JP2003081730A - Pretreatment agent for lining material of denture base and kit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pretreatment agent for the lining material of a denture base, which is a pretreatment agent for the lining material of a denture base using a nonhalogen-based organic compound having safety higher than that of a chlorine-based organic compound and has strong points of excellent initial adhesiveness between a denture base and a lining material and durability of adhesion and low smell. SOLUTION: This pretreatment agent for the lining material of a denture base comprises a dioxolane compound (e.g. 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane or 4-methyl-1,3-dioxolane) represented by general formula (1) (R<1> to R<6> are each independently a hydrogen atom or a 1-6C alkyl group).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a pretreatment agent for a denture base lining material for adhering a denture base and a lining material. More specifically, it relates to a pretreatment agent for a denture base lining material, which comprises a dioxolane compound having a specific structure.

[0002]

2. Description of the Related Art When a denture is worn for a long period of time, the denture gradually becomes less compatible with the oral mucosa due to bone resorption, gingival deformation and the like. As a result, the denture is frequently dislodged, or only a specific part of the denture comes into strong contact with the gingiva to cause inflammation. Therefore, a means for refitting the mucosal side of the denture base that has become incompatible with a denture base lining material and re-adapting it to the palate mucosal face is widely used clinically. Such an operation of remodeling the denture base is called lining.

Concretely, the lining is placed on the mucosal side of the denture base with a paste-like or rice cake-like lining material and directly inserted into the oral cavity of the patient to adapt it, or to a plaster model of the patient's palate. It is generally carried out by a method of curing by using a chemical reaction or a photochemical reaction after the molding and shaping. The former is called the direct lining method and the latter is called the indirect lining method.

Further, depending on the hardness of the lining material, it can be classified into a hard lining material and a soft lining material. Generally, the former is mainly composed of a (meth) acrylate compound and the latter is mainly. It is composed of silicone compounds.

In order to improve the adhesiveness between the lining material and the denture base regardless of the above-mentioned direct method or indirect method or the kind of the material of the lining material, the denture base is placed before the lining. It is common to perform pretreatment with a treatment agent. As a method of using the pretreatment agent, it is common to apply a liquid pretreatment agent to the denture base using a brush or a brush, and after the liquid component is naturally dried or volatilized by air blow, lining is generally performed. .

As the pretreatment agent, those having different compositions depending on the components constituting the lining material are used. For example, in a hard backing material composed of a (meth) acrylate-based polymerizable monomer, a halogen-based organic solvent such as methylene chloride alone or a solution of a specific polymer dissolved in the halogen-based organic solvent is used. Has been. For example, as such a solution-type pretreatment agent, a pretreatment agent in which methylene chloride is combined with polystyrene resin and polymethylmethacrylate (JP-A-58-72509), a chlorine-based organic solvent and polycarbonate resin are combined. Pretreatment agent (JP-A-61-50906 and JP-A-61-11-1)
34306), a pretreatment agent in which a chlorine-based organic solvent is combined with an aromatic polyester or polyester carbonate (JP-A-61-136562), and methylene chloride with a polycarbonate resin, polymethylmethacrylate, and a polyfunctional methacrylate. A combined pretreatment agent (JP-A-10-231228) is known.

On the other hand, in the case of using a soft backing material composed of a silicone compound, a pretreatment in which a reactive silicone-modified methacrylate copolymer having a specific structure is dissolved in an organic solvent such as methylene chloride. Agent (Patent 27
No. 42268) is known. Among them, a halogen-based organic compound such as methylene chloride is widely used as a constituent component of a pretreatment agent for denture base lining because it rapidly penetrates into the resin material constituting the denture base and has appropriate volatility.

However, in recent years, stricter control has been required for halogenated organic compounds in view of the environmental load and harmfulness of the volatile vapor. Therefore, it is strongly desired to replace the halogen-based organic solvent with a non-halogen organic solvent in the constituents of the pretreatment agent for denture backing material.

On the other hand, ethyl acetate or methyl ethyl ketone may be used as an alternative pretreatment agent for the halogen-based organic compound, but these alone do not have sufficient adhesive force and have a peculiar odor, and therefore they are dental. There is a problem that it gives an operator or patient such as a doctor or a hygienist an unpleasant feeling.

[0010]

As described above, a pretreatment agent for a denture base lining material using a halogen-free organic compound having a higher safety than a chlorine-based organic compound, It has not been found that it has an excellent initial adhesive strength and adhesion durability with the equipment and has a low odor. Then, this invention makes it a subject to provide the pretreatment agent for denture base lining materials which has such an outstanding performance.

[0011]

As a result of intensive studies to solve the above problems, the present inventors have found that a dioxolane compound having a specific structure has an unpleasant odor as a component of a pretreatment agent. In addition, it was found that the initial adhesive strength and the adhesive durability were equal to or higher than those in the case where the chlorine-based organic compound was used, and the present invention was completed.

That is, the present invention provides the following general formula (1)

[0013]

[Chemical 2]

(In the formula, R ^{1 to} R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) A pretreatment agent for a denture base lining material containing a dioxolane compound Is.

