JP6832579B2 - Dental adhesive pretreatment material composition containing a phosphoric acid group-containing polymerizable compound - Google Patents

Description

The present invention relates to a dental adhesive pretreatment material composition containing a phosphoric acid group-containing polymerizable compound.

For adhesion to the dentin, a dental adhesive is used for adhesion to a dental resin filler called composite resin (CR) and a prosthesis such as a crown. At that time, a material called an etching material is used as the adhesive pretreatment material. Such an etching material is an acidic aqueous solution, and is applied to the tooth surface before applying the dental adhesive, and then washed with water to roughen the dentin surface. Therefore, the dentistry to be used after that. The mechanical adhesive strength of the adhesive material for use can be improved (Patent Document 1).

An example of such an etching material is an adhesive pretreatment material containing phosphoric acid. The main inorganic component forming the hard tissue of the dentin is formed from hydroxyapatite. By applying this phosphoric acid-containing pretreatment material to the surface to be adhered after forming the cavity and before applying the adhesive, calcium is partially eluted on the surface of hydroxyapatite, and a rough surface is formed on the surface to be adhered. It is formed. In addition, the cutting powder of the tooth substance during the formation of the tooth cavity, which can be one of the causes of adhesion inhibition, can be dissolved and removed.

The hard tissue of the crown is composed of enamel and dentin, but the above-mentioned etching material containing phosphoric acid is not generally effective for these dentins, and it is necessary to use them properly.

For enamel, it is recognized that the use of the etching material is effective for subsequent adhesion by the above principle.

On the other hand, dentin is a structure in which a large amount of collagen fibers are entwined with a sponge-like calcium phosphate skeleton, and is fragile as compared with enamel because it is mostly composed of dense calcium phosphate crystals. For this reason, when dentin is excessively etched with a strong acid, collagen is exposed due to the relatively easy elution of the calcium phosphate skeleton, and the dentin is denatured to hinder the penetration of the adhesive. There is a risk that the adhesive strength will decrease. For this reason, an etching material having good operability that can be applied to dentin has been studied (Patent Document 2), but in any case, a delicate operation is required for the user.

In addition, although the etching treatment on dentin involves the above-mentioned risks, it is important in removing cutting chips generated during the formation of the cavity. Cutting chips deposited on the dentin or clogged in the dentin tubules hinder the penetration of the dental adhesive, so it is preferable to remove the cutting chips with an etching material. However, for gentle etching without damaging dentin, an etching material containing citric acid, which has a weaker acidity than phosphoric acid, is used, and the citric acid is effective for etching treatment to enamel. is not it. Therefore, it is required to properly use materials in two different hard tissues, enamel and dentin.

Further, the etching material containing phosphoric acid is considered to be effective as a surface cleaning agent for dental materials other than dentin. It is known that it is actually effective for cleaning the surface depending on the material of the prosthesis. However, it is known that when an etching material containing phosphoric acid is used for cleaning a prosthesis made of zirconia, the adhesive strength is reduced (Non-Patent Document 1).

This is because phosphoric acid is strongly adsorbed on the surface of zirconia, which hinders the binding of the dental adhesive composition applied after washing with water. For this reason, it is usually required to properly use the cleaning material depending on the material of the prosthesis, such as the use of the restoration inner surface cleaning liquid instead of the etching material.

As described above, when cleaning the prosthesis, it is necessary to select a material that matches the material of the prosthesis, and if the material is selected incorrectly, the adhesive strength will decrease or the prosthesis will fall off from the abutment tooth. It was risky. In addition, the etching process on the tooth substance also requires a detailed work of applying only the enamel, and there is a problem that the possibility of poor adhesion increases when the dentin is applied due to an operation error of the operator. Had had.

Japanese Unexamined Patent Publication No. 2015-017049 JP-A-2015-063489

J. Dent. Res., 86 (8), 2007, 749-753.

An object of the present invention is to provide a dental adhesive pretreatment material composition that can be used in the oral cavity regardless of the material of the prosthesis and can be applied to both enamel and dentin.

Another object of the present invention is to provide an adhesive pretreatment material composition capable of reducing the risk of adhesive failure in various dental materials with a single liquid material.

As a result of intensive studies to achieve the above object, the present inventors have found that a dental adhesive pretreatment material composition containing a phosphoric acid group-containing polymerizable compound, an inorganic filler, and a high-viscosity solvent has the above-mentioned problems. I found that it could be solved. The present invention has been further studied and completed based on this result.

That is, the present invention includes a dental adhesive pretreatment material composition containing the following phosphoric acid group-containing polymerizable compound, an inorganic filler, and a high-viscosity solvent.

Item 1.
(A) General formula (1):
[In the formula, R ¹ represents a hydrogen atom or an alkyl group.
X represents a nitrogen atom which may have an oxygen atom, a sulfur atom or a substituent.
Y represents a group represented by the following (Y1) or (Y2).
^{R 2, R 3, R 4} , R 5, R 6 and ^{R 7} are the same or different and are each a hydrogen atom or an alkyl group.
n and m represent integers of 1 to 1000.
* Indicates the binding site. ]
Phosphate group-containing polymerizable compound represented by,
A dental adhesive pretreatment material composition containing (B) an inorganic filler and (C) a high-viscosity solvent.
Item 2.
Item 2. The dental adhesive pretreatment material composition according to Item 1, wherein the wettability of the object to be treated is improved.
Item 3.
Item 2. The dental adhesive pretreatment material composition according to Item 1 or 2, wherein when the material has a large water contact angle, the water contact angle can be reduced.
Item 4.
Item 3. The dental adhesive pretreatment material composition according to any one of Items 1 to 3, wherein the (A) phosphoric acid group-containing polymerizable compound is soluble in water.
Item 5.
The dental adhesive pretreatment material composition according to any one of Items 1 to 4, further comprising (D) a low-viscosity solvent.
Item 6.
The dental adhesive pretreatment material composition according to any one of Items 1 to 5, further comprising (E) an additive.
Item 7.
Item 2. The dental use according to any one of Items 1 to 6, wherein the phosphoric acid group-containing polymerizable compound represented by the general formula (1) is 0.5 to 40% by weight in the total composition. Adhesive pretreatment material composition.
Item 8.
The dental adhesive pretreatment material composition according to any one of Items 1 to 7, which is an enamel and dentin etchant solution.
Item 9.
(A) General formula (1):
R ¹ represents a hydrogen atom or an alkyl group.
X represents a nitrogen atom which may have an oxygen atom, a sulfur atom or a substituent.
Y represents a group represented by the following (Y1) or (Y2).
^{R 2, R 3, R 4} , R 5, R 6 and ^{R 7} are the same or different and are each a hydrogen atom or an alkyl group.
n and m represent integers of 1 to 1000.
* Indicates the binding site. ]
Phosphate group-containing polymerizable compound represented by,
A method in which a dental composition containing (B) an inorganic filler and (C) a high-viscosity solvent is used as a pretreatment for adhesion.

