JP2017141211A - Mucosa regulating material for dental use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mucosa regulating material in which operability and handling in malaxation are high, a layer can be formed on a mucous membrane surface of a denture base with sufficient thickness, thickness is kept for a long time, and powder materials and liquid materials, which has high tear strength and can be used for a long time, are kneaded.SOLUTION: The present invention relates to the mucosa regulating material for dental use comprising a radical-polymerizable monomer represented by general formula (1).SELECTED DRAWING: None

Description

  The present invention relates to a dental mucosal preparation used for a denture wearing patient having deformation or inflammation of the oral mucosa in dental treatment.

  It is known that when a denture user has used a denture for a long period of time, the shape of the oral cavity gradually changes due to the absorption of the alveolar bone forming the ridge. Due to the change in the shape of the oral cavity, the compatibility between the denture basement mucosa and the oral mucosa deteriorates, and the denture becomes unstable. If such dentures continue to be used as they are, non-uniform pressure is applied to the mucosa below the denture base, causing ulcers and inflammation in the mucosa and causing pain due to occlusal pressure.

  As described above, if the compatibility between the denture basement mucosa and oral mucosa deteriorates, adapt the denture basement mucosa and oral mucosa by creating a new denture or lining the denture in use. It is necessary to restore sex.

  However, since the oral mucosa in which significant ulcers and inflammation have occurred is in an extremely unstable state, it is necessary to wait for the oral mucosa to be in a healthy state before making or denying a new denture.

  The material used in such a case is a dental mucosa adjusting material (hereinafter, also simply referred to as “mucosal adjusting material”). That is, the dental mucosa-adjusting material is a therapeutic material that is used while lining the mucosal surface of the denture base in use until the form and color tone of the mucosa under the denture base are restored to a normal state. That is, it is a soft polymer material used for the submucosal surface of the denture base in order to release the distortion and indentation of the mucosa of the denture base and to mark the functional form corresponding to the pressure displacement of each part.

  The mucosa adjusting material that kneads the powder and liquid at the time of use becomes a paste with high fluidity immediately after kneading. The paste exhibits viscoelasticity when the liquid component in the paste penetrates into the powder. While the paste is fluid, the paste is placed on the mucosal surface of the denture base, inserted into the oral cavity, and shaped in the oral cavity.

  The period of use of the mucosa preparation material is one week to several weeks until the oral mucosa is restored to a healthy state. For that purpose, the mucosa-adjusting material is a microscopic material that is flexible and conforms to changes in the shape of the oral mucosa while being held on the mucosal surface without being pushed out between the denture and the oral mucosa during occlusion. Deformation must be possible.

  More specifically, lining ulcers and inflammation of the oral mucosa while relieving pain by restoring the compatibility between the denture and the oral mucosa by lining the mucosal surface of the denture with a poor fit to the mucosal conditioning material Wait for it to disappear gradually. As ulcers and inflammation of the oral mucosa gradually disappear, the morphology of the oral mucosa also recovers to the original state over time. At this time, the mucous membrane adjusting material needs to be plastically deformed in accordance with the change in the shape of the oral mucosa. Because, when the mucosa adjusting material does not deform following the shape change as described above, the compatibility between the mucosa adjusting material and the oral mucosa is lost as the oral mucosa recovers, This is because it causes re-pain.

  Patent Document 1 discloses a mucosa-adjusting material comprising an acrylic or methacrylic (hereinafter abbreviated as “(meth) acrylic”) non-crosslinked polymer and a phthalic acid plasticizer. Patent Document 2 discloses a mucosa-adjusting material comprising a (meth) acrylic non-crosslinked polymer, a phthalic acid plasticizer, and an organic solvent. In these mucosa-adjusting materials, the plasticizer elutes within a short period of time, and the viscoelasticity is lost over time and becomes hard, and cannot be used for a long period of time.

  Patent Document 3 discloses a liquid material containing a (meth) acrylic non-crosslinked polymer and a polymerization initiator, a phthalic acid-based or sebacic acid-based plasticizer, a (meth) acrylic monomer, and an organic solvent. A mucosa-adjusting material is disclosed. Since this mucosa adjusting material is partially polymerized after kneading, elution of the plasticizer is suppressed, but the mucosa adjusting material after polymerization becomes hard and difficult to use over a long period of time. In addition, when a (meth) acrylic monomer that has sufficient strength to be used for a long period of time is blended, the proportion of the plasticizer is relatively reduced and sufficient flexibility cannot be obtained. It is difficult to achieve both durability.

  Patent Documents 4 and 5 disclose a mucosa-adjusting material comprising a (meth) acrylic non-crosslinked polymer, a liquid polymer, and an organic solvent. This mucosa-adjusting material suppresses the elution of the plasticizer from the mucosa-adjusting material by using a liquid polymer as the plasticizer, but the durability is not sufficient.

  On the other hand, (meth) acrylate polymerizable monomers are used in dental materials such as dental curable compositions or dental adhesives, and in particular, cured products with excellent mechanical strength can be obtained (meth). Examples of the acrylate polymerizable monomer include a polymerizable monomer having a bisphenol A skeleton represented by bisphenol A diglycidyl di (meth) acrylate (Bis-GMA) exemplified in Patent Documents 6 and 7, and Patent Document 8 , 9 are known polymerizable monomers having a biphenyl skeleton.

  From the viewpoint of facilitating handling of the polymerizable monomer, the polymerizable monomer is advantageously a low-viscosity liquid or liquid substance in a room temperature environment. For example, in general, in many cases, the polymerizable monomer is often used as a mixed composition mixed with other components according to various uses, rather than being used alone. In such a case, if the polymerizable monomer is a low-viscosity liquid or liquid substance, blending with other components is very easy.

  However, Bis-GMA exemplified in Patent Documents 6 and 7 has a very high viscosity in a room temperature environment, and the polymerizable monomer exemplified in Patent Document 8 is a solid in a room temperature environment, Inferior in mechanical strength. Moreover, although the polymerizable monomer illustrated in Patent Document 9 has a relatively low viscosity, it is also inferior in mechanical strength.

JP-A-03-020204 Japanese Patent Laid-Open No. 02-297358 JP 2002-104913 A JP 2006-225281 A JP 2009-294362 A JP 2007-126417 A JP 09-157124 A JP 05-170705 A JP-A 63-297344

  The problem to be solved by the present invention is a mucosal preparation that kneads a powder material and a liquid material, and has high operability and handleability immediately after kneading and sufficient thickness of the denture base. An object of the present invention is to provide a mucosa-adjusting material that can be layered on the mucosal surface, has a thickness maintained for a long period of time, has a high tear strength, and can be used for a long period of time.

  As a result of intensive studies on the above problems, the inventors of the present invention have a specific polymerizability that is excellent in mechanical strength of a cured product and is low in viscosity and excellent in handleability even in a room temperature environment, represented by the following general formula (1). It has been found that the above problems can be solved by blending a monomer and a polymerization initiator, and the present invention has been completed.

上記課題を解決する本発明は以下に記載するものである。
〔１〕ｉ）可塑剤、及び一般式（１）に示すラジカル重合性単量体を含む液材、
及びｉｉ）（メタ）アクリル系非架橋ポリマーを含む粉材
とに分割して包装、保存されており、重合開始剤がｉ）液材及びｉｉ）粉材の双方、又はいずれか一方に含まれ、使用時には両材を混和したペーストとして用いる歯科用粘膜調整材。

The present invention for solving the above problems is described below.
[1] i) a liquid material comprising a plasticizer and a radical polymerizable monomer represented by the general formula (1),
And ii) a powder material containing a (meth) acrylic non-crosslinked polymer and packaged and stored, and a polymerization initiator is included in i) liquid material and ii) powder material or both. A dental mucosa-adjusting material used as a paste in which both materials are mixed.

[In the general formula (1), X represents a divalent group, Ar ¹ and Ar ² each represent an aromatic group having any valence selected from divalent to tetravalent, L ¹ and L ² may be the same or different, and each of L ¹ and L ² has a main chain atom number in the range of 2 to 60, and any value selected from divalent to tetravalent Each represents a hydrocarbon group having a number, which may be the same or different, and R ¹ and R ² each represent hydrogen or a methyl group; Moreover, m1, m2, n1, and n2 are each an integer selected from the range of 1-3. ]
[2] The dental mucosa preparation material according to [1], wherein the divalent X group in the radical polymerizable monomer is —O—.
[3] In the radical polymerizable monomer, the hydrocarbon group L ¹ having a main chain atom number in the range of 2 to 60 and any valence selected from divalent to tetravalent. The dental mucosa preparation material according to [1] or [2], wherein at least one of L ² and L ² is a radical polymerizable monomer containing a hydroxyl group.
[4] The dental mucosa preparation material according to any one of [1] to [3], wherein the radical polymerizable monomer is represented by the following general formula (2).

[In the general formula (2), X, L ¹ , L ² , R ¹ and R ² are the same as those shown in the general formula (1). ]
[5] The dental mucosa-adjusting material according to any one of [1] to [4], wherein the plasticizer is a liquid polymer having a mass average molecular weight in the range of 1000 to 10,000.
[6] The dental mucosa preparation material according to any one of [1] to [5], wherein the glass transition temperature of the (meth) acrylic non-crosslinked polymer is in the range of 0 to 60 ° C.
[7] ii) The dental mucosa preparation material according to any one of [1] to [6], wherein the powder material further contains an inorganic powder.
[8] The dental mucosa preparation material according to any one of [1] to [7], wherein the liquid material further contains a water-soluble organic solvent.

  The mucosa-adjusting material of the present invention has a low initial viscosity and excellent operability, and the elution of the plasticizer is suppressed and the durability (tear strength) is improved, so that it can be used for a long time while maintaining the softness. it can.

  Hereinafter, the present invention will be described in detail.

The dental mucosa-adjusting material (hereinafter also referred to as “the present mucosa-adjusting material”) of the present invention comprises i) a liquid material and ii) a powder material described below. This mucous membrane adjusting material is used by kneading i) liquid material and ii) powder material at the time of use.
i) Liquid material The liquid material contains a plasticizer and a radical polymerizable monomer represented by the following general formula (1).