Another aspect of the present invention is a pretreatment agent which further contains a high-molecular polymer soluble in the dioxolane compound represented by the general formula (1).

Still another aspect of the present invention is a kit for lining a denture base comprising such a pretreatment agent and a lining material.

The mechanism of effect expression in the present invention is presumed as follows. The present invention is not restricted by the mechanism of manifestation of effects. The dioxolane compound in the pretreatment agent of the present invention, when applied to the denture base, quickly permeates the surface of the denture base to impart tackiness by swelling, and when the dioxolane compound volatilizes from the swelling layer, It is presumed that the denture base surface was roughened as a result of the formation of voids in the volatilization path, and the physical fitting force with the lining layer was imparted. Further, in a soft lining material containing silicone as a main component, when a dioxolane compound and a (meth) acrylate copolymer modified with a siloxane having a specific reactive functional group are combined, a denture of the dioxolane compound is obtained. Due to its excellent solubility in the resin components that make up the floor, this copolymer molecule and the molecules in the resin that are the components of the denture base are entangled well, and the bond with the denture base becomes strong, while It is presumed that the reactive siloxane residue in the united molecule reacts with each other when the backing material is cured to form a bond, so that stronger adhesive force is generated.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The pretreatment agent for a denture base lining material of the present invention comprises a dioxolane compound having a structure represented by the following general formula (1).

[0019]

[Chemical 3]

(In the formula, R ^{1 to} R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) In the above general formula, R ^{1 to} R ⁶ are each independently a hydrogen atom or It is an alkyl group having 1 to 6 carbon atoms. The R ¹
When ~ R ⁶ is an alkyl group having 7 or more carbon atoms, it is not effective because when applied to a denture base, the permeation rate into the denture base becomes slow and the volatilization rate of the excess liquid becomes remarkably slow. Further, those substituted with other than an alkyl group are difficult to obtain and synthesize and are not practical. The alkyl group having 1 to 6 carbon atoms is specifically a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or the like,
From the viewpoint of adhesiveness, an alkyl group having 1 to 2 carbon atoms is preferable.
Further, 2 to ⁶ of R ^{1 to} R ⁶ are preferably hydrogen atoms, and more preferably 4 to 6 of them are hydrogen atoms.

Specific examples of the dioxolane compound which is preferably used include 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2-ethyl-1,3-dioxolane and 2-propyl-1. , 3-dioxolane, 2
-Butyl-1,3-dioxolane, 2-pentyl-1,
3-dioxolane, 2-hexyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 2,2
-Diethyl-1,3-dioxolane, 2-ethyl-2-
Methyl-1,3-dioxolane, 2-methyl-2-propyl-1,3-dioxolane, 2-ethyl-2-propyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 2,4- Dimethyl-1,3-dioxolane,
2,2,4-trimethyl-1,3-dioxolane, 4-
Ethyl-1,3-dioxolane, 4-propyl-1,3
-Dioxolane, 4-butyl-1,3-dioxolane,
4,5-dimethyl-1,3-dioxolane, 2,2
Examples include 4,5-tetramethyl-1,3-dioxolane.

Among the above-mentioned dioxolane compounds, the penetration rate into the denture base is high, and the swelling ability of the penetration surface is high, resulting in high adhesiveness and adhesive durability 1,3
-Dioxolane, 2-methyl-1,3-dioxolane,
2,2-Dimethyl-1,3-dioxolane and 4-methyl-1,3-dioxolane are preferably used. Particularly, 1,3-dioxolane is most preferably used because it can be obtained industrially at low cost. Moreover, these may use a dioxolane compound individually and may mix and use 2 or more types of dioxolane compounds.

In the pretreatment agent for denture base lining material of the present invention, other organic solvent may be mixed with the dioxolane compound and used. The solvent for mixing is not particularly limited as long as it is a solvent that can be uniformly mixed with the dioxolane compound, and ethanol, 1-propanol,
Alcohol compounds such as 2-propanol, ether compounds such as diethyl ether, t-butyl methyl ether and diethylene glycol dimethyl ether, ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate Ester compounds and the like.

Among these, those having a low boiling point and high volatility dry quickly and are easy to handle.
Those having a boiling point of -100 ° C are preferred. In addition, ethanol, 2-propanol, and acetone are more preferable from the viewpoint of odor and harm to the living body.

These mixing solvents can be used alone or in admixture of several kinds.

The blending amount of the above-mentioned solvent for mixing is not particularly limited as long as it does not impair the high adhesiveness, the adhesive durability and the low odor obtained by using the dioxolane compound, but is preferably. The mass ratio of the dioxolane compound: mixing solvent is 100: 0 to 50:50, and more preferably 100: 0 to 80:20.

In the pretreatment agent for a denture base lining material of the present invention, it is preferable to further add a high molecular weight polymer. By adding such a high molecular weight polymer, a stable coating is formed on the pretreated denture base surface, improving the aesthetics of the treatment agent application site, and further adhering the denture base to the denture base lining material. It has the effect of improving durability. The type of the high molecular polymer is not particularly limited as long as it is soluble in the dioxolane compound, and a (meth) acrylate-based, polystyrene-based, polycarbonate-based, polysulfone-based homopolymer or copolymer is used. it can.