In the dental adhesive pretreatment material composition of the present invention, since the phosphate group-containing polymerizable compound represented by the above general formula (1) is soluble in water, a polar solvent mainly containing water can be used. After using this material before the bonding process, it can be easily washed and removed with water.

Due to this effect, the pretreatment of the bonding process can be performed only with the bonding pretreatment material of the present invention, regardless of the material of the dental material, and even in the case where different materials are mixed, without separately painting. The effect of adhesion can be enhanced.

Since the dental adhesive pretreatment material composition of the present invention is a composition that is safe for the living body, it can be directly applied to the oral cavity.

The dental adhesive pretreatment material composition of the present invention not only enamel, which is the tooth substance to be adhered, but also dentin containing collagen fibers, without damaging the tissue due to excessive decalcification, during cavity formation. It is possible to remove cutting chips and form a rough surface. Therefore, similarly to the above-mentioned dental materials, enamel and dentin, which are different tooth qualities, can be used without being used or painted separately.

For ceramic materials, specifically zirconia, in the conventional technology, a phosphoric acid-based adhesive pretreatment agent (surface cleaning agent) is a material that should be avoided because it causes a decrease in adhesive strength due to surface adsorption of phosphoric acid. However, in the dental adhesive pretreatment material composition of the present invention, the dental adhesive pretreatment material containing the phosphoric acid group-containing polymerizable compound represented by the above general formula (1) has a polymerizable group. Therefore, the pollutants on the surface are replaced with the phosphoric acid group-containing polymerized monomer, and the surface can be covered with them to give the effect of surface treatment, and the adhesive effect can be improved.

According to the dental adhesive pretreatment material composition of the present invention, for a prosthesis made of a noble metal (gold, silver, platinum, palladium and an alloy composed of them), a non-noble metal or an organic-composite material, the above general formula ( The phosphate group-containing polymerizable compound represented by 1) can be used as a cleaning agent for pollutants adhering to the metal surface such as organic substances due to its surface active action, and can improve the adhesive effect or prevent the adhesive from failing. ..

FIG. 1 shows a scanning electron microscope (desktop microscope Miniscope® TM3030: Hitachi High-Technologies Corporation) before and after treating enamel or dentin using the dental adhesive pretreatment material composition of Example 7. ) Shows the photograph observed. FIG. 2 shows photographs of the contact angle between PMMA pellets and water before application (a) and after application (b, c, d) of the adhesive pretreatment material composition and their appearance (b: Example 4, c). : Comparative Example 1, d: Comparative Example 3). FIG. 3 is a photograph of the test results showing the consistency of the adhesive pretreatment material composition (Comparative Example 2, Examples 4, 5, 1 and 8). FIG. 4 is a photograph of test results showing the consistency of the adhesive pretreatment material composition (Comparative Example 1, Examples 4, 7 and 6).

Hereinafter, the dental adhesive pretreatment material composition of the present invention will be described in detail.

[Dental Adhesive Pretreatment Material Composition]
The dental adhesive pretreatment material composition of the present invention (hereinafter, also referred to as “composition of the present invention”) is (A) a phosphate group-containing polymerizable compound represented by the general formula (1), ( It contains B) an inorganic filler and (C) a high-viscosity solvent.

(A) Phosphoric Acid Group-Containing Polymerizable Compound The composition of the present invention contains a phosphoric acid group-containing polymerizable compound represented by the general formula (1) (hereinafter, may also be referred to as “component (A)”). contains.

In the above general formula (1), X represents an oxygen atom, a sulfur atom, or a nitrogen atom which may have a substituent. That is, as shown below, the component (A) includes a (meth) acrylic acid ester compound (1-1) having a phosphoric acid group and a (meth) acrylic acid thioester compound (1-2) having a phosphoric acid group. ), Or a (meth) acrylic acid amide compound (1-3) having a phosphoric acid group. As used herein, "(meth) acrylic acid" means at least one of "acrylic acid" and "methacrylic acid".
(In the formula, R ¹ and Y are as defined above. R ⁸ indicates a hydrogen atom or substituent.)

Y represents a group represented by the following (Y1) or (Y2).
^{(Wherein, R 2, R 3, R} 4, R 5, R 6, R 7, n and m are as defined above.)

That is, the component (A) contains a phosphate group (-P (= O)-(OH) ₂ ) and a (meth) acrylic acid ester group (CH ₂ = C (-R ¹ ) -C (= O)-. O-), (meth) acrylic acid thioester group (CH ₂ = C (-R ¹ ) -C (= O) -S-), or (meth) acrylic acid amide group (CH ₂ = C (-R ¹ )) -C (= O) -NR ⁸ - between), having the (Y1) or (linker portion indicated by Y2) (connecting group).

n represents an integer of 1 to 1000, and among them, 2 to 100 is preferable, 3 to 30 is more preferable, and 4 to 15 is particularly preferable.

Examples of the linker (ethyleneoxy group) having n of 1 to 1000 include a tetraethyleneoxy chain (n = 4), a pentaethylene glycol (n = 5), a hexaethylene glycol chain (n = 6) and the like.

Even if n of the linker is increased, the water solubility of the compound having the structure represented by the general formula (1) is substantially maintained. In fact, even a polyethylene glycol 600 chain (n = 6 to 23, number average molecular weight Mn 600) is arbitrarily dissolved in water.

m represents an integer of 1 to 1000, and among them, 2 to 100 is preferable, 3 to 30 is more preferable, and 4 to 20 is particularly preferable.

Examples of the linker (alkyleneoxy group) having m of 1 to 1000 include methyleneoxy (m = 1), ethyleneoxy group (m = 2), n-propyleneoxy group (m = 3), and n-butyleneoxy (m = 3). m = 4), n-pentyleneoxy (m = 5), n-hexyleneoxy (m = 6), n-heptyleneoxy (m = 7), n-octyleneoxy (m = 8), n-nonyleneoxy (M = 9), n-decyleneoxy (m = 10), n-undecyleneoxy (m = 11) and the like can be mentioned.

The "alkyl group" in the present specification is not particularly limited, and is, for example, a chain such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Alternatively, a branched C _1-4 alkyl group can be mentioned. In the present specification, "n-" means normal, "sec-" means secondary, and "t-" means tertiary.