[In the general formula (1), X represents a divalent group, Ar ¹ and Ar ² each represent an aromatic group having any valence selected from divalent to tetravalent, L ¹ and L ² may be the same or different, and each of L ¹ and L ² has a main chain atom number in the range of 2 to 60, and any value selected from divalent to tetravalent Each represents a hydrocarbon group having a number, which may be the same or different, and R ¹ and R ² each represent hydrogen or a methyl group; Moreover, m1, m2, n1, and n2 are each an integer selected from the range of 1-3. ]
Examples of the plasticizer include phthalic acid esters such as ethyl phthalate, butyl phthalate and octyl phthalate, sebacic acid esters such as ethyl sebacate, butyl sebacate and octyl sebacate, and liquid polymers described below. Of these, it is particularly preferable to use a liquid polymer. By using a liquid polymer, the flexibility of the dental mucosa-adjusting material after curing can be increased, and the flexibility is maintained for a long time when used in the oral cavity. Moreover, since a liquid polymer does not transfer to a denture base, the denture base is not damaged.

  The liquid polymer is preferably a water-insoluble liquid polymer having a mass average molecular weight of 1000 to 10,000 and a ratio of oligomers having a molecular weight of 500 or less to 10% by mass or less.

  In the present invention, the term “liquid” means liquid at room temperature to oral temperature, that is, 18 to 40 ° C. If it is not liquid within this temperature range, it may not be kneaded with the powder material, the mucosa adjusting material will not become a paste, or appropriate viscoelasticity may not be obtained.

  In the present invention, water-insoluble means that the solubility in water at 37 ° C., which is an average oral temperature, is 5% by mass or less. In the present invention, the solubility of the liquid polymer in water is preferably 3% by mass or less, and particularly preferably 1% by mass or less.

  When the liquid polymer has a mass average molecular weight of less than 1000 or a water-soluble plasticizer, the plasticizer elutes in the oral cavity when the mucosa preparation is used, and the viscoelasticity and flexibility of the mucosa preparation are lost in a short time. May be. When the mass average molecular weight of the liquid polymer exceeds 10,000, it may not be possible to impart appropriate flexibility, and it may be difficult to use as a mucosa adjusting material. The mass average molecular weight of the liquid polymer having good kneading properties is 1200 to 7000, and more preferably 1500 to 5000.

  In general, as the molecular weight of a liquid polymer increases, the compatibility with other components tends to decrease. Therefore, the molecular weight distribution of the liquid polymer is preferably less than 10% by mass, more preferably less than 5% by mass, where the molecular weight exceeds 10,000. In addition, a liquid polymer having a molecular weight of 500 or less is likely to elute in the oral cavity and easily migrates to the denture base, which may make it difficult to use for a long time. Therefore, the molecular weight distribution of the liquid polymer is preferably less than 10% by mass and more preferably less than 7% by mass in the portion having a molecular weight of 500 or less.

  The material of the liquid polymer is not particularly limited, but has good affinity with the (meth) acrylic non-crosslinked polymer particles blended in the powder material, and is excellent in kneading properties and various physical properties of the resulting paste. A (meth) acrylic liquid polymer is preferred. Among these, a (meth) acrylic acid ester-based (hereinafter also referred to as “(meth) acrylate-based”) polymer is particularly preferable because a liquid polymer having a molecular weight within the above range can be easily obtained.

  The (meth) acrylic liquid polymer blended in the liquid material is a) (meth) acrylic blended in the powder material in that the average molecular weight is limited to the above range and the property is liquid. Different from non-crosslinked polymers.

  A liquid polymer having a mass average molecular weight of 1000 to 10,000 can be obtained by a general polymerization reaction. That is, a liquid polymer having a desired average molecular weight can be obtained by controlling the blending ratio of the monomer and the polymerization initiator. Ionic polymerization or living radical polymerization, which can easily control the average molecular weight, is preferably used. In particular, according to anionic polymerization, a polymer close to monodispersion having a very sharp molecular weight distribution and a weight average molecular weight / number average molecular weight of 2 or less can be obtained. Moreover, it is easy to reduce the content of the polymer having a molecular weight of 500 or less.

  For example, a (meth) acrylic monomer or a (meth) acrylic monomer and another monomer copolymerizable with the (meth) acrylic monomer are polymerized so as to have a mass average molecular weight of 1000 to 10,000. That's fine.

  As the (meth) acrylic monomer, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) which is an ester of an alcohol having 1 to 10 carbon atoms and (meth) acrylic acid. Acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl ( Examples include (meth) acrylate monomers such as (meth) acrylate and methoxypropyl (meth) acrylate.

  Among them, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, glycidyl ( A homopolymer obtained by polymerizing one kind selected from (meth) acrylate or a copolymer obtained by polymerizing two or more kinds of these monomers is particularly preferably used. These liquid polymers have good compatibility with the (meth) acrylic non-crosslinked polymer used for the powder material.

  Examples of other monomers copolymerizable with (meth) acrylate monomers include vinyl acetate and styrene. In this case, it is possible to use a copolymer obtained by copolymerizing one or two or more (meth) acrylate monomers and one or more other copolymerizable monomers. In view of solubility and swelling, the monomer unit derived from the (meth) acrylate monomer is preferably contained in an amount of 50 mol% or more, more preferably 80 mol% or more.

  Specific examples of preferable liquid polymers include polyethyl (meth) acrylate, polypropyl (meth) acrylate, polyisopropyl (meth) acrylate, polybutyl (meth) acrylate, poly {2-ethylhexyl (meth) acrylate}, poly {ethyl ( (Meth) acrylate-butyl (meth) acrylate}, poly {ethyl (meth) acrylate-2-ethylhexyl (meth) acrylate}, poly {ethyl (meth) acrylate-methoxyethyl (meth) acrylate}, poly {ethyl (meth) Acrylate-glycidyl (meth) acrylate}, poly {butyl (meth) acrylate-methoxyethyl (meth) acrylate}, poly {butyl (meth) acrylate-glycidyl (meth) acrylate}.

  The liquid polymer may be used in combination of two or more polymers having different molecular weight distributions. Furthermore, you may use together 2 or more types of liquid polymers from which the kind and ratio of the monomer unit which comprise a polymer differ.

  The radical polymerizable monomer contained in the liquid material is represented by the following general formula (1).

Here, in the general formula (1), X represents a divalent group, Ar ¹ and Ar ² each represent an aromatic group having any valence selected from divalent to tetravalent, Each may be the same or different, and each of L ¹ and L ² is any one selected from divalent to tetravalent in which the number of main chain atoms is in the range of 2 to 60 Each represents a hydrocarbon group having a valence, which may be the same or different, and R ¹ and R ² each represent hydrogen or a methyl group; Moreover, m1, m2, n1, and n2 are each an integer selected from the range of 1-3. The polymerizable monomer represented by the general formula (1) may be an isomer mixture including two or more isomers.

The polymerizable monomer of this embodiment is excellent in the mechanical strength of the cured product, and is excellent in handleability because it has a low viscosity even in a room temperature environment. The reason why such an effect is obtained is not clear, but the present inventors presume as follows. First, the reason why the cured product is excellent in mechanical strength is considered to be because it has a structure (Ar ¹ -X-Ar ² ) containing an aromatic group having high rigidity at the center of the molecule.

The reason why the viscosity is low even in a room temperature environment is as follows. First, as the structure of the center of the molecule, the aromatic group Ar ¹ and the aromatic group Ar ² are directly bonded via a σ bond, such as a biphenyl structure. Instead of a bonded structure (Ar ¹ -Ar ² ), a structure (Ar ¹ -X-Ar ² ) in which an aromatic group Ar ¹ and an aromatic group Ar ² are bonded via a divalent group X was adopted. Can be mentioned. The structure (Ar ¹ -Ar ² ) is easy to crystallize due to the high symmetry of the molecular structure, but in the structure (Ar ¹ -X-Ar ² ) in which a divalent group X is further introduced into such a structure, the molecular structure This increases the flexibility of the resin and lowers the symmetry. As a result, it is considered that the crystallinity is lowered and the viscosity is lowered. In addition to this, in the polymerizable monomer of the present embodiment, it is considered that the ester bond connected to the aromatic groups Ar ¹ and Ar ² greatly contributes to the decrease in viscosity.

Further, as described above, the structure (Ar ¹ -X-Ar ² ) is more flexible in molecular structure than the structure (Ar ¹ -Ar ² ). For this reason, the polymerizable monomer of the present embodiment is harder to be brittle and has excellent bending strength as compared with the polymerizable monomer having the structure (Ar ¹ -Ar ² ) introduced in the center of the molecule. .

Next, the polymerizable monomer represented by the general formula (1) will be described in detail. First, in the general formula (1), Ar ¹ and Ar ² each represent an aromatic group having any valence selected from divalent to tetravalent, and may be the same or different from each other. Good.

Specific examples of the aromatic groups Ar ¹ and Ar ² include divalent to tetravalent benzene represented by the following structural formulas Ar-a1 to Ar-a3, and divalent to 4 represented by the following structural formulas Ar-a4 to Ar-a6. Valent naphthalene, or divalent to tetravalent anthelane represented by the following structural formulas Ar-a7 to Ar-a9. In these structural formulas, the bond is provided on any carbon of the benzene ring that constitutes the aromatic groups Ar ¹ and Ar ² (excluding the carbon that forms the condensed part of the benzene ring and the benzene ring). Can do. For example, in the case of the structural formula Ar-a1 (divalent benzene), two bonds can be provided at either the ortho position, the meta position, or the para position.

Note that the valence of the aromatic group Ar ¹ is determined according to the number of m1 and is represented by m1 + 1. Similarly, the valence of the aromatic group Ar ² is determined according to the number of m2 and is represented by m2 + 1.

In addition, the aromatic groups Ar ¹ and Ar ² may each have a substituent, and in this case, the hydrogen of the benzene ring constituting the aromatic groups Ar ¹ and Ar ² is replaced with another substituent. Can do. The substituents of the aromatic groups Ar ¹ and Ar ² are not particularly limited as long as they do not contain a reactive group (that is, an acryl group or a methacryl group) shown on the left side of the general formula (1) at their ends. Those having a total number (number of atoms) of atoms constituting the substituent in the range of 1 to 60 can be appropriately selected. Specific examples include a monovalent hydrocarbon group having 1 to 20 carbon atoms, -COOR ³ , -OR ³ , a halogen group, an amino group, a nitro group, and a carboxyl group. R ³ is the same as the monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a linear or branched hydrocarbon group such as a methyl group or an ethyl group, an alicyclic hydrocarbon group such as a cyclohexyl group, a phenyl group, and a monovalent group. And heterocyclic groups such as furan.