In recent years, as a denture base and a lining material, a (meth) acrylate-based material has been widely used, and the effect of improving the adhesiveness and the adhesive durability to such a material is particularly excellent. The (meth) acrylate type is also suitable as the high molecular weight polymer to be mixed with the pretreatment agent for denture base lining material. The poly (meth) acrylate-based polymer may be a homopolymer such as poly (methyl methacrylate) or poly (ethyl methacrylate), or a copolymer such as a poly (methyl methacrylate-ethyl methacrylate) copolymer. Good.

Specific examples of the (meth) acrylate-based polymer include poly (methyl methacrylate), poly (ethyl methacrylate), poly (isopropyl methacrylate) Poly (butyl methacrylate)
Etc. homopolymers, poly (methyl methacrylate-ethyl methacrylate) copolymers, poly (methyl methacrylate-propyl methacrylate) copolymers, poly (methyl methacrylate-butyl methacrylate) copolymers, poly (ethyl methacrylate-butyl methacrylate) Examples thereof include copolymers such as copolymers. In addition, when these (meth) acrylate-based polymers are copolymers,
Any of a random copolymer, an alternating copolymer, and a block copolymer can be preferably used. In addition, as the polymerized units including those other than (meth) acrylate type, polystyrene-poly (methyl methacrylate) block copolymer, polycarbonate-poly (methyl methacrylate) block copolymer, polycarbonate-poly (ethyl methacrylate) block Also suitable are block copolymers of (meth) acrylate units and other polymerized units such as copolymers such as polysulfone-poly (methyl methacrylate) block copolymers and polysulfone-poly (ethyl methacrylate) block copolymers. Used. When the denture base is made of a material other than the (meth) acrylate-based material, it is particularly effective that the other polymerized units are of the same quality as that material. For example, in a denture base containing a polycarbonate polymer as a main component, a polycarbonate-poly (methyl methacrylate) block copolymer or the like is used, and in a denture base containing a polysulfone polymer as a main component, a polysulfone-poly (methyl methacrylate) block is used. A copolymer etc. can be used conveniently.

The molecular weight of the above high molecular weight polymer is preferably in the range of 5,000 to 1,000,000 in terms of weight average molecular weight, and more preferably 50,000 to 800,000.
It is more preferable that the range is. Molecular weight is 5,0
By using a high molecular weight polymer of 00 or more, a stable film can be formed, and it becomes easy to obtain high aesthetics without clouding the coated surface, while the molecular weight is 1,000,
By setting the viscosity to 000 or less, the viscosity of the pretreatment material solution becomes a viscosity suitable for coating, and it becomes easy to obtain excellent operability.

The compounding amount of the above-mentioned high molecular weight polymer is not particularly limited as long as the effect is exhibited, but the larger the compounding amount is, the higher the effect is, and the smaller the compounding amount is, the lower the solution viscosity is. Since it will be excellent in operability,
0.05 to 100 parts by mass of the total amount of the dioxolane compound and the mixing solvent, which is blended as necessary.
It is preferably 20 parts by mass.

When the backing material is made of a (meth) acrylate-based material, the above-mentioned (meth) acrylate-based polymer does not need to be modified with any substituent.
When the backing material is a silicone-based material, the above (meth) acrylate-based polymer contains CH = CH ₂ groups or Si.
It is preferably modified with a siloxane having an H group. The CH = CH ₂ group or SiH group (hereinafter, both may be collectively referred to as a reactive functional group) reacts together during a hydrosilylation reaction which is a curing reaction of a silicone-based backing material, The denture base material and the lining material have extremely high adhesion and durability.

(Meth) acrylate-based polymer modified with siloxane having a reactive functional group (hereinafter referred to as reactive siloxane-modified (meth) acrylate-based polymer)
For example, JP-A-7-70246 and JP-A-7-7
Those described in Japanese Patent No. 6611 can be preferably used.

Specifically, the (meth) acrylate polymer has a (poly) siloxane group as a side chain, and the siloxane group further has a CH = CH group such as a vinyl group or an allyl group.
It is a compound that is substituted with a group having _two groups or at least one of the Si atoms in the (poly) siloxane group has a Si-H bond. Alternatively, it may have both groups. Those having a SiH group are particularly preferable because they have high reactivity and the effect of improving adhesiveness and adhesive durability is remarkable.

The (poly) siloxane group having a reactive functional group is preferably a (poly) siloxane group having an average number of repeating units of siloxane units (SiO) of 1 to 200, preferably 10 to 100. This (poly)
The siloxane group is preferably contained in an average ratio of 0.001 to 0.9 with respect to one (meth) acrylate-based polymer unit constituting the (meth) acrylate-based polymer, and 0.01 to It is more preferable that the number is 0.9.

The number of the reactive functional groups contained in one (poly) siloxane group is preferably 1 to 100, more preferably 3 to 100.