The "substituent" in the present specification is not particularly limited, and may have, for example, 1 to 5 halogen atoms such as the above-mentioned alkyl group; acyl group, trifluoromethylcarbonyl group, and perfluorobenzoyl group. Good C _1-4 alkylcarbonyl groups and the like can be mentioned.
The "halogen atom" in the present specification is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specifically, the component (A) of the present invention combines a known production method (for example, J. Am. Chem. Soc., 1982, 586., Etc.), the production method described in Japanese Patent Application No. 2015-228130, and the like. As a result, it can be manufactured.
For example, a step of reacting a compound represented by the following general formula (2) with a compound represented by the following general formula (3) to obtain a compound represented by the following general formula (4) (reaction formula 1).
(Wherein, R ^1, X and Y are as defined above .Z represents a functional group capable of reacting with X.);
By reacting the compound represented by the general formula (4) with phosphorus oxychloride (hereinafter, _{also referred to as "phosphoryl chloride" or "POCl 3} "); and through a hydrolysis step, the general formula (1) The compound represented by can be produced.

Examples of Z include -OH group, -OR'group (R' indicates an alkyl group), -Cl group, -OC (= O) C (-R ¹ ) = CH ₂ group and the like. ..

Further, for example, the (meth) acrylic acid ester compound (1-1) having a phosphoric acid group is first prepared as an activated carboxylic acid derivative such as (meth) acrylic acid or (meth) acrylic acid chloride or acid anhydride. And a diol compound (for example, ethylene glycol, propylene glycol, decanediol, etc.) are reacted in the presence of a condensing agent and, if necessary, in the presence of an auxiliary base to obtain a (meth) acrylate having a hydroxyl group as a precursor. The step of obtaining, the step of reacting the (meth) acrylate having the hydroxyl group with phosphoryl chloride under the condition of controlling the water content, and the hydrolysis reaction (if necessary, water is added in the presence of a base such as triethylamine. It can be produced through a step of (hydrolyzing by adding).

The (meth) acrylic acid thioester compound (1-2) having a phosphate group first has a hydroxy group with an activated carboxylic acid derivative such as (meth) acrylic acid or (meth) acrylic acid chloride or acid anhydride. A step of obtaining a (meth) acrylic acid thioester having a hydroxyl group as a precursor in the presence of a thiol compound (for example, thioethanol or the like) as a condensing agent and an auxiliary base, and the thioester and phosphoryl chloride are added to water. It can be produced through a step of reacting under the conditions for controlling the above, and a step of hydrolysis reaction (hydrolyzed by adding water in the presence of a base such as triethylamine, if necessary).

The (meth) acrylic acid amide compound (1-3) having a phosphoric acid group first has a hydroxy group with an activated carboxylic acid derivative such as (meth) acrylic acid or (meth) acrylic acid chloride or acid anhydride. A step of obtaining a (meth) acrylic acid amide having a hydroxyl group as a precursor by using an amine compound (for example, aminoethanol or the like) as a condensing agent, and reacting the acrylic acid amide with phosphoryl chloride under conditions for controlling water content. It can be produced through a step of allowing the compound to be subjected to a hydrolysis reaction (if necessary, hydrolysis is carried out by adding water in the presence of a base such as triethylamine).

The component (A) is an amphipathic radically polymerizable monomer that is soluble in water (soluble in water) and also soluble in an organic solvent that is not mixed with water. By containing the component (A), the composition of the present invention can impart a decalcifying action to the tooth substance.

The component (A) has a structure in which one hydroxyl group of phosphoric acid is substituted with an organic group, has a larger molecular weight than phosphoric acid, and is sterically bulky. With such a molecular design, the reactivity with hydroxyapatite can be controlled by the shape. That is, hydroxyapatite, which has become cutting chips generated during the formation of the cavity, can be selectively reacted and removed, and hydroxyapatite in the uncut hard tissue is less likely to elute. In particular, dentin is very different from enamel in which hydroxyapatite is highly crystallized, and has pores extending from the pulp called dentin tubules. When cutting dentin, cutting chips invade the dentin tubules and block the holes (hereinafter, such cutting chips are also referred to as "smear plugs").

When the adhesive pretreatment material composition of the present invention containing the component (A) is applied to dentin, among the smear layer and smear plug composed of hydroxyapatite at the edge of the dentin capillary and powdered hydroxyapatite as cutting chips. The smear layer and smear plug can be selectively dissolved and removed. Therefore, the adhesive pretreatment material composition of the present invention containing the component (A) can be used as an etchant solution effective for enamel and dentin.

Further, with respect to zirconia, the portion of the phosphate group of the component (A) is adsorbed on the zirconia due to chemical interaction or the like, and the polymerizable (meth) acryloyl group is present on the surface. When the polymerizable adhesive is applied to such a modified surface and cured, it can be composited with the polymer by forming a sigma bond with the surface by copolymerization. Due to this effect, the polymer / zirconia interface can be strongly chemically bonded. Therefore, the adhesive strength to the zirconia material can be improved.

When used in precious metals, non-precious metals, organic-inorganic composite fillers, etc., component (A) is an organic substance or an inorganic substance-derived pollutant adhering to the surface due to the nature of the acidic group and the surfactant action derived from the ethylene glycol chain. Can be removed. In particular, even in a material that is easily discolored chemically, such as silver or a silver alloy, the surface can be cleaned without discoloration. Although a composition containing a strong alkali such as sodium hydroxide is effective in the conventional cleaning agent, such a strong alkali compound is harmful to the living body, and its use is limited to the use outside the oral cavity.

On the other hand, the component (A) in the present invention can be safely used for a living body.

As described above, due to the water-soluble and amphipathic effects of (A) used in the dental adhesive pretreatment material composition of the present invention, comprehensive use for each material and intraoral and extraoral use. It contributes to the realization of materials that can be used effectively regardless of conditions.