X represents a divalent group, specifically, the number of atoms in the main chain that bridges the aromatic group Ar ¹ and the aromatic group Ar ² as exemplified by the following structural formulas X-1 to X-13 Is a divalent group of 1 to 3.

The number of atoms in the main chain of the divalent group X is more preferably 1 or 2, and most preferably 1. The divalent group X is an electron donating group capable of donating electrons to a benzoate structure (electron withdrawing group) composed of an aromatic group Ar ¹ (or Ar ² ) and an ester bond connected thereto. It is preferable. Examples of such an electron-donating divalent group X include —O—, —CH ₂ —, —CH (R ⁵ ) —, and —S—, and among these, —O— or —CH ₂ —. Is more preferable, and -O- is particularly preferable. Here, R ⁵ is an alkyl group having 1 to 6 carbon atoms. The electron-donating divalent group X can have a resonance structure as exemplified in the following resonance structural formula, so that the polarity at the center of the molecule is relatively high. For this reason, it is possible to further improve the affinity with a hydrophilic material having a high polarity. As a result, the compatibility with the hydrophilic material is improved, and the affinity / adhesion to the hydrophilic surface is improved. It becomes easy. In the resonance structural formula below, the divalent group X is —O— and the aromatic groups Ar ¹ and Ar ² are phenylene groups (however, two bonds are provided at the para position). It shows about the molecule | numerator center part of the polymerizable monomer of this embodiment.

L ¹ and L ² each represent a hydrocarbon group having a main chain number of 2 to 60 and a valence selected from divalent to tetravalent, each being the same Or different. The number of atoms in the main chain is preferably in the range of 2 to 12, more preferably in the range of 2 to 10, more preferably in the range of 2 to 6, and particularly preferably in the range of 2 to 3. In particular, when the number of atoms in the main chain is in the range of 2 to 3, it becomes easy to further increase the bending strength of the cured product.

  The atoms constituting the main chain are basically composed of carbon atoms, and all atoms may be carbon atoms, but some of the carbon atoms constituting the main chain may be replaced with heteroatoms. it can. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. When the main chain contains an oxygen atom as a hetero atom, an ether bond or an ester bond can be introduced into the main chain. The number of heteroatoms that can be introduced into the main chain is preferably about half or less of the number of atoms in the main chain. When the number of atoms in the main chain is 2, the number of heteroatoms that can be introduced into the main chain is one. .

In addition, a substituent may be bonded to at least one of the atoms constituting the main chain (usually a carbon atom). Examples of such a substituent include an alkyl group having 1 to 3 carbon atoms such as a methyl group, a hydroxyl group, a monovalent hydrocarbon group having a hydroxyl group, halogen, —COOR ⁴ , and —OR ⁴ . R ⁴ is the same as the alkyl group having 1 to 3 carbon atoms. The monovalent hydrocarbon group having a hydroxyl group preferably has 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms. Specific examples of the monovalent hydrocarbon group having a hydroxyl group include —CH ₂ OH, —CH ₂ CH ₂ OH, —CH (CH ₃ ) OH, and the like.

When it is desired to improve the compatibility with the hydrophilic material or to improve the affinity for the hydrophilic surface, at least one of L ¹ and L ² contains a hydroxyl group, in other words, L ¹ and L ^In at least one of ² , the substituent is preferably a hydroxyl group and / or a monovalent hydrocarbon group having a hydroxyl group. The number of hydroxyl groups contained in each of L ¹ and L ² may be at least one or more, but typically is preferably one. Further, it is more preferable that one hydroxyl group is contained in each of L ¹ and L ^{2. In} this case, if m 1 and m 2 = 1, two hydroxyl groups are contained in the molecule.

In general, a compound having a plurality of hydroxyl groups in a molecule forms an intermolecular hydrogen bond, and as a result, the viscosity tends to increase. Therefore, when the polymerizable monomer of this embodiment has a hydroxyl group in the molecule, the viscosity tends to increase. However, it is more preferable that a hydroxyl group is present in the vicinity of the ester bond directly bonded to the aromatic groups Ar ¹ and Ar ² because the increase in viscosity is relatively suppressed. Here, the "case where the hydroxyl group is present in the vicinity of the ester bonds", specifically, when any one or both of L ¹ and L ² having a hydroxyl group, primary of L ¹ and L ² having a hydroxyl group The number of chain atoms means a range of 2 to 10, and the number of main chain atoms is particularly preferably a range of 2 to 3. Although the reason why the above-described effect is obtained is not clear, the present inventors I guess as follows.

When a hydroxyl group is present in the vicinity of the ester bond directly bonded to the aromatic groups Ar ¹ and Ar ² , the hydrogen of the hydroxyl group present in the divalent groups L ¹ and L ² is aromatic as shown in the structural formula shown below. It is expected that an intramolecular hydrogen bond is easily formed between the oxygen of the carbonyl group of the ester bond directly bonded to the group Ar ¹ and Ar ² . In the general formula (1), the structural formulas exemplified below are Ar ¹ , Ar ² = phenylene group, X = —O—, L ¹ , L ² = —CH ₂ CH (OH) CH ₂ —. , R ¹ , R ² = methyl group, m1, m2, n1 and n2 = 1.

  That is, when an intramolecular hydrogen bond is formed, formation of an intermolecular hydrogen bond is suppressed. For this reason, in the polymerizable monomer of the present embodiment, when the hydroxyl group is not contained in the molecule, the viscosity increases when the hydroxyl group is contained in the molecule, but the conventional molecule has a hydroxyl group. It is suppressed that the viscosity is remarkably increased to the same level as that of a polymerizable monomer having a viscosity (such as Bis-GMA).

In addition to this, when the intramolecular hydrogen bond is formed, compared to the case where the intermolecular hydrogen bond is not formed as a reference, the benzene rings constituting the aromatic groups Ar ¹ and Ar ² and Distortion occurs in the benzoate structure consisting of the ester bond to be bonded, and the symmetry of the molecular structure at the center of the molecule is lowered. Therefore, it is considered that the crystallinity of the molecule is lowered and the significant increase in viscosity is further suppressed. In addition, since formation of an intramolecular hydrogen bond weakens the bond between molecule | numerators, there exists a possibility of causing the fall of the mechanical strength of hardened | cured material. However, when the polymerizable monomer of the present embodiment has a hydroxyl group in the vicinity of the ester bond directly bonded to the aromatic groups Ar ¹ and Ar ² , the hydroxyl group is more precisely the molecule than the intermolecular hydrogen bond. The degree of contribution to the internal hydrogen bond is considered to be relatively higher, and it is also considered that it contributes to the formation of a slow hydrogen bond network between molecules. Further, when a plurality of hydroxyl groups are contained in the molecule as in the case where both L ¹ and L ² have a hydroxyl group, a hydrogen bond network having a high density between the molecules is easily formed. In this case, it is considered that the mechanical strength of the cured product can be further increased as compared with the polymerizable monomer of the present embodiment having no hydroxyl group in the molecule.

Specific examples of L ¹ and L ² include the following structural formulas Lb1 to Lb14 when n1 and n2 = 1 (when L ¹ and L ² are divalent hydrocarbon groups). it can. Of the two bonds shown in these structural formulas, the bond marked with * means a bond bonded to an oxygen atom of an ester bond constituting the benzoate structure at the center of the molecule. Here, in the following structural formulas Lb1 to Lb14, a represents an integer selected from the range of 1 to 11, b represents an integer selected from the range of 1 to 19, and c represents 0 to 11 Represents an integer selected from the range of 0, d represents an integer selected from the range of 0 to 5, e represents an integer selected from the range of 2 to 5, and f is selected from the range of 1 to 6 Represents an integer. Note that the values of a to f are preferably selected in the range where the number of atoms of the main chain is 12 or less in the structural formulas Lb1 to Lb14.

On the other hand, when n1 and n2 = 2 (when L ¹ and L ² are trivalent hydrocarbon groups), in structural formulas Lb1 to Lb14, among the carbon atoms constituting the main chain, * The carbon atom farthest from the carbon atom having the attached bond has two bonds. Further, when n1 and n2 = 3 (when L ¹ and L ² are tetravalent hydrocarbon groups), structural formulas Lb1 to Lb2, Lb6 to Lb8, Lbb10 to L In -b14, among the carbon atoms constituting the main chain, the carbon atom located farthest from the carbon atom having a bond marked with * has three bonds.

The polymerizable monomer represented by the general formula (1) is particularly preferably a polymerizable monomer represented by the following general formula (2). Note that the general formula (2) has a structure in which m1, m2, n1, n2 = 1, Ar ¹ , Ar ² = —C ₆ H ₄ — (structural formula Ar-a1) in the general formula (1). Is shown.

Moreover, it is preferable that the polymerizable monomer of this embodiment is a polymerizable monomer shown by following General formula (3). Here, in the general formula (3), X is the same as that shown in the general formula (1), and Ar ¹ and Ar ² have the general formula (1) except that the valence can take only two valences. And L ³ and L ⁴ each represents a divalent hydrocarbon group having 1 to 8 atoms in the main chain, and each may be the same or different. R ³ and R ⁴ each represent hydrogen or a methyl group. Further, j is 0, 1 or 2, k is 0, 1 or 2, and j + k = 2. In general formula (3) are the compounds of formula ^{(1), m1, m2,} n1, n2 = 1, L 1 = -L 3 -CH (OH) CH 2 - or _-CH (CH 2 OH) -L ^{4 -, L 2 = -L 3} -CH (OH) CH 2 - or ^{_{-CH (CH 2 OH) -L 4}} -, R 1 corresponds to ^{R 3} or ^{R 4, R 2} is ^{R 3} or ^{R 4} The structure (bifunctional structure) in the case of corresponding to is shown. In the general formula (3), the groups shown in parentheses on the left and right sides can be bonded to any of the two bonds of the group shown in the center; —Ar ¹ —X—Ar ² —. That is, depending on the values of j and k, the group shown in the left parenthesis in the general formula (3) may be bonded to both sides of the group shown in the center, or the right side in the general formula (3) In some cases, groups shown in parentheses are bonded to both sides of the group shown in the center.

