter, if necessary, neutralization with an alkali metal or amines, removal of excess water under reduced pressure, or the like may be performed.

In the present invention, the structure of the phosphate ester polymerizable monomer represented by the general formula (1) can be confirmed by the following method. That is, the elements (carbon, hydrogen, nitrogen) constituting the phosphate ester polymerizable monomer of the present invention can be quantified by elemental analysis. Moreover, the molecular structure of the phosphate ester polymerizable monomer of the present invention can be determined from the observation of chemical shift and spin-spin coupling by measurement of nuclear magnetic resonance spectrum ( ¹ H-NMR). Specifically, protons on carbon bonded to a phosphate group are observed for 2H in the vicinity of δ3.4 to 3.9 ppm by nuclear magnetic resonance ( ¹ H-NMR) measurement. Furthermore, absorption of a specific substituent can be confirmed by measurement of an infrared absorption spectrum (IR). Specifically absorption of P-OH sites 900~1050cm ^-1, absorption of P = O sites is observed 1250~1320cm ^-1. Moreover, the mass (molecular weight) of the phosphate ester polymerizable monomer of the present invention can be measured by mass spectrometry (MASS).

  In the present invention, the phosphate ester-based polymerizable monomer represented by the general formula (1) is not particularly limited in use, but in general, the tooth and the dental restorative material or crown. Used as an adhesive component for dental adhesive compositions such as dental adhesives used when adhering dental restoration materials, and primers that are pre-treated before applying such dental adhesives to tooth surfaces . Thus, the dental adhesive composition containing the phosphate ester-based polymerizable monomer of the present invention is highly excellent in tooth decalcification action and tooth penetration action. In addition, for the reasons described above, the initial adhesive strength is excellent, and the initial adhesive strength can be kept high with time even after use for restoration of teeth, and the adhesive strength is excellent in long-term durability.

  When the phosphate ester polymerizable monomer of the present invention is used as an adhesive component of a dental adhesive composition, these are monofunctional ones (hereinafter PM1 type) in which m in the general formula (1) is 2. May be used alone, or a bifunctional compound having the same m of 1 (hereinafter abbreviated as PM2 type) may be used alone, and these may be used as a mixture. . When used as a mixture, the mixing ratio of the PM1 type and the PM2 type is preferably 60:40 to 10:90 in terms of mass ratio from the viewpoint of the mechanical strength of the adhesive composition.

  It is preferable to add water to the dental adhesive composition from the viewpoint of highly exhibiting the tooth decalcification action and obtaining high adhesiveness. In that case, even if the reagent is stored for a long period of time, the initial adhesive strength can be maintained at a high level, so that the effect of the present invention is remarkably exhibited, which is preferable. It is preferable to use water that does not contain impurities that adversely affect the development of the adhesive strength between the tooth and the restorative material. Generally, distilled water or ion-exchanged water is used. used.

  In the dental adhesive composition, the amount of water added is generally the total polymerization contained in the dental adhesive composition from the viewpoint of improving the decalcification action on the tooth and improving the mechanical strength of the cured product. The amount is preferably in the range of 5 to 40 parts by mass, more preferably 7 to 30 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Furthermore, it is preferable to mix | blend a polymerization initiator with a dental adhesive composition. As the polymerization initiator, either a photopolymerization initiator or a chemical polymerization initiator can be used. It is also possible to use a dual cure type in which a photopolymerization initiator and a chemical polymerization initiator are used in combination, and polymerization can be initiated by either photopolymerization or chemical polymerization.

  Representative photopolymerization initiators include diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, camphorquinone, 9, Α-diketones such as 10-phenanthrenequinone and acenaphthenequinone, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether, 2,4-diethoxythioxanthone and 2-chlorothioxan Thioxanthone derivatives such as Son, methylthioxanthone, benzophenone, benzophenone derivatives such as p, p'-dimethylaminobenzophenone, p, p'-methoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6 - Toxibenzoyl) -2,4,4-trimethylpentylphosphine oxide, acylphosphine oxide derivatives such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and aryl borate compounds / dyes / photoacid generators The system which becomes is mentioned. Among these, an α-diketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and a photopolymerization initiator composed of a combination of an aryl borate compound / dye / photoacid generator are particularly preferable. is there.

  In the case of using α-diketone or acyl phosphine oxide derivative, these alone show photopolymerization activity, but ethyl 4-dimethylaminobenzoate, lauryl 4-dimethylaminobenzoate, dimethylaminoethyl (meta ) It is preferable to use in combination with an amine compound such as acrylate because higher polymerization activity can be obtained.

  Typical chemical polymerization initiators include combinations of organic peroxides and amines, organic peroxides, combinations of amines and sulfinates, combinations of acidic compounds and aryl borates, barbituric acid, alkylboranes. And the like, and the like.