As a specific example of the component (A) in the general formula (1) when Y is (Y1) in the formula, for example,
11- (meth) acryloyloxytetraethylene glycol dihydrogen phosphate (MTEGP),
14- (Meta) Acryloyl Oxypentaethylene Glycol Dihydrogen Phosphate (M5EGP),
16- (meth) acryloyloxyhexaethylene glycol dihydrogen phosphate (M6EGP),
(Meta) Acryloyloxypolyethylene glycol 300 dihydrogen phosphate (MPEG300P: A plurality of phosphate group-containing polymerizable monomers having a structure represented by the above general formula (1) having a number average molecular weight Mn = 300 as a polyethylene glycol unit. Mixture containing),
(Meta) Acryloyloxypolyethylene glycol 400 dihydrogen phosphate (MPEG400P: contains a plurality of phosphoric acid polymerizable monomers having a structure represented by the above general formula (1) having a number average molecular weight Mn = 400 as a polyethylene glycol unit. blend),
(Meta) Acryloyloxypolyethylene glycol 600 dihydrogen phosphate (MPEG600P: contains a plurality of phosphoric acid polymerizable monomers having a structure represented by the above general formula (1) having a number average molecular weight Mn = 600 as a polyethylene glycol unit. blend),
(Meta) Acryloyloxypolyethylene glycol 800 dihydrogen phosphate (MPEG800P: contains a plurality of phosphoric acid polymerizable monomers having a structure represented by the above general formula (1) having a number average molecular weight Mn = 800 as a polyethylene glycol unit. blend),
(Meta) Acryloyloxypolyethylene glycol 1000 dihydrogen phosphate (MPEG1000P: contains a plurality of phosphoric acid polymerizable monomers having a structure represented by the above general formula (1) having a number average molecular weight Mn = 1000 as a polyethylene glycol unit. blend),
(Meta) Acryloyloxypolyethylene glycol 2000 dihydrogen phosphate (MPEG2000P: contains a plurality of phosphoric acid polymerizable monomers having a structure represented by the above general formula (1) having a number average molecular weight Mn = 2000 as a polyethylene glycol unit. blend),
(Meta) Acryloyloxypolypropylene glycol 400 dihydrogen phosphate (MPPG400P: contains a plurality of phosphoric acid polymerizable monomers having a structure represented by the above general formula (1) having a number average molecular weight Mn = 400 as a polypropylene glycol unit. Mixture) and the like. Among these, MTEGP, M5EGP, or M6EGP is preferable, and MTEGP is particularly preferable, from the viewpoint of obtaining good decalcification, permeability, and adhesiveness of the tooth substance.

Specific examples of the component (A) in the general formula (1) when Y is (Y2) in the formula include 6-methacryloyloxyhexyldihydrogen phosphate and 8-methacryloyloxyoctyldi. Examples thereof include hydrogen phosphate, 10-methacryloyloxydecyldihydrogenphosphate (MDP), 12-methacryloyloxide decyldihydrogen phosphate and the like.

The component (A) can be used alone or in combination of two or more.

The blending amount of the component (A) in the dental adhesive composition of the present invention is not particularly limited and may be appropriately determined from a wide range. From the viewpoint of obtaining good decalcification, surface modifying action, and surface active action of the tooth substance, the blending amount of the component (A) is usually 0.5 to 40% by weight based on the total weight of the composition of the present invention. %, preferably 1 to 35% by weight, more preferably 3 to 30% by weight. In the present specification,% by weight is synonymous with% by mass.

(B) Inorganic Filler The composition of the present invention contains an inorganic filler (hereinafter, may be referred to as “component (B)” or “inorganic filler (B)”) as a thickener. The inorganic filler is not particularly limited, and for example, inorganic oxide particles such as silica, alumina, titania, and zirconia, or composite oxide particles composed of these, calcium phosphate, hydroxyapatite, yttrium fluoride, itterbium fluoride, and the like. Spherical or amorphous inorganic fillers and the like can be mentioned.

The inorganic filler is preferably particles of silica, alumina, titania or the like produced by a flame thermal decomposition method, and more specifically, for example, manufactured by Nippon Aerozil Co., Ltd., trade name: Aerozil (registered trademark), Aerocside (registered trademark) Aluc, Aeroxide TiO ₂ P25, Aeroxide TiO ₂ P25S, VP Zirconium Oxide 3-YSZ, VP Zirconium Oxide 3-YSZ PH and the like can be mentioned.

The inorganic filler (B) can be used alone or in combination of two or more.

The average particle size of the inorganic filler (B) is usually 5 to 500 nm, preferably 5 to 200 nm, and more preferably 5 to 100 nm. Among them, the inorganic filler having an average particle size of 50 nm or less is less likely to cause sedimentation and phase separation of the composition, so that the decalcification ability for the dentin, the surface treatment ability for the adherend, and the operability of the composition do not deteriorate. Is particularly preferable.

Specifically, for example, when a silica filler is used, the silica filler is an amorphous glass-like, spherical or amorphous primary particle of silica gel having no pores, and the primary particle diameter is 5 nm to 200 nm. The surface may be a hydrophilic filler to some extent, or a hydrophobic filler obtained by reacting an organic group such as a methyl group with a coupling agent.

The average particle size of the inorganic filler (B) can be measured as an average value of the particle size of 100 randomly selected ultrafine particles obtained by taking an electron micrograph of the ultrafine particles. When the ultrafine particles are non-spherical, the particle size is defined by the arithmetic mean of the longest and shortest lengths of the ultrafine particles.

The blending amount of the inorganic filler (B) is usually 1 to 30% by weight, preferably 3 to 20% by weight, and more preferably 5 to 15% by weight, based on the total weight of the composition of the present invention.

(C) High Viscosity Solvent The composition of the present invention contains a high viscosity solvent (hereinafter, may be referred to as "component (C)" or "high viscosity solvent (C)").

The high-viscosity solvent (C) of the present invention is essential for improving the coatability, wettability or operability of the composition with respect to the adherend. The component (C) is not particularly limited as long as it is a compound capable of maintaining a uniform composition while imparting viscosity to the composition of the present invention, and known organic compounds or inorganic compounds can be used.

The high-viscosity solvent (C) is not particularly limited as long as it is 20 mPa · s (20 ° C.) or higher. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol. , High-viscosity organic liquids such as polyethylene glycol (average number of molecular weights 200 to 20000); non-volatile or refractory high-viscosity inorganic liquids such as silicone oils and mineral oils.

The high-viscosity solvent (C) can be used alone or in combination of two or more.

The blending amount of the high-viscosity solvent (C) is usually 1 to 90% by weight, preferably 10 to 88% by weight, and more preferably 25 to 87% by weight, based on the total weight of the composition of the present invention.

(D) Low-viscosity solvent The composition of the present invention can further contain a low-viscosity solvent (hereinafter, may be referred to as "component (D)" or "low-viscosity solvent (D)"). The low-viscosity solvent (D) is not particularly limited as long as it is a solvent having a viscosity lower than that of the high-viscosity solvent (C). For example, a low-viscosity solvent having a viscosity of less than 20 mPa · s (20 ° C.) can be used. Can be used.

The low-viscosity solvent (D) is preferably a compound capable of dissolving the component (A) and other components. Further, water having high polarity or an organic solvent is desirable from the viewpoint of imparting an effective decalcifying action on the tooth substance to the pretreatment material of the present invention.