In L ³ and L ⁴ , the atoms constituting the main chain are basically composed of carbon atoms, and all atoms may be carbon atoms, but some of the carbon atoms constituting the main chain Can be replaced by a heteroatom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. When the main chain contains an oxygen atom as a hetero atom, an ether bond or an ester bond can be introduced into the main chain. The number of heteroatoms that can be introduced into the main chain is preferably one or two. However, when the number of atoms in the main chain is 2, the number of heteroatoms that can be introduced into the main chain is one.

In L ³ and L ⁴ , the number of atoms in the main chain may be 1 to 8, more preferably 1 to 5, still more preferably 1 to 3, and most preferably 1. Specific examples of L ³ and L ⁴ include an alkylene group having 1 to 8 carbon atoms in the main chain such as a methylene group, an ethylene group, an n-propylene group, and an n-butylene group, and a main chain of the alkylene group. Examples include a group in which a part or all of them are substituted with an ether bond or an ester bond (provided that the number of atoms in the main chain of the alkylene group is 2 or more).

  Examples of the combination (j, k) of the values j and k shown in the general formula (3) include (2, 0), (1, 1) and (0, 2). Among these, the polymerizable monomer (1, 1) and (0, 2) are more preferable from the viewpoint that suppression of decomposition of body molecules can be expected.

  Further, in the polymerizable monomer of the present embodiment, the combination (j, k) of the values j and k shown in the general formula (3) is (2, 0), (1, 1) and (0, 2). It is preferable that any two or more structural isomers selected from the group consisting of: When the polymerizable monomer contains two or more kinds of structural isomers with respect to the combination of (j, k) shown in the general formula (3), the mechanical strength of the cured product and the storage stability are well balanced. It becomes easy to improve. In this case, the average value k of all polymerizable monomer molecules is in the range of 0.05 or more and less than 2.0 (in other words, the average value of the value j is greater than 0 and less than or equal to 1.95). Is preferred. Further, the lower limit of the average value of the value k is preferably 0.1 or more, the upper limit of the average value of the value k is more preferably 1.7 or less, and further preferably 1.5 or less. , 0.4 or less is particularly preferable. In order to improve the mechanical strength and the storage stability of the cured product in a well-balanced manner, the average value k is 0.05 or more even when the value k = 2 (state not including the structural isomer). It is suitable as in the case where the range is less than 0. However, the mechanical strength in the initial state without a certain storage period is higher in the state containing two or more kinds of structural isomers than in the value k = 2 (state not containing the structural isomer). be able to. In this respect, it is more advantageous that the average value of the values k is smaller as long as the average value of the values k is not less than 0.05.

  The polymerizable monomer of this embodiment can be synthesized by appropriately combining known starting materials and known synthetic reaction methods, and the production method thereof is not particularly limited. For example, when producing a polymerizable monomer represented by the general formula (3), a production method including at least a reaction step of reacting a compound represented by the following general formula (4) with a compound represented by the following general formula (5) May be used. In this case, a polymerizable monomer containing two or more types of structural isomers selected from the group consisting of compounds represented by the following general formulas (6) to (8) can be produced.

Here, in the general formulas (4) to (8), X, Ar ¹ and Ar ² are the same as those shown in the general formula (3), and L ⁵ has 1 to 7 atoms in the main chain. Represents a divalent hydrocarbon group. P is 0 or 1. Here, the average value of the values k, in other words, the abundance ratio of the structural isomers represented by the general formulas (6) to (8) can be easily adjusted by appropriately selecting the synthesis conditions. In addition, by performing a purification treatment after synthesis as necessary, the average value of the values k (the abundance ratio of the structural isomers represented by the general formulas (6) to (8)) is adjusted so as to be closer to the desired value. May be.

In L ⁵ represented by the general formulas (4) to (8), the atoms constituting the main chain are basically composed of carbon atoms, and all the atoms may be carbon atoms, but the main chain is composed. It is also possible to replace some of the carbon atoms to be replaced with heteroatoms. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. When the main chain contains an oxygen atom as a hetero atom, an ether bond or an ester bond can be introduced into the main chain. The number of heteroatoms that can be introduced into the main chain is preferably one or two. However, when the number of atoms in the main chain is 2, the number of heteroatoms that can be introduced into the main chain is one.

Further, the number of atoms in the main chain in L ⁵ may be 1 to 7, but 1 to 4 is preferable, and 1 to 2 is more preferable. Specific examples of L ³ and L ⁴ include an alkylene group having 1 to 7 carbon atoms in the main chain such as a methylene group, an ethylene group, an n-propylene group, and an n-butylene group, and a main chain of the alkylene group. Examples thereof include a group in which a part or all of them are substituted with an ether bond or an ester bond (provided that the number of atoms in the main chain of the alkylene group is 2 or more).

In the general formula (6), each L ⁵ may be the same or different. The same applies to the general formulas (7) and (8). In the case where it is assumed that different respective L ⁵ each other, as a compound represented by the general formula (5) used for the synthesis, can be used which L ⁵ different two or more compounds. Further, p is preferably 0.

  If necessary, after obtaining a polymerizable monomer containing two or more kinds of structural isomers by the above-described production method, a polymerizable monomer substantially free of structural isomers (for example, a general formula Only the polymerizable monomer shown in (6) may be isolated and purified. However, the polymerizable monomer obtained by isolation and purification is compared with the polymerizable monomer containing two or more types of structural isomers before the isolation and purification treatment, and the mechanical strength and the storage stability of the cured product. It tends to be inferior in terms of compatibility with sex. In addition, when the polymerizable monomer is produced, further isolation and purification treatment is required, which tends to be disadvantageous in terms of cost. Therefore, it is preferable to omit the isolation and purification treatment from these viewpoints.

  The blending amount of the radical polymerizable monomer is preferably 1 part by mass or more with respect to 100 parts by mass of the plasticizer from the viewpoint of improving the tear strength. From the viewpoint of application, it is preferably within 30 parts by mass, and particularly preferably 3 to 20 parts by mass, which can obtain particularly good operational feeling and durability.

  The liquid material in the mucosa-adjusting material of the present invention may be blended with a radically polymerizable monomer other than the polymerizable monomer represented by the general formula (1) as long as the effects of the present invention are not hindered. As the radically polymerizable monomer, known ones that can be generally used for dental materials can be used. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, β-methacryloyloxyethyl pro Monofunctional (meth) acrylic polymerizable monomers such as pionate, 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl Propane, 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane), And these Acrylates corresponding to tacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) Acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-hydroxyethyl (meth) acrylate Bifunctional (meth) acrylic polymerizable monomers such as 2-hydroxypropyl (meth) acrylate and 3-chloro-2-hydroxypropyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol And trifunctional (meth) acrylic polymerizable monomers such as ethanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylolmethane tri (meth) acrylate.

  The compounding amount of the polymerizable monomer is 30 masses with respect to 100 parts by mass of the plasticizer, from the viewpoint of imparting flexibility as a mucosa-adjusting material, with the polymerizable monomer represented by the general formula (1). It is preferable that it is within a part. Moreover, it is preferable that ratio of the polymerizable monomer shown to General formula (1) and the said other polymerizable monomer is 8/2-10/0 from a viewpoint of tear strength improvement.

  The liquid material in the mucosa-adjusting material of the present invention preferably further contains a water-soluble organic solvent. By mix | blending a water-soluble organic solvent, the fluidity | liquidity of a liquid material improves and it becomes easy to handle. Moreover, the operativity at the time of mixing and kneading a powder material and a liquid material improves. Furthermore, the initial fluidity of the composition after mixing the powder material and the liquid material is improved. This is because by blending a water-soluble organic solvent, the plasticizer is easy to penetrate the plasticizer when the (meth) acrylic non-crosslinked polymer blended in the powder material is dissolved or swollen. This is considered to improve the familiarity. In addition, since the mucosa-adjusting material of the present invention is used in the oral cavity for a relatively long period of time, a water-insoluble organic solvent that is harmful to the human body is not preferable.

  Examples of the water-soluble organic solvent include alcohols such as ethanol, isopropyl alcohol and isobutyl alcohol, ketones such as methyl ethyl ketone and acetone, and amines such as diethanolamine and triethanolamine. In particular, alcohols such as ethanol and isopropyl alcohol are preferable, and ethanol is particularly preferable from the viewpoints of harm to the living body and odor.

The amount of the water-soluble organic solvent is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 1 part by mass or more from the viewpoint of improving the operability with respect to 100 parts by mass of the plasticizer, It is preferably 30 parts by mass or less from the viewpoint of the handleability of the composition and the change in physical properties of the composition after the organic solvent is eluted from the composition, and particularly 3 to 20 parts by mass that can obtain a good operational feeling. It is particularly preferred.
ii) Powder material The powder material comprises a (meth) acrylic non-crosslinked polymer.

  As the (meth) acrylic non-crosslinked polymer, a homopolymer obtained by homopolymerizing a polymerizable monomer having an acrylic group or a methacrylic group as a polymerizable group (hereinafter referred to as a (meth) acrylic monomer), 2 Copolymers obtained by copolymerizing more than one kind of (meth) acrylic monomers, and (meth) acrylic monomers and polymerizable monomers other than (meth) acrylic monomers Copolymer (wherein the proportion of monomer units based on the (meth) acrylic monomer is 50 mol% or more). The (meth) acrylic polymer has a good familiarity with the (meth) acrylic denture base and easily obtains appropriate viscoelasticity.

  In addition, the present mucosa-adjusting material requires that a composition obtained by kneading a powder material and a liquid material becomes a paste having an appropriate viscosity. Therefore, the (meth) acrylic non-crosslinked polymer needs to be a non-crosslinked polymer that can be dissolved in the liquid material component.