  The blending amount of the polymerization initiator in the dental adhesive composition may be an effective amount, and is generally 0.1% with respect to 100 parts by mass of all polymerizable monomers contained in the dental adhesive composition. It is preferable that it is the range of -10 mass parts, and it is more preferable that it is 0.5-8 mass parts. Most preferably, it is in the range of 1 to 6 parts by mass.

  In the dental adhesive composition, a polymerizable monomer other than the phosphate ester polymerizable monomer represented by the general formula (1) can be used as an optional component. As such other polymerizable monomers, conventionally known monomers can be used without any limitation, but from the viewpoints of polymerizability and safety to living bodies, a (meth) acrylic acid ester-based polymerizable monomer is used. It is preferable to use a monomer. Specific examples of these other polymerizable monomers are as follows.

Monofunctional polymerizable monomer:
Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2,3-dihydroxybutyl methacrylate, 2,4-dihydroxybutyl methacrylate 2-hydroxymethyl-3-hydroxypropyl methacrylate, 2,3,4-trihydroxybutyl methacrylate, 2,2-bis (hydroxymethyl) -3-hydroxypropyl methacrylate, 2,3,4,5-tetrahydroxypentyl Methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, tetraethylene glycol Call monomethacrylate, pentaethylene glycol monomethacrylate, N, N-dimethylaminoethyl methacrylate methacrylate, and the like, and corresponding acrylates to these methacrylates.

Bifunctional polymerizable monomer:
(I) Aromatic compounds; 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane), 2,2-bis (4- Methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2- (4-methacryloyloxydiethoxyphenyl) ) -2- (4-Methacryloyloxy) Diethoxyphenyl) propane, 2- (4-methacryloyloxydiethoxyphenyl) -2- (4-methacryloyloxyditriethoxyphenyl) propane, 2- (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxy) Triethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane, and acrylates corresponding to these methacrylates; diisocyanate methylbenzene, A diisocyanate compound having an aromatic group such as 4,4′-diphenylmethane diisocyanate, a methacrylate having a hydroxyl group, a methacrylate having an amino group, or a compound thereof. Diadduct and the like obtained from the addition of the corresponding acrylates acrylates such. (Hydroxyl group-containing methacrylates include 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol monotacrylate, Examples include tetraethylene glycol monomethacrylate, pentaethylene glycol monomethacrylate, etc. In addition, amino group-containing methacrylates include 2-aminoethyl methacrylate, 3-aminopropyl methacrylate, 2-aminopropyl methacrylate, 4-aminobutyl methacrylate, 5 -Aminopentyl methacrylate, 3-aminopentyl methacrylate, etc.)

  (Ii) those based on aliphatic compounds; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and acrylates corresponding to these methacrylates; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate) Diisocyanate compounds such as Methacrylates having amino groups, methacrylates having amino groups, or diadducts obtained from addition of acrylates corresponding to these methacrylates, etc. The hydroxyl group-containing methacrylates and amino group-containing methacrylates are as exemplified above. .)

Trifunctional polymerizable monomer:
Methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, and acrylates corresponding to these methacrylates;

Tetrafunctional polymerizable monomer:
Pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, diadducts obtained from the addition of a diisocyanate compound and glycidol dimethacrylate, and the like. The above diisocyanate compounds include diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 4,4-diphenylmethane diisocyanate, tolylene-2,4-diisocyanate. Etc.

  One of these other polymerizable monomers may be used alone, or two or more thereof may be used in combination.

  In the dental adhesive composition, the amount of the other polymerizable monomer is 100 to 800 parts by mass with respect to 100 parts by mass of the phosphate ester polymerizable monomer represented by the general formula (1). It is preferable to add in a range. More preferably, it is the range of 200-600 mass parts.

  As such other polymerizable monomers, acidic group-containing polymerizable monomers other than the phosphoric acid ester-based polymerizable monomer represented by the general formula (1) described above also impair the effects of the present invention. If it is not a small amount, it is acceptable to blend. Suitably, it is preferable to set it as 5 mass parts or less with respect to 100 mass parts of phosphate ester type | system | group polymerizable monomers shown by General formula (1).

  Furthermore, you may add an organic solvent and a filler to a dental contact composition. It is effective to mix the organic solvent when the dental adhesive composition is used as a primer. As such an organic solvent, a conventionally known organic solvent can be used without any limitation. However, in view of harmful effects on a living body, it is preferable to use ethanol, isopropanol, or acetone. It is preferable that the compounding quantity is the range of 40-150 mass parts with respect to 100 mass parts of all the polymerizable monomers contained in a dental adhesive composition, and it is more preferable that it is 50-125 mass parts. preferable.