The silicone-modified (meth) acrylic copolymer having such a reactive functional group is shown below.
Structural unit represented by the following general formula (2) (structural unit A)
When,

[0038]

[Chemical 4]

(In the formula, R ⁷ is a hydrogen atom or a methyl group, R 7
⁸ represents an alkyl group having 1 to 13 carbon atoms or an aryl group having 6 to 14 carbon atoms. ) A structural unit (structural unit B) represented by the following general formula (3a) or (3b) or (4):

[0040]

[Chemical 5]

(In the formula, R ⁹ represents a hydrogen atom or a methyl group,
R ^{10 to} R ¹⁹ each independently represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ²⁰ and R ²¹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon atom. An aryl group of the formula 6 to 14, Y represents a divalent organic residue having 1 to 18 carbon atoms which may have an ether bond or an ester bond in a bond or a main chain, and a to c each represent an average. Indicates the number of repeating units, a is 1, b is 1 to 100,
c is 0 to 100, and 10 ≦ (b + c) ≦ 10
0, 0 ≦ (c / b) ≦ 10, and within this range, the units may be arranged in any order. )

[0042]

[Chemical 6]

(In the formula, R ²² is a hydrogen atom or a methyl group,
R ²³ , R ²⁴ and R ²⁵ each independently represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms, and Y
Represents a divalent organic residue having 1 to 18 carbon atoms which may have an ether bond or an ester bond in the bond or in the main chain, m is 0 to 100, and n is 1, 2 or 3. ), And the structural unit A and the structural unit B have a structural unit A / (structural unit A + structural unit B) = 99.9-10% unit number ratio, and it can use conveniently.

Further, instead of a part of the structural unit A, a structural unit represented by the following general formula (5) (structural unit C)

[0045]

[Chemical 7]

(Wherein R ²⁶ is a hydrogen atom or a methyl group,
Y represents a bond or a divalent organic residue having 1 to 18 carbon atoms which may have an ether bond or an ester bond in the main chain. ) Is (structural unit A + structural unit C) / (structural unit A + structural unit B + structural unit C) = 99.9 to 10%, and structural unit A / (structural unit A + structural unit B + structural unit C)> 10 It is also possible to use compounds having a unit number ratio of%.

R ⁷ in the above general formulas (2) to (5),
R ⁹ , R ²² and R ²⁶ are each a hydrogen atom or a methyl group. In addition, a hydrogen atom and a methyl group may coexist in one polymer.

R ⁸ is an alkyl group having 1 to 13 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group and a tridecyl group, and a phenyl group, a benzyl group, 6 to 6 carbon atoms such as naphthyl group
It is selected from 14 aryl groups, and an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and an n-propyl group is most suitable, and one or more kinds selected from these are selected. A mixed system using groups together is preferable.

R ^{10 to} R ²¹ and R ^{23 to} R ²⁵ are each independently a methyl group, an ethyl group, an n-propyl group, or n.
A C1-6 alkyl group such as a hexyl group, or a C6-14 aryl group such as a phenyl group, a benzyl group, or a naphthyl group; A methyl group, a phenyl group, or a combination thereof is preferable in view of the synthesis and availability of the polysiloxane contained therein and the high reactivity of the resulting copolymer.

Y is a bond or a divalent hydrocarbon group having 1 to 18 carbon atoms which may have an ether bond or an ester bond in the main chain, and an ether bond or an ester bond is selected for ease of synthesis. It is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms which may be possessed. Specifically, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group,
1-8 carbon atoms such as heptamethylene group and octamethylene group
Of or alkylene _{group, -CH 2 CH 2 OCH 2 CH} 2 -
_{Group, -CH 2 CH 2 OCH 2 CH} 2 OCH 2 - group, -C
H ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ — group and other derivative groups of alkylene glycol groups, —CH ₂ CH
_{2 OC (= O) CH 2} CH 2 CH 2 - group, and the like groups.

In the general formulas (3a) and (3b), a to c represent the number of units of each siloxane unit (SiO), a is 1, b is 1 to 100, and c is 0 to 100,
And 10 ≦ (b + c) ≦ 100, 0 ≦ (c / b) ≦ 10
In this range, the units may be arranged in any order. Usually, it is obtained as a mixture of different b and c from the requirement of synthesis, but in this case, the average value of b and c in the mixture may be within the above range. Particularly preferred are compounds having an average value of c of 3 or more.

The weight average molecular weight of these copolymers is 5,
It is preferably 000 to 1,000,000, and b and c, the copolymerization ratio of the structural unit A, the structural unit B and the structural unit C, and the total number of polymerization thereof may be determined so as to fall within this range. .

Further, the molecular weight of the siloxane portion and the molecular weight of the (meth) acrylic polymer portion are determined by the compatibility with the acrylic resin and the silicone rubber portion of the denture base, the reactivity, and the ease of synthesis. It is preferred to choose a combination such that the ratio is from 1: 0.1 to 1: 2.

Typical examples of the reactive siloxane-modified (meth) acrylic copolymer according to the present invention are specifically shown by the structure of the structural unit and the average number of repeating units thereof.

[0055]

[Chemical 8]

[0056]

[Chemical 9]

[0057]

[Chemical 10]

[0058]

[Chemical 11]

(However, Ph represents a phenyl group) and the like. These polymers are generally white powdery solids.