  Homopolymers obtained by homopolymerizing (meth) acrylic monomers include poly (methyl methacrylate), poly (iso-propyl methacrylate), poly (t-butyl methacrylate), poly (phenyl methacrylate), poly (phenyl methacrylate), Dicyclopentenyl acrylate), poly (isobornyl acrylate), poly (cyclohexyl methacrylate), poly (ethyl methacrylate), poly (urethane acrylate), poly (benzyl acrylate), poly (4-butoxycarbonylphenyl acrylate), poly { 3-chloro-2,2-bis (chloromethyl) propyl acrylate}, poly (2-chlorophenyl acrylate), poly (4-chlorophenyl acrylate), poly (4-methoxyphenyl acrylate), poly (2,4-di Rolophenyl acrylate), poly (cyclohexyl acrylate), poly (cyclododecyl acrylate), poly (2-methoxycarbonylphenyl acrylate), poly (3-methoxycarbonylphenyl acrylate), poly (2-ethoxycarbonylphenyl acrylate), poly ( 3-ethoxycarbonylphenyl acrylate), poly (4-ethoxycarbonylphenyl acrylate), poly (heptafluoro-2-propyl acrylate), poly (hexadecyl acrylate), polymethyl acrylate, polyneopentyl acrylate, polyphenyl acrylate, poly (M-tolyl acrylate), poly (o-tolyl acrylate), poly (p-tolyl acrylate), poly (N-butylacrylamide), poly (pro Methacrylate), poly (n-butyl methacrylate), poly (i-butyl methacrylate), poly (neopentyl methacrylate), poly (cyclohexyl methacrylate), poly (hexadecyl methacrylate), poly (octadecyl methacrylate), poly (3- Oxabutyl methacrylate), poly (benzyl methacrylate), poly (2-t-butylaminoethyl methacrylate), poly (butylbutoxycarbonyl methacrylate), poly (1H, 1H-heptafluorobutyl methacrylate), poly (1H, 1H, 5H) -Octafluoropentyl methacrylate) and poly (1H, 1H, 7H-dodecafluoroheptyl methacrylate).

  Copolymers for copolymerizing only (meth) acrylic monomers include poly (methyl methacrylate-ethyl methacrylate), poly (t-butyl methacrylate-n-butyl methacrylate), poly (iso-propyl methacrylate-butyl acrylate), Poly (ethyl methacrylate-butyl methacrylate), poly (methyl methacrylate-butyl acrylate), poly (urethane acrylate-methyl acrylate), poly (methyl methacrylate-n-butyl acrylate), poly (ethyl methacrylate-n-butyl acrylate), poly (Propyl methacrylate-n-butyl acrylate), poly (methyl methacrylate-n-butyl methacrylate), poly (ethyl methacrylate-n-butyl methacrylate), poly ( B pills methacrylate -n- butyl methacrylate), poly (i-butyl methacrylate -n- butyl methacrylate) are exemplified.

  Copolymers for copolymerizing (meth) acrylic monomers with other polymerizable monomers include poly (styrene-methyl methacrylate), poly (styrene-ethyl methacrylate) and poly (styrene-n-butyl methacrylate). Illustrated.

  These copolymers (copolymers) may be any copolymer such as a random copolymer, an alternating copolymer, and a block copolymer as long as the above conditions are satisfied.

  Among the above-mentioned (meth) acrylic non-crosslinked polymers, it is composed of (meth) acrylic acid ester monomer units such as ethyl methacrylate and n-butyl methacrylate in terms of solubility and ease of handling. Non-crosslinked polymers are preferred.

  The (meth) acrylic non-crosslinked polymer preferably has a Tg (glass transition temperature) of 0 to 60 ° C, particularly preferably 10 to 50 ° C. The polymer having a Tg of less than 0 ° C aggregates the non-crosslinked polymer particles extremely strongly during the storage of the powder material at room temperature (about 18 to 35 ° C, which is the environmental temperature at which the mucosa-adjusting material before use is stored). Therefore, the composition obtained by kneading with the liquid material may not become a paste. If the polymer has a Tg of more than 60 ° C., the composition obtained by kneading with the liquid material becomes hard, and it may not be possible to impart adequate flexibility to the mucosa-adjusting material. In the present invention, moderate flexibility means that the Shore A hardness is 20 or less.

  The shape and size of the (meth) acrylic non-crosslinked polymer is not particularly limited as long as it is in powder form, but is easy to handle as a powder material (fluidity, cohesiveness), mixed with a liquid material, In view of kneadability and the like, the volume average particle diameter is preferably 0.1 to 100 μm, more preferably 1 to 90 μm, and particularly preferably 5 to 50 μm.

  The average molecular weight and molecular weight distribution of the (meth) acrylic non-crosslinked polymer is not particularly limited as long as it is in a powder form, but is easy to synthesize or obtain, and operability of a paste obtained by kneading with a liquid material. In view of the above, those having a mass average molecular weight of 20,000 to 5,000,000 are preferable, and those having a mass average molecular weight of 50,000 to 1,000,000 are more preferable.

  In the present specification, the mass average molecular weight refers to a standard polystyrene equivalent molecular weight measured by gel permeation chromatography (hereinafter sometimes abbreviated as “GPC”).

  The (meth) acrylic non-crosslinked polymer blended in the mucosa-adjusting material is composed of two or more kinds of powdery polymers having different types and ratios of monomers constituting the polymer, average molecular weight and molecular weight distribution, and average particle diameter. May be used in combination.

  Furthermore, in addition to the above components, an inorganic powder may be added to ii) the powder material in the dental mucosa preparation material of the present invention as long as the effects of the present invention are not hindered. By adding inorganic powder, the viscoelasticity of the final composition can be adjusted. That is, the final hardness is increased by blending the inorganic powder. Therefore, when the hardness of the obtained mucous membrane adjusting material becomes too soft, an inorganic powder can be added to obtain an appropriate desired hardness. In general, the blending amount of the inorganic powder is desirably 5 parts by mass or less, more preferably 2 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic non-crosslinked polymer.

  The kind of such inorganic powder is not particularly limited, and can be selected from reinforcing materials and fillers added to general resin compositions. Specifically, calcium carbonate, calcium sulfate, magnesium oxide, barium carbonate, barium sulfate, titanium oxide, potassium titanate, barium titanate, aluminum hydroxide, magnesium hydroxide, meteorite powder, glass powder, diatomaceous earth, silica, Examples include calcium silicate, talc, alumina, bentonite, zeolite, kaolin clay, mica, and quartz glass. Silica and alumina are preferably used from the viewpoints of ease of handling, compatibility with liquid materials, solubility in saliva (elution), and the like.

  The particle size of these inorganic powders is not particularly limited, but those having a volume average particle size of 1 μm or less are preferred, and those having a particle size of 0.1 μm or less are more preferred from the viewpoints of storage stability and kneadability. Considering the availability of such inorganic particles, fumed silica is most preferable. Of course, you may use together 2 or more types of inorganic powder from which a material, an average particle diameter, etc. differ. The powder material may be blended in any amount as long as the cross-linked polymer is a small amount that does not affect the effects of the present invention.

  As a polymerization initiator contained in i) liquid material and / or ii) powder material, or i), a polymerizable monomer represented by the general formula (1) contained in the liquid material is polymerized and cured. Any known polymerization initiator can be used as long as it can be used. For example, radical polymerization initiators used in the dental field include chemical polymerization initiators (ordinary temperature redox initiators), photopolymerization initiators, thermal polymerization initiators, etc. A polymerization initiator and / or a photopolymerization initiator are preferred.

  The chemical polymerization initiator is a polymerization initiator that is composed of two or more components and generates polymerization active species near room temperature by mixing all the components immediately before use. Such a chemical polymerization initiator is typically an organic peroxide / amine compound type.

  Typical organic peroxides used as such chemical polymerization initiators include ketone peroxide, peroxyketal, hydroperoxide, diaryl peroxide, peroxyester, diacyl peroxide, peroxydioxide. Specific examples include carbonates, such as methyl ethyl ketone peroxide, cyclohexanoperoxide, P-methane hydroperoxide, diisopropylbenzene peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, benzoyl peroxide, di- Examples thereof include n-propyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate and the like.

  Although the suitable amount of these organic peroxides varies depending on the type of organic peroxide used, it cannot be unconditionally limited, but is preferably based on 100 parts by mass of the polymerizable monomer represented by the general formula (1). Is in the range of 0.05-5 parts by mass, more preferably 0.1-3 parts by mass.

  In addition, known compounds are not particularly limited and used as the tertiary amine for generating radicals upon contact with these organic peroxides. Specific examples of suitably used tertiary amine compounds include N, N-dimethylaniline, N, N-diethylaniline, N, N-dipropylaniline, N, N-dibutylaniline, N-methyl, Anilines such as N-β-hydroxyethylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dipropyl-p-toluidine, N, N-dibutyl-p- Toluidines such as toluidine, p-tolyldiethanolamine, p-tolyldipropanolamine, N, N-dimethyl-anisidine, N, N-diethyl-p-anisidine, N, N-dipropyl-p-anisidine, N, N- Anisidines such as dibutyl-p-anisidine, morpholines such as N-phenylmorpholine and N-tolylmorpholine, bis (N, - dimethylaminophenyl) methane, bis (N, N-dimethylaminophenyl) ether. These amine compounds may be used as salts with organic acids such as hydrochloric acid, phosphoric acid, acetic acid and propionic acid. Among the above tertiary amine compounds, N, N-diethyl-p-toluidine, N, N-dipropyl-p-toluidine, p-tolyldiethanolamine, p from the viewpoint of high polymerization activity and low irritation and low odor. -Tolyldipropanolamine is preferably used.

  The amount of the tertiary amine compound used is preferably 0.1% by weight relative to 100 parts by weight of the polymerizable monomer represented by the general formula (1). It is 05-5 mass parts, More preferably, it is the range of 0.1-3 mass parts.

  Specific examples of the combination of the organic peroxide and the tertiary amine compound include BPO / N, N-diethyl-p-toluidine, BPO / N, N-dipropyl-p-toluidine. , BPO / p-tolyldiethanolamine, BPO / p-tolyldipropanolamine and the like. In particular, when long-term storage is required in a state where a tertiary amine compound is mixed with a radical polymerizable monomer, BPO / N, N-diethyl-p-toluidine, BPO / N are used from the viewpoint of storage stability. The combination of N, dipropyl-p-toluidine is most preferred.