Specific compounds of the component (D) include, for example, water; methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol, tert-butanol, n-pentyl alcohol, 2-pentyl alcohol, and the like. Alcohol-based solvents such as neopentyl alcohol; Ketone-based solvents such as acetone and methyl ethyl ketone; ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether (average molecular weight 200), tetrahydrofuran (THF), etc. System solvent; N, N-dimethylformamide (DMF); dimethylsulfoxide and the like.

Among them, as the low-viscosity solvent, water, ethanol, n-propanol, 2-propanol, n-butanol, tert-butanol, or acetone is preferable.

The low-viscosity solvent (D) can be used alone or in combination of two or more.

When the low-viscosity solvent (D) is used, the blending amount thereof is the total weight of the composition of the present invention from the viewpoint of good decalcification and surface modifying action of the dentin and easy washing with water after application. On the other hand, it is usually 0.1 to 90% by weight, preferably 0.5 to 40% by weight, and more preferably 1 to 30% by weight.

(E) Additive The composition of the present invention is further referred to as an additive (E) (hereinafter, also referred to as "(E) component") in order to supplement functionality in addition to the above components (A) to (D). ) Can be contained.

The component (E) is not particularly limited, and for example, a pigment (for example, Blue No. 1, Red No. 40, Green No. 3, Ultramarine, etc.) for enhancing the visibility of the adhesive pretreatment material, a dye, etc. , A polymerization inhibitor or a polymerization inhibitor for imparting chemical stability of the component (A), a radically polymerizable monomer having no special functional group distinct from the component (A), an inorganic filler, Examples thereof include fillers such as organic fillers and inorganic-organic composite fillers, and additives for enhancing the cleaning action of the composition.

The component (E) can be blended within a range that does not impair the effects of the present invention. When the component (E) is used, the blending amount thereof is usually 30% by weight or less, preferably 20% by weight or less, and more preferably 0.1 to 3 based on the total weight of the composition of the present invention. By weight%.

These can be used alone or in combination of two or more as appropriate.

Contact Angle The dental adhesive pretreatment material composition of the present invention can improve the wettability of the coated surface to be treated. Further, the dental adhesive pretreatment material composition of the present invention can reduce the contact angle of water when the contact angle of water is large. For example, the surface of the object to be treated (adhesion) whose contact angle with water is usually in the range of 65 to 75 degrees can be less than 60 degrees for the dental adhesive pretreatment material composition of the present invention, and then applied to dentistry. It can contribute to improving the affinity between the adhesive material for use and the surface of the adherend.

Consistency The dental adhesive pretreatment material composition of the present invention has an appropriate consistency and is in the form of a paste, so that it can be used in a wide range of situations.

When 0.25 g of the dental adhesive pretreatment material composition of the present invention is collected and held on a plate having an inclination of 30 ° for 1 minute, it is preferably less than 5 cm, more preferably less than 3 cm, and 0. It is particularly preferably ~ 1 cm.

When the consistency is within the above range, the dental adhesive pretreatment material composition of the present invention can be washed with the same cleaning material regardless of the material of the prosthesis, and can be made into dentin in the oral cavity, enamel and dentin. Can also be applied.

The method for producing the composition of the present invention is not particularly limited, and a known method for producing a dental adhesive composition may be followed. Generally, all the components to be blended are weighed to obtain a uniform solution. Can be manufactured by mixing well.

The composition of the present invention can also be used according to the method of using a dental adhesive pretreatment material containing a known water-soluble polymerized monomer. Specifically, regarding the adhesion of the dentin, generally, it may be applied to the dentin to be the adherend by removing the caries portion and washed with water. For example, when used for enamel, the adhesive pretreatment material of the present invention is applied, left for about 10 to 30 seconds, and then in water for about 10 seconds or until the color of the dye derived from the adhesion pretreatment material disappears. Cleaning completes the pre-bonding process. When it is used for dentin, it may be left for about 30 to 60 seconds and then washed with water in the same manner as described above. Further, when both tooth substances are mixed, it may be left for about 30 to 60 seconds and then washed with water in the same manner as described above.

For dental materials other than dentin, that is, in the case of adhesive pretreatment for precious metals, non-precious metals, ceramics and organic-inorganic composite materials, the adhesive pretreatment material composition of the present invention is applied and left for about 10 to 30 seconds. , Wash with water for about 10 seconds or until the color of the dye derived from the adhesive pretreatment material disappears to complete the cleaning or surface modification of the dental material.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The components used in Examples and Comparative Examples and their abbreviations and abbreviations are as follows.

[Component (A)] Phosphate group-containing polymerizable compound:
[a1] MTEGP:
11-methacryloyloxytetraethylene glycol dihydrogen phosphate (molecular weight 342.28)
[a2] MPEG600P:
Methacryloyloxypolyethylene glycol 600 dihydrogen phosphate (molecular weight 748.09)
[a3] MDP:
10-methacryloyloxydecyldihydrogen phosphate 342.00;
[Comparison component]
Phosphoric acid (manufactured by Wako Junyakusha)
[Component (B)] Inorganic filler:
[b1] Aerosil (registered trademark) OX50 (primary average particle size: 16 nm; manufactured by Nippon Aerosil)
[Component (C)] High-viscosity solvent:
[c1] Glycerin (viscosity: 1410 mPa · s (20 ℃); manufactured by New Japan Chemical Co., Ltd.)
[c2] PEG (Molecular weight 200, Viscosity: 45-65 mPa · s (20 ℃); manufactured by Wako Pure Chemical Industries, Ltd.)
[Comparison component]
Butanol (viscosity: 3.0 mPa · s (20 ° C); manufactured by Sigma-Aldrich)
[Component (D)] Low viscosity solvent:
[d1] Water (purified water, viscosity: 1.0 mPa ・ s; manufactured by Showa Pharmaceutical Co., Ltd.)
[d2] Ethanol (viscosity: 1.2 mPa · s; manufactured by Nippon Alcohol Co., Ltd.)
[d3] Acetone (viscosity: 0.32 mPa ・ s; manufactured by Junsei Chemical Co., Ltd.)
[Component (E)] Additive:
[e1] Blue No. 1 (manufactured by Saneigen FFI)

<Method of producing component (A)>
Reference example 1: M-TEG-P
Under water-free conditions, a solution of phosphorus oxychloride (1.00 mol) in THF (1.0 L) was cooled to −30 ° C., and then tetraethylene glycol monomethacrylate (0.95 mol) and triethylamine (triethylamine) were added to this solution. A mixed solution of 0.99 mol) and THF (1.0 L) was added dropwise. The obtained solution was stirred at 0 ° C. for 1 hour, an excess amount of water was added thereto, and a mixed solution of triethylamine (1.60 mol) and THF (0.2 L) was added dropwise, and the mixture was returned to room temperature and stirred overnight. After suction filtration of the insoluble material, the filtrate was concentrated. Water (2.0 L) was added to the concentrate, and the mixture was extracted 3 times with dichloromethane (1.5 L). The organic layers were combined, washed successively with saturated brine (1.0 L) and water (1.0 L), and dried over anhydrous sodium sulfate (300 g) for 3 hours or longer. The desiccant is separated by filtration, MEHQ (100 mg), which is a polymerization inhibitor, is added to the filtrate, and after concentration, BHT (150 mg), which is a polymerization inhibitor, is added to obtain the desired component (A) (pale yellow oil). The product was 114 g, the yield was 41.7%, and the purity confirmed by HPLC was 95% or more).