Incidentally, these copolymers and the examples described later,
The bonding order of the structural units and the siloxane units in the copolymer used in the comparative examples is completely arbitrary, and the number of repeating units shown in the structural formula merely indicates the average total amount of each structural unit and each siloxane unit. Absent. The terminal of the (meth) acrylic polymer portion in the above copolymer is determined depending on the polymerization catalyst for polymerizing the (meth) acrylic acid ester used as a raw material.

The amount of the reactive siloxane-modified (meth) acrylic polymer blended is 100 parts by mass of the dioxolane compound and 100 parts by mass of the solvent for mixing which is blended as necessary.
It is preferably 0.1 to 20 parts by mass, and 0.1 to 10 parts by mass.
More preferably, it is parts by mass. Within this range, a suitable viscosity with good operability and high adhesiveness can be obtained.

When the pretreatment agent for denture base lining material according to the present invention is to be applied to adhesion of a (meth) acrylate-based material as a lining material, a radical-polymerizable monomer is used as the pretreatment agent. It is more preferable to add a monomer.
The addition of the radical-polymerizable monomer increases the initial adhesive strength, reduces the uneven adhesion, and further improves the aesthetic appearance of the surplus adhesive-coated surface.

The type of radical-polymerizable monomer is not particularly limited as long as it is a radical-polymerizable monomer.
A methacrylate-based polymerizable monomer is preferably used.
Specific examples of such radically polymerizable monomers include monofunctional radical polymerization of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, acetylacetoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, etc. Monomer; ethylene glycol dimethacrylate,
Bifunctional radically polymerizable monomers such as diethylene glycol dimethacrylate, triethylene glycol trimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and 1,9-nonanediol dimethacrylate; trimethylolpropane Trifunctional radical polymerizable monomers such as trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate and trimethylolmethane trimethacrylate; tetrafunctional radical polymerizable monomers such as tetramethylolethane tetramethacrylate and pentaerythritol tetramethacrylate. Etc.

The amount of these radical-polymerizable monomers to be blended is 0.1 to 100 parts by weight per 100 parts by weight of the dioxolane compound and the solvent for mixing which is added if necessary. It is preferably used in the range of parts. Further, the radical-polymerizable monomer may be used in combination with the above-mentioned polymer.

The pretreatment agent for a denture base lining material of the present invention may contain additives such as colorants and fragrances within a range that does not impair the effects of the present invention.

The method for preparing the pretreatment agent for a denture base lining material of the present invention is not particularly limited, and if there are additional components other than the dioxolane compound, they can be prepared by weighing and mixing the components. The method of use is not particularly limited, but generally, the pretreatment agent of the present invention is thinly applied with a brush or brush on the oral mucosa side of the denture base exposed with a stamp bar or the like, and after drying. The denture backing material may be placed, shaped, and then cured. The pretreatment agent for a denture base lining material of the present invention exhibits a particularly high effect in the case of a (meth) acrylate-based denture base.

The general form of denture base lining material is as follows: A paste having an appropriate viscosity is piled up on the denture base, in the gypsum model for the indirect lining method, and in the oral cavity for the direct lining method. After shaping into a shape conforming to the oral mucosa surface, curing is performed.
The curing mechanism is generally based on a chemical reaction mechanism and a photochemical reaction mechanism, but its mode is different depending on the difference of the mechanism. A backing material for a direct backing method that cures by a chemical reaction mechanism starts to cure when all components are mixed. Therefore, it is common to store the components in several portions so that curing does not begin and mix them at the time of use. There are various separate storage formats at this time,
For example, in the case of a (meth) acrylate-based backing material, a powder component containing a synthetic resin powder and a radical polymerization initiator such as an organic peroxide in a predetermined ratio, a radical polymerization monomer and a tertiary amine. A mode in which a liquid component in which a polymerization initiation auxiliary agent such as a compound is blended in a predetermined ratio is housed and stored in separate containers; a paste component in which a synthetic resin powder and a polymerization initiator are dissolved in a radical polymerizable monomer In general, the paste component in which the synthetic resin powder and the polymerization initiation aid are dissolved in the radical-polymerizable monomer is housed in another container and stored. In the case of a silicone-based backing material, a paste component made of a silicone compound having a hydrosilyl group and a paste component made of a silicone compound having a vinyl group and a hydrosilylation reaction catalyst such as chloroplatinic acid are used. It is common to store in a separate container for storage. The chemical reaction-curing backing material for the indirect backing method and the backing material that cures by the photochemical reaction mechanism may be stored in any form, but a powder liquid type or a paste type is preferably used. It is preferable to use the storage container for these lining materials and the storage container for the pretreatment agent for denture base lining material of the present invention as a kit. In this case,
It is preferable to combine the pretreatment material with a material containing the above-mentioned various additives depending on whether the backing material is a (meth) acrylate type or a silicone type. With such a kit, it is possible to perform a series of operations on the chair side from pretreatment of the denture base to lining, and it is also possible to line up with other pretreatment agents such as pretreatment agents for dentin. It is possible to prevent misuse due to an incorrect combination with a material.

[0068]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

The high molecular weight polymers and polymerizable monomers used in Examples and Comparative Examples are as follows.