  In addition to such a chemical polymerization initiator composed of an organic peroxide and an amine compound, a sulfinic acid such as benzenesulfinic acid, p-toluenesulfinic acid and its salt, or a barbituric acid-based initiator such as 5-butylbarbituric acid Even if an agent is added, it can be used without any problems.

  As the photopolymerization initiator, a known initiator system such as α-diketone-reducing agent, ketal-reducing agent, thioxanthone-reducing agent and the like is preferably used. Examples of A-diketones include camphorquinone, benzyl, 2,3-pentadione, and 3,4-heptadione. Examples of the ketal include benzyl dimethyl ketal, benzyl diethyl ketal, and benzyl (2-methoxyethyl ketal). Examples of thioxanthone include thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone. The reducing agent as one component of the photopolymerization initiator includes tertiary amines such as 2- (dimethylamino) ethyl methacrylate, ethyl 4-dimethylaminobenzoate and N-methyldiethanolamine, lauryl aldehyde, dimethylaminobenzaldehyde, terephthalate Examples include aldehydes such as aldehyde, 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid, and thiobenzoic acid.

  A suitable amount of these photopolymerization initiators varies depending on the type of photopolymerization initiator used, and thus cannot be unconditionally limited, but is preferably based on 100 parts by mass of the polymerizable monomer represented by the general formula (1). Is in the range of 0.05-5 parts by mass, more preferably 0.1-3 parts by mass.

  The organic peroxide and the tertiary amine compound are used separately for i) liquid material and ii) powder material, respectively, either of which may be used, and i) liquid from the viewpoint of handleability. It is preferable to mix an organic peroxide in the material and ii) a tertiary amine compound in the powder material. When a photopolymerization initiator is used, it may be used separately for i) liquid material and ii) powder material, or may be used for either one. Moreover, you may use together a chemical polymerization initiator and a photoinitiator.

  In the mucosa preparation material of the present invention, the mixing ratio of the powder material and the liquid material is not particularly limited, but the plastic compounded in the liquid material with respect to 100 parts by mass of the (meth) acrylic non-crosslinked polymer. The range which becomes 50-300 mass parts of an agent is preferable. Moreover, if there is a large difference in the ratio between the powder material and the liquid material, the paste may not be formed even if both are mixed. Therefore, it is preferable that the powder material and the liquid material are powder / liquid = 0.5 to 2.5 in mass ratio. From the viewpoint of easy measurement and mixing during use, the powder / liquid = mass ratio. More preferably, it is about 0.8 to 2.0. Further, the kneading of the powder material and the liquid material may be performed until both become a uniform paste, but it is usually uniformized in the range of 5 to 100 seconds.

  In addition to the above components, the dental mucosa preparation material of the present invention may contain coloring materials such as dyes and pigments, fragrances, antibacterial agents, antifungal agents, and the like, if necessary.

  EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples. The evaluation methods of various physical properties in each example and comparative example are as follows.

(1) Measuring method Tg of glass transition point (Tg) was measured using a differential scanning calorimeter (DSC6200 / Seiko Co., Ltd.). The initial temperature increase was continued at a rate of 10 ° C./min up to about 30 ° C. higher than the approximate Tg, where after holding for 5 minutes, the temperature was decreased at 50 ° C./min. Next, the temperature at the intersection of the three tangents obtained in the signal obtained by immediately raising the temperature was determined, and the intermediate temperature was defined as Tg.

(2) Measuring method of kneading time To a rubber cup in which the liquid material has been measured in advance, 1.1 mass times of the powder material is added to start the kneading, and the added powder material is uniform with the liquid material. It was kneaded with a spatula until it became a paste. The time from the start of kneading until a uniform paste was obtained was measured and used as the kneading time.

(3) Initial viscosity measurement method during kneading It was measured using a dynamic viscoelasticity measuring device CS rheometer “CVO120HR” (manufactured by Borin). Measurement was performed under the conditions of a measurement temperature (plate temperature) of 23 ° C. and a shore rate of 10 (1 / sec) using a 20 mm diameter and 1 ° cone. Kneading was carried out by the method described in (3) Measuring method of kneading time, and the viscosity after 30 seconds from the time (kneading time) when a uniform paste was obtained was measured. In addition, in order to have a sufficient margin for operation, it is desirable that the initial viscosity be suppressed to 300 Pas or less.

(4) Consistency measurement method
Measured based on JIS-T6519 (short-term elastic lining material for denture base). The measurement was carried out by the method described in (3) Method of measuring the kneading time, and 2 ml of the sample was weighed and placed on one glass plate. 30 seconds after the completion of mixing, another cover glass plate (100 g) was gently placed on the sample, and the sample was immediately placed in an incubator maintained at 37 ° C. 120 seconds after mixing was completed, a 1000 g weight was gently placed vertically on the cover glass plate, and after 60 seconds, the weight was removed. The length of the maximum part and the minimum part between the parallel tangents of the sample that spread 8 minutes after the end of mixing was measured, and the average value was obtained to obtain the consistency. The consistency at the time of this measurement is small (standard 60 or less) because the paste obtained by kneading the powder material and the liquid material is put on the denture base adhesive surface and inserted into the oral cavity is viscoelastic. Means that it is difficult to be pushed out even when the mounting pressure is applied.

(5) Measuring method of hardness The Shore A hardness which is a parameter | index of a softness | flexibility was measured based on JIS-K7215 (durometer type A). The measurement was performed when the mixture was allowed to stand overnight at 37 ° C after kneading and when it was immersed in water at 37 ° C for one month (hereinafter referred to as "initial hardness" and "hardness after one month", respectively). Say).

(6) Thickness change rate measurement method 30 × 30 × 2 mm on a square acrylic plate having a side of about 30 mm and a thickness of about 2 mm, prepared using a denture base resin material (“Acron” (manufactured by GC Corporation)) And then kneading by the method described in (2) Measuring method of kneading time, pouring a paste after 10 seconds from the time when a uniform paste was obtained, Welded with a single acrylic plate. After 30 minutes from the start of mixing, the mold was removed and immersed in water at 37 ° C. for 1 day, and then the thickness of the test piece was measured using a micrometer. The thickness obtained by subtracting the thickness of the two acrylic plates from the thickness of the test piece was defined as the thickness before the test of the mucosa adjusting material layer. After the thickness measurement, a repeated load test was performed under the following conditions using a fatigue tester “Electropulse” (manufactured by Instron).

<Test conditions>
Maximum load: 27kgf
Load: Load load frequency based on sine curve: 1 Hz
Number of repetitions: 2700 times Temperature: 37 ° C. (in water)
After the test, the thickness of the test piece was measured using a micrometer. The amount obtained by subtracting the thickness of the two acrylic plates from the thickness of the test piece was taken as the post-test thickness of the mucosa adjusting material layer, and the rate of change was determined by the following formula.
Thickness change rate of mucosa adjusting material layer [%] = (Thickness before test−Thickness after test) [mm] / 2 [mm] × 100
(7) Tear Strength Tested based on JIS K6252 “Vulcanized Rubber and Thermoplastic Rubber—How to Obtain Tear Strength”. An angle-shaped (thickness 2 mm) test piece was prepared, immersed in water at 37 ° C. overnight, and then autographed (AG-1 manufactured by Shimadzu Corporation) using a load cell capacity of 5 kgf and a crosshead speed of 10 mm / min. The stress was measured and the tear strength was calculated.

  The various compounds used in each example and comparative example are as follows.

1. Liquid Material Components Plasticizers in the liquid materials used in Examples and Comparative Examples are as shown in Table 1. These were obtained by the methods described in Production Examples 1 to 3 below.

(Production Example 1)
PBA-1: 3.0 ml (3.0 mmol) of a toluene solution (1.0 mol / l) of tri (n-butyl) aluminum was mixed with 40 ml of toluene and cooled to -78 ° C. To this was added 7.4 ml (7.4 mmol) of a toluene solution of t-butyllithium (1.0 mol / l), and after stirring for several minutes, 16.1 g (126 mmol) of butyl acrylate was added at a temperature in the reaction system. It was added with care not to go up. This reaction was performed in a standard Schlenk tube under a nitrogen atmosphere, and the reagent was transferred using a syringe. Toluene was refluxed over sodium and then distilled under a nitrogen atmosphere. Butyl acrylate was purified through a basic alumina column and a molecular sieves 4A column. After stirring for 24 hours, methanol was added to stop the reaction. After washing with a 50% aqueous methanol solution using a separatory funnel, it was vacuum dried at 120 ° C. to obtain 11.6 g of a colorless and transparent liquid compound (yield 72%). As a result of GPC measurement, the mass average molecular weight was 2000 (polystyrene conversion), Mw / Mn = 1.15, and 5% by mass of the molecular weight less than 500 was included.

(Production Example 2)
PBA-2: Tri (n-butyl) aluminum in toluene (1.0 mol / l) 1.0 ml (1.0 mmol), t-butyllithium in toluene (1.0 mol / l) 2.5 ml (2. 5 mmol) was synthesized in the same manner as in Production Example 3 to obtain 10.1 g of a colorless and transparent liquid compound (yield 63%). As a result of GPC measurement, the mass average molecular weight was 6000 (polystyrene conversion), Mw / Mn = 1.12, and the molecular weight less than 500 was less than 1% by mass.

(Production Example 3)
PPA: 3.0 ml (3.0 mmol) of a toluene solution (1.0 mol / l) of tri (n-butyl) aluminum was mixed with 40 ml of toluene and cooled to -78 ° C. To this was added 7.4 ml (7.4 mmol) of a toluene solution of t-butyllithium (1.0 mol / l), and after stirring for several minutes, 14.8 g (130 mmol) of propyl acrylate was added at a temperature in the reaction system. It was added with care not to go up. This reaction was performed in a standard Schlenk tube under a nitrogen atmosphere, and the reagent was transferred using a syringe. Toluene was refluxed over sodium and then distilled under a nitrogen atmosphere. Propyl acrylate was purified through a basic alumina column and a molecular sieves 4A column. After stirring for 24 hours, methanol was added to stop the reaction. After washing with a 50% aqueous methanol solution using a separatory funnel, it was vacuum dried at 120 ° C. to obtain 10.2 g of a colorless and transparent liquid compound (yield 69%). As a result of GPC measurement, the mass average molecular weight was 2000 (polystyrene conversion), Mw / Mn = 1.15, and 5% by mass of the molecular weight less than 500 was included.