The purity confirmed by HPLC was 95% or more, and the structure was confirmed by ^{1 1 H-NMR.} NMR was measured by JNM-ECX400 (400 MHz) manufactured by JEOL Ltd. In the measured ¹ H-NMR, the chemical shift value of each sample was shown by the σ value (ppm) when tetramethylsilane (0 ppm) and chloroform (7.24 ppm) were used as internal standards. Coupling patterns are represented by singlet (s), triplet (t), multiplet (m), and broad (br). For the method for producing the above component (A), refer to the method described in Reference 1 (J. Dent., 2008, 36, 171-177.). However, as the reagent used for phosphorylation, the above synthesis method using phosphorus oxychloride is preferable to using polyphosphoric acid in producing the component (A) effective in dentistry.

[M-TEG-P]
^{1 1} H NMR (CDCl ₃ , Me ₄ Si) σ 1.94 (s, 3H), 3.67 (m, 12H), 4.17 (m, 2H), 4.30 (m, 2H), 5. 58 (s, 1H), 6.13 (s, 1H), 8.45 (brs, 2H).
³¹ P NMR (CDCl ₃ , Me ₄ Si) σ 1.00.

Reference example 2: M-PEG300-P
M-PEG300-P (light) according to the method described in Reference Example 1 except that 153 g of phosphorus oxychloride, 285 g of tetraethylene glycol monomethacrylate, 263 g of triethylamine in total, and 46 g of water were used instead. 198 g of yellow oil, 44% yield, 95% or more purity confirmed by HPLC) was produced.
[ M-PEG300-P ]
^{1 1} H NMR (CDCl ₃ , Me ₄ Si) σ 1.94 (s, 3H), 3.60-3.74 (m, 14H), 4.29 (t, 2H), 5.57 (s, 1H) ), 6.13 (s, 1H), 8.40 (brs, 2H).
³¹ P NMR (CDCl ₃ , Me ₄ Si) σ 1.00.

Reference example 3: M-PEG600-P
M-PEG600-P (pale yellow) according to the method described in Reference Example 1 except that 153 g of phosphorus oxychloride, 570 g of tetraethylene glycol monomethacrylate, 263 g of triethylamine in total, and 46 g of water were used instead. 288 g of oil, yield 38.4%, purity confirmed by HPLC was 95% or more) was produced.

[M-PEG600-P]
^{1 1} H NMR (CDCl ₃ , Me ₄ Si) σ 1.95 (s, 3H), 3.49 (brs, 2H), 3.64-3.75 (m, 42H), 4.30 (t, 2H) ), 5.57 (s, 1H), 6.13 (s, 1H).
³¹ P NMR (CDCl ₃ , Me ₄ Si) σ 1.04.

Reference example 4: MDP
A diethyl ether solution (100 ml) of 55 g of phosphorus oxychloride was cooled to −40 ° C. under a nitrogen atmosphere. A diethyl ether solution (100 ml) of 125 g of decanediol monomethacrylate and 37 g of triethylamine was slowly added dropwise to this solution at the same temperature. After completion of the dropping, the reaction solution was kept at −30 ° C. for 3 hours, and then set to 0 ° C. Next, 30 g of water was added dropwise at the same temperature, and then 72.9 g of triethylamine in a diethyl ether solution was added dropwise. After completion of the dropping, the reaction solution was kept at 0 ° C. and allowed to stand overnight. The precipitated triethylamine hydrochloride was filtered through a glass filter, and the filtrate was washed with an aqueous sodium chloride solution three times. The organic layer was dried over anhydrous sodium sulfate, and diethyl ether was distilled off under reduced pressure to obtain a yellow liquid. The obtained yellow liquid was washed with n-hexane three times to remove impurities. The n-hexane was distilled off under reduced pressure from a viscous oil insoluble in n-hexane to obtain 64.8 g of the desired MDP (purity confirmed by HPLC was 59%).

[MDP]
^{1 1} H NMR (CDCl ₃ , Me ₄ Si) σ 1.28 (m, 12H), 1.64 (m, 4H), 1.95 (s, 3H), 3.96 (m, 2H), 4. 20 (t, 2H), 5.54 (s, 1H), 6.12 (s, 1H), 6.20 (brs, 2H),
³¹ P NMR (CDCl ₃ , Me ₄ Si) σ 0.61.

Reference Example 5: Phosphate ester in which X is a sulfur atom (2-methacryloylthioglycol dihydrogen phosphate)
Under water-free conditions, a solution of phosphorus oxychloride (1.00 mol) in THF (1.0 L) was cooled to −30 ° C., and then 2-hydroxyethylmonothiomethacrylate (0.95 mol) was added to this solution. A mixed solution of triethylamine (0.99 mol) and THF (1.0 L) was added dropwise. The obtained solution was stirred at 0 ° C. for 1 hour, an excess amount of water was added thereto, and a mixed solution of triethylamine (1.60 mol) and THF (0.2 L) was added dropwise, and the mixture was returned to room temperature and stirred overnight. After suction filtration of the insoluble material, the filtrate was concentrated. Water (2.0 L) was added to the concentrate, and the mixture was extracted 3 times with dichloromethane (1.5 L). The organic layers were combined, washed successively with saturated brine (1.0 L) and water (1.0 L), and dried over anhydrous sodium sulfate (300 g) for 3 hours or longer. The desiccant is separated by filtration, MEHQ (100 mg), which is a polymerization inhibitor, is added to the filtrate, and after concentration, BHT (150 mg), which is a polymerization inhibitor, is added to obtain a pale yellow oil as the target component (A). It can be obtained as a product (115.34 g, 51%).