(A) Polymer PMMA: polymethylmethacrylate (Mw = 500,00)
0) PEMA: polyethylmethacrylate (Mw = 500,00)
0) P (MMA-EMA): copolymer with methylmethacrylate-ethylmethacrylate {Mw = 500,000, MMA / EMA
Molar ratio = 30/70} (b) Polymerizable monomer 3G: triethylene glycol dimethacrylate TMPT: trimethylolpropane trimethacrylate TMMT: tetramethylolmethane tetramethacrylate (c) polysiloxane compound DMS-M20H20:

[0071]

[Chemical 12]

(KF9901, manufactured by Shin-Etsu Chemical) DHS-P30H30:

[0073]

[Chemical 13]

(HPM502 manufactured by Asmax) ME-91:

[0075]

[Chemical 14]

(TOSHIBA SILICONE, ME-91) A9723:

[0077]

[Chemical 15]

(Toshiba Silicone, XC86-A972
3) TSL9586

[0079]

[Chemical 16]

(TOSHIBA SILICONE, TSL9586) MTVDS

[0081]

[Chemical 17]

(SIM 6487.8, manufactured by Azumax) (C) Reactive siloxane-modified (meth) acrylic polymer The polymers used are shown below.

[0083]

[Chemical 18]

These polymers were obtained by synthesizing by the method shown below. The polymer and the polymer are produced by a method according to the description of JP-A-7-70246 and JP-A-7-76611.

Polymer synthesis method 25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 0.26 g of azobisisobutyronitrile and 30 ml of toluene were placed in a flask and heated to 70 ° C. while stirring with nitrogen bubbling. Thus, a copolymer (weight average molecular weight: 120,000) having a copolymerization ratio of methyl methacrylate and allyl methacrylate of 50: 1 (molar ratio) was obtained.

In the flask, 27.7 g of hydrogen siloxane compound DMS-M20H20 and 3 toluene were added.
Then, 0.33 g of a platinum / divinylsiloxane complex solution adjusted to 100 ml of platinum and 1000 ppm of platinum was added, and the mixture was heated to 80 ° C. and stirred while bubbling nitrogen. A solution prepared by dissolving 5 g of a copolymer (weight average molecular weight 120,000) of methyl methacrylate and allyl methacrylate having a copolymerization ratio of 50: 1 (molar ratio) synthesized by the above method in 100 ml of toluene is added dropwise over 1 hour. Then, after completion of dropping, the mixture is heated and stirred for another 6 hours to remove toluene under reduced pressure, and then excess DMS-M20H20 is added with a methanol / ethanol mixed solvent.
Was washed, filtered and dried to obtain a copolymer. The weight average molecular weight of the obtained polymer is a polystyrene standard,
It was 180,000.

25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 0.31 g of azobisisobutyronitrile and 30 ml of toluene were placed in a flask for synthesizing the copolymer, and the mixture was heated and stirred at 70 ° C. while bubbling nitrogen. As a result, a copolymer (weight average molecular weight 100,000) having a copolymerization ratio of methyl methacrylate and allyl methacrylate of 50: 1 (molar ratio) was obtained.

Hydrogen siloxane compound DHS-
P20H20 and a copolymer of methyl methacrylate and allyl methacrylate synthesized by the above method with a copolymerization ratio of 50: 1 (molar ratio) was used to perform the synthesis in the same manner as the synthesis of the copolymer. , A copolymer was obtained. The weight average molecular weight of the obtained polymer was 200,000 based on polystyrene standard.

25 g of methyl methacrylate, 2.3 g of the reactive siloxane compound MTVDS, 0.26 g of azobisisobutyronitrile and 30 ml of toluene were placed in a flask for synthesizing the copolymer, and 30 ml of toluene was bubbled with nitrogen at 80 ° C. for 5 hours. Obtained by heating and stirring. The weight average molecular weight of the obtained copolymer was 100,000 based on polystyrene standard. In addition, the ¹ H-NMR spectrum of the obtained product shows Si-
Proton absorption of CH ₃ group, proton absorption from acrylic chain at 0.5 to 2.0 ppm, COO-C at 3.5 ppm
Proton absorption of H ₃ group: Si-at 5.5-6.1 ppm
Absorption of the double bond protons of the CH = CH ₂ group had appeared.

(1) Evaluation of Adhesiveness of (Meth) Acrylate-Based Denture Base Lining Material A denture base material made of polymethylmethacrylate resin (manufactured by GC, trade name: Akron) was used to form a resin plate (10 ×).
10 × 2 mm) and made the resin plate water-resistant abrasive paper # 3
After polishing with 20 and immersing in water for 24 hours, the adhesive strength was compared with that of a denture base model.