  The radical polymerizable monomer represented by the general formula (1) in the liquid material used in the examples is as follows. These were obtained by the methods described in Production Examples 4 to 10 below.

4-DPEGMA is obtained as a mixture of the following compounds (a), (b), and (c), and the ratio is 65: 30: 5 in molar ratio. The values g and h shown together with the above structural formula are average values of the mixture of the compounds (a), (b) and (c). The values g and h shown together with the above structural formula and the structural formula shown below mean an average value, but in each molecule, the values of g and h can take an integer value of 0, 1 or 2. . Except for the case where the average value of the values g and h is 0 or 2, the structural formulas indicating the average values of the values g and h are two or three types with different combinations of integer values (g, h). It means a mixture of structural isomers. Further, in the general formula (3), when Ar ¹ = Ar ² = phenylene group, the value g is a value corresponding to the value j shown in the general formula (3), and the value h is the general formula (3 ) Is a value corresponding to the value k shown in FIG.

(Production Example 4)
<Synthesis of Acid Chloride (A)>
A first mixed solution of 25.3 g (0.096 mol) of 4,4′-diphenyl ether dicarboxylic acid, 0.85 g (0.012 mol) of dimethylformamide and 80 ml of toluene was prepared. A second mixed solution consisting of 58.4 g (0.46 mol) thionyl chloride and 20 ml of toluene was gradually added dropwise to the stirred first mixed solution at room temperature. The liquid obtained after completion of the dropwise addition was heated to 95 ° C. and refluxed for 3 hours. The yellow transparent liquid obtained after heating / refluxing is allowed to cool, and may be referred to as 4,4′-diphenyl ether dicarboxylic acid chloride (hereinafter referred to as “acid chloride (A)”) having the molecular structure shown below. There was obtained a toluene solution. Furthermore, this toluene solution was subjected to a rotary evaporator to remove toluene, thionyl chloride and hydrogen chloride at 40 ° C. to obtain 26.9 g (0.091 mol, yield 95%) of 4,4′-diphenyl ether dicarboxylic acid chloride solid. It was.
<Synthesis of 4-DPEHE>
A dispersion containing the acid chloride (A) was obtained by adding 120 ml of methylene chloride to 15.3 g (0.052 mol) of the acid chloride (A). A mixed solution of 16.9 g (0.13 mol) of 2-hydroxyethyl methacrylate, 7.7 g (0.13 mol) of triethylamine, 0.16 g (0.0013 mol) of 4-dimethylaminopyridine, 0.002 g of BHT and 10 ml of methylene chloride Was gradually added dropwise to the dispersion of the acid chloride (A) at −78 ° C. using a dropping funnel and further stirred for 5 hours. Water was added to the liquid obtained after dropping and stirring, and the solvent was removed using a rotary evaporator. The residue obtained after removal of the solvent was dissolved in 100 ml of toluene, washed with 0.5 N hydrochloric acid solution, washed with saturated brine, dried over magnesium sulfate, and filtered. The obtained filtrate was concentrated with a rotary evaporator, and then the concentrated solution was further vacuum-dried to obtain 4-DPEHE (yield 19.0 g, yield 76%, HPLC purity 97%). The data of ¹ H NMR spectrum of the obtained 4-DPEHE was as follows.
¹ H NMR δ 1.93 (s, 6H), 4.58 (t, 4H), 4.63 (t, 4H), 5.59 (s, 2H), 6.14 (s, 2H), 7. 06 (d, 4H), 7.96 (d, 4H)

(Production Example 5)
<Synthesis of 2-DPEHE>
Except for using 25.3 g (0.096 mol) of 2,2′-diphenyl ether dicarboxylic acid instead of 25.3 g of 4,4′-diphenyl ether dicarboxylic acid, the same method as in the case of synthesizing acid chloride (A) was used. 2,2′-diphenyl ether dicarboxylic acid chloride 27.8 g (0.094 mol, yield 98%) was obtained.

The same method as that for synthesizing 4-DPEHE except that 15.3 g (0.052 mol) of 2,2′-diphenyl ether dicarboxylic acid chloride was used instead of 15.3 g (0.052 mol) of acid chloride (A). Gave 2-DPEHE (19.5 g, yield 78%, HPLC purity 97%). The data of ¹ H NMR spectrum of the obtained 2-DPEHE were as follows.
¹ H NMR δ 1.93 (s, 6H), 4.54 (t, 4H), 4.62 (t, 4H), 5.58 (s, 2H), 6.16 (s, 2H), 7. 06 (d, 4H), 7.45 (d, 2H), 7.96 (d, 2H)

(Production Example 6)
<Synthesis of 4-DPEHH>
-Process 1
8.6 g (0.1 mol) of methacrylic acid, 23.6 g (0.2 mol) of 1,6-hexanediol, 0.86 g (0.005 mol) of p-toluenesulfonic acid, and 0.1 g of BHT as a polymerization inhibitor It put in the glass container, and it heated and stirred at 85 degreeC. Next, the heated and stirred reaction system was depressurized, and stirring was continued for 5 hours while removing moisture from the reaction system. Thereafter, the obtained liquid was cooled, purified using silica gel column chromatography, and concentrated to obtain 19.7 g of 6-hydroxyhexyl methacrylate (53% yield) and 16.0 g (43% yield).
-Process 2-
Next, while stirring a solution containing 3.0 g (0.01 mol) of acid chloride (A), 70 ml of methylene chloride and 0.001 g of di-tertbutylmethylphenol in another glass container, A solution of 4.1 g (0.022 mol) of 6-hydroxyhexyl methacrylate, 2.0 g (0.02 mol) of triethylamine and 0.025 g (0.0002 mol) of 4-dimethylaminopyridine in 10 ml of methylene chloride was prepared. The solution was slowly added dropwise over 1 hour. The solution obtained after completion of the dropwise addition was stirred at room temperature for 1 hour, water was added, and the solvent was removed using a rotary evaporator. The residue obtained after removal of the solvent was dissolved in 100 ml of toluene, washed with 0.5 N hydrochloric acid solution, washed with saturated brine, dried over magnesium sulfate, and filtered. The obtained filtrate was again concentrated with a rotary evaporator, and the concentrated solution was further vacuum-dried to obtain 4-DPEHH (yield 4.6 g, yield 78%, HPLC purity 98%). In addition, the data of ¹ H NMR spectrum of the obtained 4-DPEHH were as follows.
¹ H NMR δ 1.29 (m, 8H), 1.57 (t, 4H), 1.77 (t, 4H), 1.93 (s, 6H), 4.16 (t, 4H), 4. 22 (t, 4H), 5.58 (s, 2H), 6.14 (s, 2H), 7.04 (d, 4H), 7.96 (d, 4H)

(Production Example 7)
<Synthesis of 4-DPEUE>
While stirring a solution obtained by dissolving 50.0 g (0.8 mol) of ethylene glycol, 40.5 g (0.4 mol) of triethylamine, and 0.49 g (4 mol) of N, N-dimethylaminopyridine in 100 ml of methylene chloride, the mixture was stirred. And cooled to 0 ° C. Next, a solution obtained by dissolving 44.8 g (0.2 mol) of the acid chloride (A) in methylene chloride (200 ml) was slowly added dropwise to this solution over 2 hours. The solution obtained after the dropwise addition was further stirred for 1 hour, water was added, and the solvent was removed using a rotary evaporator. The residue obtained after removal of the solvent was dissolved in 100 ml of toluene, washed with 0.5 N hydrochloric acid solution, washed with saturated brine, dried over magnesium sulfate, and filtered. The obtained filtrate was concentrated again with a rotary evaporator, and then the concentrated solution was purified by silica gel column chromatography to obtain 41.6 g (yield 60%) of 4,4′-bis (2-hydroxyethoxycarbonyl) diphenyl ether. .

Into a solution obtained by dissolving 34.6 g (0.1 mol) of 4,4′-bis (2-hydroxyethoxycarbonyl) diphenyl ether and 3.2 g (5 mmol) of dibutyltin dilaurate in 100 ml of anhydrous dimethylformamide. Further, 39.8 g (0.2 mol) of 2- (2-methacryloyloxyethyloxy) ethyl isocyanate was added and stirred at room temperature for 3 hours. To the solution after stirring, 100 ml of methylene chloride was added, washed three times with distilled water using a separatory funnel, and the methylene chloride layer was dried using magnesium sulfate. After drying, magnesium sulfate was filtered off, the filtrate was concentrated on a rotary evaporator, and the concentrate was further vacuum-dried to obtain 4-DPEUE (yield 70.3 g, yield 95%, HPLC purity 96%). . In addition, the data of ¹ H NMR spectrum of the obtained 4-DPEUE were as follows.
¹ H NMR δ 1.93 (s, 6H), 3.10 (m, 4H), 3.66 (m, 8H), 4.33 (t, 4H), 4.54 (m, 8H), 5. 58 (s, 2H), 6.14 (s, 2H), 7.06 (d, 4H), 7.96 (d, 4H), 8.02 (s, 2H)

(Production Example 8)
<Synthesis of 4-DPEGMA>
12.8 g of glycidyl methacrylate (0.09 mol), 12.9 g (0.05 mol) of 4,4′-diphenyl ether dicarboxylic acid, 0.02 g (0.00009 mol) of benzyltriethylammonium chloride, 0.02 g of BHT ( 0.00009 mol) and 20 g of dimethylformamide were reacted at 100 ° C. for 4 hours. 40 ml of ethyl acetate was added to the liquid obtained by the reaction to make a uniform solution. Next, this solution was transferred to a separatory funnel, washed with 40 ml of 10 wt% aqueous potassium carbonate solution three times, and further washed three times with distilled water, and then the ethyl acetate layer was recovered. Thereafter, magnesium sulfate was added to the recovered ethyl acetate layer to remove water contained in the ethyl acetate layer. Subsequently, magnesium sulfate was filtered off from the ethyl acetate layer, and the filtrate was concentrated by a rotary evaporator to obtain a concentrate. This concentrate was further dried in vacuo to give 4-DPEGMA (22.8 g, 84% yield, 95% HPLC purity). The data of ¹ H NMR spectrum of the obtained 4-DPEGMA was as follows.
¹ H NMR δ 1.93 (s, 6H), 3.90 (d, 0.8H), 4.30 to 4.70 (m, 9.2H), 5.59 (s, 2H), 6.16 (S, 2H), 7.07 (d, 4H), 8.07 (d, 4H)

(Production Example 9)
<Synthesis of 4-DPSHE>
After dissolving 48.4 g (0.2 mol) of 4,4-diformyldiphenyl sulfide synthesized by the synthesis method described in JP-A-2005-154379 in 200 ml of t-butanol and 50 ml of water, phosphoric acid was dissolved. A reaction solution was prepared by adding 50 ml of an aqueous sodium hydrogen solution and 140 g (2 mol) of 2-methyl-2-butene, and further adding 36 g (0.4 mol) of sodium chlorite. Next, this reaction solution was stirred for 5 hours, and then the reaction solution was acidified with 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and then the precipitated solid was washed with water. The solid (compound) obtained after washing was vacuum-dried to obtain 4,4′-dicarboxydiphenyl sulfide (yield 45.5 g, yield 83%).