Reference Example 6: Phosphate ester in which X is an NH group (N- (2-hydroxyethylacrylamide dihydrogen phosphate)
Under water-free conditions, a solution of phosphorus oxychloride (0.50 mol) in THF (0.75 L) was cooled to −30 ° C., and then 2-hydroxyethylacrylamide (0.45 mol) and triethylamine ( A mixed solution of 0.49 mol) and THF (0.75 L) was added dropwise. The obtained solution was stirred at 0 ° C. for 1 hour, an excess amount of water was added thereto, and a mixed solution of triethylamine (0.80 mol) and THF (0.15 L) was added dropwise, and the mixture was returned to room temperature and stirred overnight. After suction filtration of the insoluble material, the filtrate was concentrated. Water (0.30 L) was added to the concentrate, and the mixture was extracted 3 times with chloroform (0.5 L). The organic layers were combined, washed successively with saturated brine (0.15 L) and water (0.30 L), and dried over anhydrous sodium sulfate (50 g) for 3 hours or longer. The desiccant is separated by filtration, MEHQ (100 mg), which is a polymerization inhibitor, is added to the filtrate, and after concentration, BHT (30 mg), which is a polymerization inhibitor, is added to obtain a yellow oil as the target component (A). It can be obtained by (26.01 g, 23%).

[Dental Adhesive Pretreatment Material Composition]
Example 1
According to the composition shown in Table 1 below, each component was mixed and then stirred until they became uniform to produce a dental adhesive pretreatment material composition according to Example 1. In addition, 0.03% by weight of Blue No. 1 was added as a pigment to the composition in order to improve visibility.

Examples 2 to 13 and Comparative Examples 1 to 4
Each dental adhesive pretreatment material composition according to Examples 2 to 13 and Comparative Examples 1 to 4 was produced in the same manner as in Example 1 except that the composition was produced based on the compositions shown in Tables 1 to 5 below. did. In addition, in Example 12 and Comparative Example 3 of Table 5, the pigment Blue No. 1 was not added. These dental adhesive pretreatment material compositions were evaluated as follows.

Test Example 1 (Measurement of Adhesive Strength to Enamel and Dentin)
First, the bovine anterior teeth removed within 24 hours after slaughter were polished with water-resistant abrasive paper of P600 under running water, and the enamel plane and the dentin plane were carved so as to be parallel to the lip surface. Next, compressed air was blown onto these surfaces for about 10 seconds to dry them, and then double-sided tape with a circular hole having a diameter of 3 mm was fixed to each of these surfaces to define the adhesive area. Next, a silicone rubber mold having a diameter of 5 mm and a thickness of 2.0 mm is attached onto the double-sided tape at a position where the hole is at the same center as the circular hole of the double-sided tape to form a simulated cavity. did. The adhesive pretreatment material compositions according to Examples 1 to 17 and Comparative Examples 1 to 4 were applied to the simulated cavities and left for 30 seconds for enamel and 60 seconds for dentin, and then about 10 Rinse with running water for a second, apply a dental adhesive (product name: Grouma Self Etch, manufacturer: Heleus Kurzer), apply according to the specified method, leave it to stand, and then dry it with compressed air for a specified period of time. I let you.

Next, the dental adhesive composition was cured by irradiating with light for 10 seconds using a visible light irradiator (product name: Pencure 2000, manufacturer: Morita Seisakusho). Furthermore, a dental composite resin (product name: Clearfill AP-X A3 shade, manufacturer: Clarenoritake Dental) is filled on the resin, and the adhesion test piece is irradiated with light for 30 seconds using a visible light irradiator. Made.

After immersing the above adhesion test piece in water at 37 ° C for 24 hours, a tensile test was performed using a tensile tester (product name: Autograph, manufacturer: Shimadzu Seisakusho) under the condition of a crosshead speed of 1 mm / min. The adhesive strength of each of the dental adhesives according to Examples 1 to 13 and Comparative Examples 1 to 4 with respect to the enamel plane and the dentin plane was measured. The tensile adhesive strength of 5 pieces per test was measured by the above method, and the average value was taken as the adhesive strength, and the standard deviation was also calculated.

The measurement results obtained above were compared with the average value based on the significant difference in effectiveness using the adhesion test result without etching treatment with the pretreatment material of the present invention as a negative control.

Test Example 2 (Measurement of Adhesive Strength to Zirconia)
A zirconia test piece (KZR-CAD zirconia; made of Yamamoto Precious Metal Bullion) molded and sintered into a disk shape according to the specified procedure is polished under running water until the surface to be adhered becomes uniform with water-resistant abrasive paper up to P1000. went. After ultrasonic cleaning, air-drying was performed, and Examples 4, 6, 7, 8 and 9 and Comparative Examples 1 and 2 were left for 10 seconds after application, and washed with running water for 10 seconds. After air-drying again, double-sided tape having a circular hole with a diameter of 3 mm was fixed to define the adhesive area. Here, a dental resin cement (product name: Panavia V5, manufacturer: Kurarenoritake) was irradiated with light for 20 seconds using a visible light irradiator to prepare an adhesion test piece. After immersing it in water at 37 ° C for 24 hours as in the case of dentin, use a tensile tester (product name: Autograph, manufacturer: Shimadzu Corporation) to comply with the JIS standard for dental resin cement. A tensile test was performed under the condition of a crosshead speed of 0.75 mm / min.

If the average value of the adhesive strength is 5 MPa or more, it is judged that excellent adhesiveness is exhibited.

The results of each test are shown in Tables 1 to 6 below.
[Examination of (D) component content]

<Test result>
From the results in Table 1 above, the dental adhesive pretreatment material composition of the present invention (Examples 1 to 5) showed equally excellent decalcification ability with respect to both enamel and dentin, and the adhesive strength. It became clear that it reinforces.

[(A) Examination of component content]

<Test result>
From the results in Table 2 above, the dental adhesive pretreatment material composition of the present invention (Examples 4, 6 and 7) showed equally excellent decalcification ability for both enamel and dentin. It was revealed that the adhesive strength was reinforced. On the other hand, the composition containing no MTEGP had a reduced adhesive strength with respect to both enamel and dentin.
Further, the dental adhesive pretreatment material composition of the present invention (Examples 4, 6 and 7) was surface-treated with respect to zirconia, and the adhesive strength of the material was improved as in the case of enamel and dentin. .. On the other hand, the composition containing no MTEGP had a reduced adhesive strength against zirconia.

[Examination of (A) component]

<Test result>
From the results in Table 3 above, the dental adhesive pretreatment material composition (Examples 4, 8 and 9) in which the component (A) is the above-mentioned various phosphate group-containing polymerizable compounds is of enamel and dentin. It was clarified that the decalcification ability was equally excellent for all of them and the adhesive strength was reinforced.

On the other hand, the dental adhesive pretreatment material composition containing phosphoric acid instead of the phosphoric acid group-containing polymerizable compound (Comparative Example 2) had some adhesiveness to enamel, but dentin. It was found that the adhesiveness decreased with respect to the quality.