The Akron plate was taken out of the water, and the surface water was wiped off with a Kimwipe (made by Crecia) to remove the surface water. A pretreatment agent for a denture backing material was applied to the polished surface of the Akron plate with a brush, allowed to dry as it was, and a double-sided tape having a hole with a diameter of 3 mm was attached to define the adhesion area. After that, the dough-like material obtained by kneading the powder and liquid of the (meth) acrylate-based resin backing material (Tokuyama Corp., Tokusori Base First Type) at the specified kneading ratio was used to fill the holes in the double-sided tape. After mounting the plugging amount, a methylmethacrylate resin attachment was quickly pressure-bonded, and subsequently, the sample was cured at 37 ° C. under a wet condition to obtain an adhesive sample. Then, the adhesive sample was immersed in water at 37 ° C., and strength was measured 24 hours later. The strength was measured by setting the sample in a tensile tester (manufactured by Shimadzu Corporation, Autograph) and measuring the tensile strength at a crosshead speed of 1 mm / min. In the test, ten measurements were made for one item, and the average value was used to evaluate the strength.

(2) Evaluation of Adhesiveness of Silicone Denture Base Lining Material The adhesive strength evaluation shown in Examples and Comparative Examples was carried out according to the method described below. Two types of pastes A and B shown below were prepared as addition type silicone rubbers for evaluation of adhesive strength to prepare silicone-based denture base lining materials. These abbreviations and structures are shown below. These are kneaded in the same amount and hardened to form a silicone rubber. The tensile strength of the silicone rubber prepared here is about 2.0 MPa. A paste: ・ ME91: 50 parts by mass ・ A9723: 50 parts by mass ・ Platinum / vinyl siloxane complex solution (platinum 1000 pp
m, Pt / V2) 0.3 parts by mass, polymethylsilsesquioxane fine particles (particle size 3 μm,
Obtained by hydrolyzing methyltrimethoxysilane) 40 parts by mass B paste: ・ ME91: 50 parts by mass ・ A9723: 50 parts by mass ・ DMS-M20H20: 2 parts by mass ・ TSL9586: 7 parts by mass Surface No. 800 The prepared pretreatment agent is applied to an acrylic plate (Akron, GC) that has been water-polished with the above water-resistant abrasive paper.
Equal amounts of both A and B pastes were taken, kneaded well, and placed on an acrylic plate coated with a pretreatment agent. This at 25 ℃
After allowing to stand for 10 minutes to cure the paste, the adhesiveness was evaluated.

After curing, an attempt was made to peel from the interface between the acrylic plate and the cured silicone rubber with a spatula, and the state of breakage at that time was observed and evaluated. The evaluation was performed on five samples, and the evaluation points were from A to D according to the following judgments.
It was evaluated in four stages. A: Cohesive failure of all silicone rubber (adhesive strength> 2.0M
Pa) B: Mixed failure of cohesive failure and interfacial failure (adhesive strength of approximately 2.0)
MPa) C: Interface failure (adhesive strength <2.0 MPa) D: Interface failure that peels off very easily (adhesive strength almost 0MP)
a) (3) Evaluation of adhesion durability An adhesion test sample prepared by the same method as in (1) and (2) above was subjected to a thermal shock tester (manufactured by Thomas Kagaku Kikai Co., Ltd.).
Was used to carry out a thermal cycle test at 4 ° C. and 60 ° C. In the case of a test sample of methacrylate-based denture base lining material after the thermal shock was applied 10,000 times, a strength test was conducted by a tensile tester, and the strength was compared with that before the thermal shock was applied. The durability was evaluated. Also, in the case of silicone-based denture base lining material, 4 ° C and 60 ° C as well.
The heat cycle test was performed 10000 times, and the adhesive strength of the sample after the heat cycle test was evaluated by the above method.

Example 1 Using 1,3-dioxolane as a pretreatment agent, an adhesion test between a Toxorri base and an Akron plate was conducted. 1,3-
When dioxolane was used as the pretreatment agent, the odor was less than that of ethyl acetate and toluene, and the pretreatment could be performed without discomfort. Regarding the adhesiveness,
Initial adhesion strength of 11.5MPa, which is an index of adhesion durability 1
The adhesive strength after applying 0000 thermal shocks was 9.8 MPa, which was almost the same as that when methylene chloride was used as a pretreatment agent.

[0095]

[Table 1]

Examples 2 to 4 Evaluations were performed in the same manner as in Example 1 except that the type of dioxolane compound was changed as the pretreatment agent. Table 1 shows the types of dioxolane compounds used and the evaluation results.

Examples 5 to 7 Evaluations were performed in the same manner as in Example 1 except that 3 parts by mass of the high molecular weight polymer was added to 100 parts by mass of 1,3-dioxolane as a pretreatment agent. The type of high molecular polymer used,
The evaluation results are shown in Table 1.

Examples 8 to 10 Evaluations were performed in the same manner as in Example 1 except that 3 parts by mass of the polymerizable monomer was added to 100 parts by mass of 1,3-dioxolane as a pretreatment agent. The type of polymerizable monomer used,
The evaluation results are shown in Table 1.

Examples 11 to 13 In the same manner as in Example 1 except that 3 parts by mass of a high molecular polymer and 3 parts by mass of a polymerizable monomer were added to 100 parts by mass of 1,3-dioxolane as a pretreatment agent. An evaluation was made. Table 1 shows the types of the high molecular polymer and the polymerizable monomer used and the evaluation results.