  As the filler, a conventionally known filler can be used without any limitation. Specifically, an organic filler, an inorganic filler, and an organic-inorganic composite filler can be exemplified, and these can be used alone or in combination of two or more. The blending amount is preferably in the range of 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the total polymerizable monomer contained in the dental adhesive composition. preferable.

  In addition, in the dental contact composition, if necessary, an organic thickener, a polymerization inhibitor, a polymerization regulator, a UV absorber, a dye, an antistatic agent, a pigment, as long as the performance is not deteriorated. Various additives such as fragrances can be added.

Hereinafter, in order to specifically describe the present invention, examples and comparative examples will be described. However, the present invention is not limited to these examples. The abbreviations of the compounds used in Examples and Comparative Examples are as follows.
[Phosphate ester polymerizable monomer of the present invention]
Compounds (A) to (D), (I) to (T); each of the aforementioned structures [comparative phosphate ester polymerizable monomer]
Compounds (E) to (H); each of the aforementioned structures / compound (U);

Compound (V);

Compound (W);

-Compound (X);

PM1; 2-methacryloyloxyethyl dihydrogen phosphate PM2; bis (2-methacryloyloxyethyl) hydrogen phosphate [other polymerizable monomers]
MDP; 10-methacryloxydecyl phosphoric acid BM; Bis-GMA (2,2-bis (4- (2-hydroxy-3-methacryloxypropoxy) phenyl) propane): 3G (triethylene glycol dimethacrylate) = 3: 2 mixture-HEMA; hydroxyethyl methacrylate [polymerization initiator]
· CQ; camphorquinone · DMBE; p-dimethylaminobenzoic acid ethyl ester [other ingredients]
IPA; isopropyl alcohol, SiO ₂ ; silica particles

Example 1
Following formula

2.10 g (0.1 mol) of dibutyl phosphate was added to 20.0 g (0.1 mol) of the epoxy compound represented by the following formula, and the mixture was aged at 60 ° C. for 1 hour.

The phosphoric acid ester compound shown by this was produced | generated. To this reaction liquid, 18.0 g (1 mol) of water was added and stirred at 80 ° C. for 1 hour to hydrolyze the butoxy group in the phosphate ester compound. Thereafter, the pressure was reduced, excess water and butanol produced by hydrolysis were distilled off, and purification by chromatography on silica gel gave 11.3 g of a pale yellow highly viscous liquid product. . The yield was 42.5%.

The elemental analysis values of this product were C46.08% and H7.32%, which were in good agreement with the calculated values of C45.11% and H7.14% for this compound. The measured nuclear magnetic resonance ^{(1 H-NMR, 500MHz,} CDCl 3) spectrum, a peak of 1H derived from broad -O H near δ6.5~6.8ppm, δ5.5~6.5ppm 3H peak derived from C H ₂ = C H -C in the vicinity, 1 H peak derived from C (= O) -O-C H ₂ -C in the vicinity of δ 4.1 to 4.2 ppm, around δ 3.7 ppm -CH (OH) _-C H 2 2H peaks derived from -O-P, a peak of 1H derived from _{O-CH 2 -C H (OH} ) -CH 2 in the vicinity δ3.6ppm in the vicinity δ3.5ppm the _{O-C H 2 -CH (OH} ) -CH 2 -O-P peak of 2H derived from, near _{δ3.3~3.4ppm CH 2 -C H 2 -O-} CH 2 -CH (OH) -H peak derived from-, δ 1.3-1.6 ppm And a peak of 4H derived from near the _{O-CH 2 -C H 2 -C} H 2 -CH 2 -O. It was further measured for infrared absorption spectrum (IR), the absorption of P-O sites 998 ^-1, and an absorption at P = O site 1287cm ^-1. Moreover, when mass spectrometry (MASS) was measured, M + 1 showed 267. From the above results, the obtained product has the following structural formula (A)

It confirmed that it was a phosphate ester type | system | group polymerizable monomer shown by.

Examples 2 to 16, Comparative Examples 1 to 4
Each phosphate ester polymerizable monomer was synthesized using the raw materials shown in Table 1 in the same manner as in Example 1. As a result of structural analysis of the obtained product using the same structure confirmation means as in Example 1, the compounds shown in Table 1 were confirmed. Table 2 shows the results of elemental analysis, characteristic spectra of ¹ H-NMR spectrum, and mass spectrometry (MASS).

Example 17
10.0 g of the phosphate ester polymerizable monomer (A) produced in Example 1 was mixed with 18.0 g of BM and 12.0 g of HEMA as other polymerizable monomers. A dental adhesive was prepared by mixing 10.0 g of the obtained polymerizable composition, 2.0 g of water, 0.175 g of CQ, 0.175 g of DMBE, 9.0 g of IPA, and 1.0 g of MT-10. Manufactured.