In addition, the dental adhesive pretreatment material composition of the present invention (Examples 4, 8 and 9) was surface-treated with respect to zirconia, and the adhesive strength of the material was improved as in the case of enamel and dentin. .. Adhesion of existing phosphoric acid-based etchant solutions is reduced by the adhesion of phosphoric acid to the surface of zirconia, but good surface treatment on the surface of zirconia was achieved by using a phosphoric acid-containing polymerizable compound. Therefore, from the results shown in Tables 2 and 3, the present invention can be effectively used for all tooth substances as described above, and is an epoch-making treatment agent.

[Examination of (D) component]

<Test result>
From the results in Table 4 above, the dental adhesive pretreatment material composition of the present invention (Examples 10 and 11) in which an organic solvent such as ethanol or acetone was used instead of water as the solvent for the component (D) was found. It was clarified that it showed equally excellent decalcification ability for both enamel and dentin and reinforces the adhesive force.

[Examination of (C) component]

<Test result>
From the results in Table 5 above, the dental adhesive pretreatment material composition of the present invention (Example 12) using PEG instead of glycerin as the high-viscosity solvent of the component (C) is made of enamel and dentin. It was clarified that the decalcification ability was equally good for all of them and the adhesive strength was reinforced. On the other hand, the dental adhesive pretreatment material composition using butanol as the thickener of the component (C) had some adhesiveness to enamel, but adhered to dentin. It was found that the sex was reduced.

Test Example 3 (SEM imaging)
Further, in the present invention, the tooth surface after treatment with the dental adhesive pretreatment material composition of Example 7 was imaged by SEM, and the state of the surface was observed.

<Test result>
The dental adhesive pretreatment material composition of the present invention selectively removes the smear layer and / or the smear plug without causing excessive decalcification of dentin, which was not possible with existing phosphoric acid-based etching materials. It was shown to be achieved, and this effect was equally effective for both enamel and dentin (see Figure 1).

Test Example 4 (Wetability: Contact angle)
Dissolve bovine serum albumin (manufacturer and distributor: Sigma Aldrich) in commercially available artificial saliva (product name: salivat, manufacturer: Teijin Pharma Limited) to a concentration of 2000 mg / l, and adjust to a protein concentration such as the general saliva phase. Then, a pseudo artificial saliva was prepared. 6 to 8 mg of water droplets were dropped on the surface of the polymethacrylic acid (red colored) test piece, and the angle formed by the water droplets and the test piece was measured as the contact angle. Further, the pseudo-artificial saliva was applied to the entire surface of the test piece and air-blown (after contamination with pseudo-artificial saliva), and the surface was washed with distilled water and dried by air-blow (after washing with water). The same test was carried out on a surface (after application of Examples / Comparative Examples) to which each dental adhesive pretreatment material composition was applied, washed with water and dried.

The results are shown in Table 7 and FIG.

<Test result>
From the results shown in Table 7, the dental adhesive pretreatment material composition of the present invention (Example 4) had a reduced water contact angle as compared with the composition of Comparative Example 1. In other words, it was shown that the wettability (contact angle) of the applied surface was significantly different depending on the presence or absence of M-TEG-P, and it was confirmed that the wettability of the applied surface was improved by M-TEG-P.
On the other hand, the composition of Comparative Example 3 when phosphoric acid was added did not have a wettability effect.

Test Example 5 (Consistency test)
On a plastic tray with lines drawn every 1 cm (FIGS. 3 and 4), 0.25 g of each sample having the composition shown in Table 9 below was collected and held on a plate at an inclination of 30 ° for 1 minute. As a result, the consistency was determined by the length of each sample dripping.
[Judgment]
◯: The length of the drooping sample is less than 5.0 cm.
X: The length of the drooping sample is 5.0 cm or more.

<Test result>
From the results in Table 8, the dental adhesive pretreatment material composition of the present invention (Examples 1, 4, 6 and 7) has an appropriate consistency and is in the form of a paste, and is therefore used in a wide range of situations. I found that I could do it.
On the other hand, it was found that the compositions of Comparative Examples 1 and 4 had poor consistency results and were difficult to use as a pretreatment agent.

Claims (9)

(A) General formula (1):
[In the formula, R ¹ represents a hydrogen atom or an alkyl group.
X represents an oxygen atom, a sulfur atom or a nitrogen atom having a substituent or a hydrogen atom.
Y represents a group represented by the following (Y1) or (Y2).
^{R 2, R 3, R 4} , R 5, R 6 and ^{R 7} are the same or different and are each a hydrogen atom or an alkyl group.
n and m represent integers of 1 to 1000.
* Indicates the binding site. ]
Phosphate group-containing polymerizable compound represented by,
A dental adhesive pretreatment material composition containing (B) an inorganic filler and (C) a solvent having a viscosity of 20 mPa · s (20 ° C.) or higher. The dental adhesive pretreatment material composition according to claim 1, wherein the wettability of the object to be treated is improved. The dental adhesive pretreatment material composition according to claim 1 or 2, wherein when the material has a large water contact angle, the water contact angle can be reduced. The dental adhesive pretreatment material composition according to any one of claims 1 to 3, wherein the (A) phosphoric acid group-containing polymerizable compound is soluble in water. (D) The dental adhesive pretreatment material composition according to any one of claims 1 to 4, which contains a solvent having a viscosity of less than 20 mPa · s (20 ° C.). The dental adhesive pretreatment material composition according to any one of claims 1 to 5, further comprising (E) an additive. The dentistry according to any one of claims 1 to 6, wherein the phosphoric acid group-containing polymerizable compound represented by the general formula (A) is 0.5 to 40% by weight in the total composition. Adhesive pretreatment material composition for. The dental adhesive pretreatment material composition according to any one of claims 1 to 7, which is an enamel and dentin etchant solution. (A) General formula (1):
R ¹ represents a hydrogen atom or an alkyl group.
X represents an oxygen atom, a sulfur atom or a nitrogen atom having a substituent or a hydrogen atom.
Y represents a group represented by the following (Y1) or (Y2).
^{R 2, R 3, R 4} , R 5, R 6 and ^{R 7} are the same or different and are each a hydrogen atom or an alkyl group.
n and m represent integers of 1 to 1000.
* Indicates the binding site. ]
Phosphate group-containing polymerizable compound represented by,
A dental composition containing (B) an inorganic filler and (C) a solvent having a viscosity of 20 mPa · s (20 ° C.) or higher is selected from the group consisting of precious metals, non-precious metals, ceramics and organic-inorganic composite materials. A method used for pretreatment of adhesions to at least one dental material.