Comparative Example 1 An adhesion test between a Toxori base and an Akron plate was conducted without pretreatment. As a result, the initial adhesive strength was 6.9 MPa,
The adhesive durability was 2.5 MPa, the initial adhesiveness was low, and the adhesiveness was almost lost by applying thermal shock.

Comparative Example 2 Evaluation was carried out in the same manner as in Example 1 except that ethyl acetate was used as the pretreatment agent. As a result, the initial adhesive strength is 8.8MP
a, Adhesion durability was 4.2 MPa, and the adhesive strength was low and the effect was insufficient as compared with the case of using the dioxolane compound of the present invention. In addition, there was a peculiar strong odor when the pretreatment agent was dried.

Reference Example 1 Evaluation was carried out in the same manner as in Example 1 except that methylene chloride which was a halogen-based organic solvent was used as a pretreatment agent. As a result, the initial adhesive strength was 12.5 MPa and the adhesive durability was 10.
It was 1 MPa.

As is apparent from Table 1 above, each Example which is the result when the pretreatment material of the present invention using the dioxolane compound is used is Comparative Example 1 which is the result when the pretreatment agent is not used. It was possible to obtain a higher initial adhesive strength as compared with Comparative Example 2, which is the result when ethyl acetate was used. The odor was also lower than that of ethyl acetate.

Further, by incorporating a high molecular weight polymer, the adhesion durability was further improved, and by incorporating a polymerizable monomer, the initial adhesive strength was further improved. Further, as is clear from the results of Examples 1 to 4, the pretreatment agent of the present invention using the dioxolane compound is comparable to Reference Example 1 using methylene chloride, which is a halogen-based solvent that has been conventionally used. It is a pretreatment agent with no performance.

Example 14 As a pretreatment agent, 1.5 parts by mass of a copolymer as a polymer modified with silicone having a reactive functional group was added and mixed with 100 parts by mass of 1,3-dioxolane. Then, a pretreatment agent of the present invention in a solution form was prepared.

Using the prepared adhesive, the adhesiveness between the above-mentioned silicone-based denture base lining material and the acrylic plate was evaluated. The results are shown in Table 2, and both had good initial adhesive strength and adhesive durability, and had little odor.

[0107]

[Table 2]

Examples 15 to 21 and Comparative Examples 3 to 6 Initial adhesion and adhesion durability were the same as in Example 14 except that pretreatment agents for denture base lining materials were prepared with the compositions shown in Table 2. The sex was evaluated.

Reference Example 2 A sample was prepared and evaluated in the same manner as in Example 14 except that methylene chloride was used instead of the dioxolane compound. The evaluation results are shown in Table 2.

As shown in Table 2 above, when the pretreatment agent of the present invention using a dioxolane compound is used, both initial adhesiveness and adhesive durability are excellent, and
The odor was also lower than that of ethyl acetate, acetone and ethyl methyl ketone.

On the other hand, as shown in Comparative Examples 3 to 6, when another solvent such as ethyl acetate was used, the initial adhesiveness was high, but the adhesiveness was significantly reduced after the thermal shock test. From these results, it can be understood that the pretreatment agent of the present invention is extremely excellent. Further, in this case, the adhesion durability was higher than that of Reference Example 2 using methylene chloride.

From these results, when the backing was performed using the dioxolane compound as a pretreatment agent, low odor was obtained without using a halogen-based compound which has a problem in terms of environmental load and harmfulness. It has been clarified that the pretreatment agent has an adhesive ability equal to or higher than that of the halogen-based compound.

[0113]

EFFECTS OF THE INVENTION A pretreatment agent for a denture base lining material that uses a halogen-free organic compound that is more safe than chlorine-based organic compounds, and also has an initial adhesiveness between the denture base and the lining material, The adhesion durability is remarkably higher than that using ethyl acetate, acetone, etc., and is equal to or higher than that using methylene chloride. Furthermore, it has the feature of low odor.

Continued front page    (72) Inventor Toshio Kawaguchi             1-1 Mikagecho, Tokuyama City, Yamaguchi Prefecture             In Kuyama F-term (reference) 4C089 AA03 AA08 AA12 BC02 BD04                       BE11

Claims (6)

[Claims] 1. The following general formula (1): (In the formula, R ^{1 to} R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) A pretreatment agent for a denture base lining material, which comprises a dioxolane compound. 2. A high molecular weight polymer 0.0 soluble in the dioxolane compound with respect to 100 parts by mass of the dioxolane compound.
The pretreatment agent for a denture base lining material according to claim 1, which comprises 5 to 20 parts by mass. 3. The pretreatment agent for a denture base lining material according to claim 2, wherein the high molecular polymer is a (meth) acrylate polymer. 4. All or part of the high molecular polymer is CH =
The pretreatment agent for a denture base lining material according to claim 2, which is a high-molecular polymer modified with siloxane having a CH ₂ group or a SiH group. 5. A pretreatment for a denture base relining material according to claim 2, which comprises 0.1 to 100 parts by mass of a polymerizable monomer with respect to 100 parts by mass of a dioxolane compound. Agent. 6. A kit for lining a denture base comprising the pretreatment agent according to any one of claims 1 to 5 and a lining material.