About this dental adhesive, the adhesiveness with respect to a tooth substance was evaluated by the following method. The results show that the initial bond strength is 14.2 MPa for enamel and 14.4 MPa for dentin, and the bond strength after the endurance test is 14.0 MPa for enamel and 14.5 MPa for dentin. Was 14.1 MPa.
[Adhesion test of dental adhesive to tooth]
Within 24 hours after slaughter, the front teeth of the cow were removed, and the enamel and dentin planes were cut out in parallel with the labial surface using # 600 emery paper in the water. Next, air is blown onto these surfaces for about 10 seconds to dry, and then a double-sided tape with a hole having a diameter of 3 mm is fixed to the flat surface, followed by paraffin wax having a hole with a thickness of 0.5 mm and a diameter of 8 mm. A simulated cavity was formed by fixing to the same center on the circular hole. The adhesive of the present invention was applied in the simulated cavity and left for 20 seconds, and then dried by blowing compressed air for about 10 seconds. Next, the adhesive was cured by irradiating with a visible light irradiator (Power Light, manufactured by Tokuyama Dental Co., Ltd.) for 10 seconds. Furthermore, a dental composite resin (Estellite Σ Quick, manufactured by Tokuyama Dental Co., Ltd.) was filled thereon, and irradiated with a visible light irradiator for 30 seconds to produce an adhesion test piece.

  After immersing the above-mentioned adhesion test piece in 37 ° C. water for 24 hours, using a tensile tester (Autograph, manufactured by Shimadzu Corp.), it is pulled at a crosshead speed of 2 mm / min, and the tensile bond strength between the tooth and the composite resin is measured. did. Four tensile bond strengths per test were measured by the above method, and the average value was taken as the initial bond strength.

  Moreover, the adhesion test piece produced similarly was immersed in the water of 4 degreeC and 60 degreeC alternately for 1 minute at a time with a thermal shock tester, and after doing this 3000 times, it measured tensile adhesive strength similarly to the above. The value was defined as the adhesive strength after the durability test.

Examples 18-43 , Comparative Examples 5-15
Dental adhesives having the compositions shown in Tables 3 and 4 using the phosphate ester-based polymerizable monomers that are the compounds produced in Examples 1 to 16 and Comparative Examples 1 to 4 (amounts are in parts by mass) Was prepared in the same manner as in Example 17 .

Moreover, in order to show the comparison with the dental adhesive using the phosphate ester polymerizable monomer of the present invention, the phosphate ester polymerizable property in which the —OH group is not substituted at the beta position of the phosphate ester group. Using the monomer (EH, UX), PM1, PM2 and MDP as other comparison targets, the dental adhesive (amount in parts by mass) having the composition shown in Table 5 is the same as in Example 17 . Each was prepared by a method and subjected to a comparative test (Comparative Examples 9 to 15 ).

  About each dental adhesive material, the result of having evaluated the adhesiveness with respect to a tooth | gum is shown in Table 6-8.

In Examples 18 to 43 , each component was formulated so as to satisfy the constitution shown in the present invention. In any case, both the initial adhesive strength to the tooth and the adhesive strength after the durability test were In both cases, good values are obtained.

On the other hand, Comparative Examples 9 to 12 were bonded using phosphate ester polymerizable monomers in which the -OH group was substituted at a position other than the position specified by the present invention of R2. Although the material is used, the mechanical strength of the cured body is low, and the initial adhesive strength to the tooth and the adhesive strength after the durability test are low. Comparative Example 13 to 15, -OH group R ₂ is not substituted, it is an adhesive material using other phosphate-based polymerizable monomer, for interaction with the tooth is weakened, The adhesive strength after the durability test is low.

Claims (5)

The following general formula (1)

(Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group, or alkylene oxyalkylene group having 3 to 7 carbon atoms, m represents. A integer of 1 or 2) shown in A phosphate ester polymerizable monomer. General formula (2)

(In the formula, R ₁ and R ₂ are the same as those in the general formula (1).)
An epoxy compound represented by the general formula (3)

(In the formula, R ′ represents a primary alkyl group having 1 to 6 carbon atoms, and m represents an integer of 1 to 2).
And the resulting general formula (4)

(In the formula, R ₁ , R ₂ and m are the same as those in the general formula (1).)
The method for producing a phosphate ester polymerizable monomer represented by the general formula (1) according to claim 1, wherein the group represented by -OR 'is hydrolyzed with respect to the phosphate ester compound represented by formula (1). . A dental adhesive composition comprising a phosphate ester polymerizable monomer represented by the general formula (1) according to claim 1 .   The dental adhesive composition according to claim 3, further comprising water.   The dental adhesive according to claim 3, further comprising a polymerization initiator.