  Next, an acid chloride (A) was used except that 26.4 g (0.096 mol) of 4,4′-dicarboxydiphenyl sulfide was used instead of 25.3 g (0.096 mol) of 4,4′-diphenyl ether dicarboxylic acid. ), 28.4 g (0.091 mol) of 4,4′-diphenylsulfide dicarboxylic acid chloride was synthesized by the same method as in the synthesis method.

Subsequently, a method similar to the synthesis method of 4-DPEHE was conducted except that 16.1 g (0.052 mol) of 4,4′-diphenylsulfide dicarboxylic acid chloride was used instead of 15.3 g of acid chloride (A). -DPSHE (yield 18.9 g, yield 73%, HPLC purity 91%) was obtained. The data of ¹ H NMR spectrum of the obtained 4-DPSHE was as follows.
¹ H NMR δ 1.93 (s, 6H), 4.52 (t, 4H), 4.63 (t, 4H), 5.58 (s, 2H), 6.11 (s, 2H), 7. 30 (d, 4H), 7.81 (d, 4H)

(Production Example 10)
<Synthesis of 4-DPAHE>
Other than using 27.2 g (0.096 mol) of 2,2-bis (4-carboxyphenyl) propane synthesized by the synthesis method described in British Patent GB753384 instead of 25.3 g of 4,4′-diphenyl ether dicarboxylic acid Obtained 29.6 g (yield 96%) of 2,2-bis (4-chlorocarbonylphenyl) propane by a method similar to the method for synthesizing acid chloride (A).

Subsequently, it was the same as that of 4-DPEHE except that 16.7 g (0.052 mol) of 2,2′-bis (4-chlorocarbonylphenyl) propane was used instead of 15.3 g of acid chloride (A). By the method, 4-DPAHE (yield 19.3 g, yield 73%, HPLC purity 92%) was obtained. The obtained ¹ H NMR spectrum data of 4-DPAHE was as follows.
¹ H NMR δ 1.64 (s, 6H), 1.93 (s, 6H), 4.53 to 4.64 (m, 8H), 5.59 (s, 2H), 6.12 (s, 2H) ), 7.22 (d, 4H), 7.90 (d, 4H)

2. Powder Material Components Non-crosslinked polymers in the powder materials used in Examples and Comparative Examples are as shown in Table 3.

3. Polymerization initiator The polymerization initiators used in Examples and Comparative Examples are as follows.
BPO: benzoyl peroxide CQ: camphorquinone DEPT: N, N-diethyl-p-toluidine DMPT: N, N-dimethyl-p-toluidine

4). Others Other components used in Examples and Comparative Examples are as follows.
Silica: Fumed silica (monomethyltrichlorosilane treatment, average particle size 0.012 μm)
·ethanol

Example 1
A liquid material consisting of 100 parts by mass of PBA-1, 10 parts by mass of M1, and 0.1 parts by mass of DEPT;
A powder material consisting of 100 parts by mass of PBMA and 0.1 parts by mass of BPO;
To obtain a mucosa-adjusting material. Kneading time is 80 seconds, initial viscosity (30 seconds) is 80 Pas, initial viscosity (90 seconds) is 460 Pas, consistency is 35, both initial hardness and hardness after 1 month are 11, thickness change rate is 35%, tear strength Is 6.2 N / mm. The preferred physical properties of the dental mucosa preparation material of the present invention include kneading time within 100 seconds, initial viscosity of 300 Pas or less, consistency of 60 or less, hardness of 20 or less, rate of change of 50% or less, and tear strength of 4. Since the initial viscosity is low, the initial viscosity is good and the operability is good because the mucosa-adjusting material of Example 1 has a low initial viscosity. Furthermore, since the tear strength is high and the rate of change in thickness is small, the durability is excellent.

(Examples 2-9)
A mucosa-adjusting material was prepared and evaluated in the same manner as in Example 1 except that the type and blending amount of the radical polymerizable monomer were changed as shown in Table 4. The evaluation results are shown in Table 5.

(Examples 10 to 13)
A mucosa-adjusting material was prepared and evaluated in the same manner as in Example 1 except that the type of plasticizer was changed as shown in Table 4. The evaluation results are shown in Table 5.

(Examples 14 to 15)
A mucosa-adjusting material was prepared and evaluated in the same manner as in Example 1 except that the type of (meth) acrylic non-crosslinked polymer was changed as described in Table 4. The evaluation results are shown in Table 5.

(Examples 16 to 17)
A mucosa-adjusting material was prepared and evaluated in the same manner as in Example 1 except that silica was blended as shown in Table 4. The evaluation results are shown in Table 5.

(Examples 18 to 20)
A mucosa-adjusting material was prepared and evaluated in the same manner as in Example 1 except that ethanol was blended as shown in Table 4. The evaluation results are shown in Table 5.

(Example 21)
A mucosa-adjusting material was prepared and evaluated in the same manner as in Example 1 except that the polymerization initiator was changed as described in Table 4. The evaluation results are shown in Table 5.

  The mucosa-adjusting materials of Examples 2 to 21 have a low initial viscosity, so that the initial fluidity is good and the operability is good. Furthermore, since the tear strength is high and the rate of change in thickness is small, the durability is excellent.

(Comparative Example 1)
A mucosa-adjusting material was prepared and evaluated in the same manner as in Example 1 except that no radical polymerizable monomer was blended. The compositions and evaluation results are shown in Tables 6 and 7.

(Comparative Example 2)
A mucosa-adjusting material was prepared and evaluated in the same manner as in Example 12 except that no radical polymerizable monomer was added. The compositions and evaluation results are shown in Tables 6 and 7.

(Comparative Examples 3-4)
A mucosa-adjusting material was prepared and evaluated in the same manner as in Example 1 except that the radical polymerizable monomer was changed as described in Table 6. The evaluation results are shown in Table 7.

  Since the mucosa preparation materials of Comparative Examples 1 and 2 do not contain a radical polymerizable monomer, the tear strength is low and the durability is poor. Furthermore, the mucosa-adjusting material of Comparative Example 2 has a large change in hardness after one month from the initial hardness due to elution of the plasticizer over time, and the softness is not sustained. The mucosa-adjusting material of Comparative Example 3 uses a conventional radical polymerizable monomer. Since this radical polymerizable monomer has a low viscosity, the initial fluidity is good and the operability is good. On the other hand, the mechanical strength is inferior, so the tear strength is low and the durability is inferior. The mucosa-adjusting material of Comparative Example 4 uses a conventional radical polymerizable monomer. Since this radical polymerizable monomer has excellent mechanical strength, it has low tear strength and excellent durability, while it has a high viscosity, so its initial fluidity is poor and operability is poor.

Claims (8)

i) a liquid material comprising a plasticizer and a radical polymerizable monomer represented by the general formula (1),
And ii) a powder material comprising a (meth) acrylic non-crosslinked polymer,
It is divided and packaged and stored,
A polymerization initiator is included in both or either i) liquid material and ii) powder material,
A dental mucosa-adjusting material used as a paste in which both materials are mixed.

[In the general formula (1), X represents a divalent group, Ar ¹ and Ar ² each represent an aromatic group having any valence selected from divalent to tetravalent, L ¹ and L ² may be the same or different, and each of L ¹ and L ² has a main chain atom number in the range of 2 to 60, and any value selected from divalent to tetravalent Each represents a hydrocarbon group having a number, which may be the same or different, and R ¹ and R ² each represent hydrogen or a methyl group; Moreover, m1, m2, n1, and n2 are each an integer selected from the range of 1-3. ] In the radical polymerizable monomer,
The dental mucosa preparation material according to claim 1, wherein the divalent X group is -O-. In the radical polymerizable monomer,
A radical in which at least ^{one of the} hydrocarbon groups L ¹ and L ² has a hydroxyl group in which the number of atoms of the main chain is in the range of 2 to 60 and is selected from divalent to tetravalent The dental mucosa-adjusting material according to claim 1 or 2, which is a polymerizable monomer. In the radical polymerizable monomer,
It is shown by following General formula (2), The dental mucosa adjustment material as described in any one of Claim 1 thru | or 3 characterized by the above-mentioned.

[In the general formula (2), X, L ¹ , L ² , R ¹ and R ² are the same as those shown in the general formula (1). ] The dental mucosa-adjusting material according to any one of claims 1 to 4, wherein the plasticizer is a liquid polymer having a mass average molecular weight in the range of 1000 to 10,000. The dental mucosa-adjusting material according to any one of claims 1 to 5, wherein the glass transition temperature of the (meth) acrylic non-crosslinked polymer is in the range of 0 to 60 ° C. The dental mucosa-adjusting material according to any one of claims 1 to 6, wherein the powder material further comprises an inorganic powder. The dental mucosa-adjusting material according to any one of claims 1 to 7, wherein i) the liquid material further contains a water-soluble organic solvent.