JP6629088B2 - Dental mucosal conditioner - Google Patents

Description

  The present invention relates to a dental mucosal conditioner used for a denture-wearing patient who has deformation or inflammation of an oral mucosa in dental treatment.

  It is known that when a denture user uses a denture for a long period of time, the shape of the oral cavity gradually changes due to absorption of the alveolar bone forming the jaw ridge and the like. Due to the change in the shape of the oral cavity, the compatibility between the denture base mucous membrane and the oral mucosa deteriorates, and the denture becomes unstable. If such a denture is used as it is, uneven pressure is applied to the mucous membrane under the denture base, so that ulcer or inflammation occurs on the mucous membrane or pain due to occlusal pressure is caused.

  As described above, if the compatibility between the denture base mucosa and the oral mucosa deteriorates, create a new denture or line the denture in use to make the denture base mucosa and the oral mucosa compatible. It is necessary to restore sex.

  However, the oral mucous membrane with significant ulcers and inflammation is in an extremely unstable state, so it is necessary to wait for the oral mucosa to be healthy before making or lining a new denture.

  The material used in such a case is a dental mucosa conditioner (hereinafter, also simply referred to as "mucosa conditioner"). That is, the dental mucosa conditioner is a therapeutic material used by lining the mucosal surface of the denture base in use until the shape and color tone of the denture base mucous membrane are restored to a normal state. That is, it is a soft polymer material used on the mucous membrane under the denture base in order to release the strain and indentation of the mucous membrane below the denture base and to mark a functional form corresponding to the pressure displacement of each part.

  The mucous membrane adjusting material that mixes the powder and the liquid at the time of use becomes a highly fluid paste immediately after the mixing. The paste develops viscoelasticity by the liquid component in the paste penetrating into the powder. The paste is applied to the mucous membrane of the denture base while it is fluid, inserted into the oral cavity, and shaped in the oral cavity.

  The use period of the mucosal conditioner is one week to several weeks until the oral mucosa recovers to a healthy state. For that purpose, the mucosal conditioning material is soft and small enough to follow the shape change associated with the recovery 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, by lining the mucosal conditioning material on the mucosal surface of the denture that has become incompatible, it restores the compatibility between the denture and the oral mucosa and alleviates pain while reducing ulcers and inflammation of the oral mucosa. Wait for it to disappear. As the ulcer and inflammation of the oral mucosa gradually disappear, the morphology of the oral mucosa recovers to the original state over time. At this time, the mucous membrane adjusting material needs to be plastically deformed in accordance with a change in the shape of the oral mucosa. Because, if the mucosal conditioner does not deform following the shape change as described above, the compatibility between the mucosal conditioner and the oral mucosa will be lost as the oral mucosa recovers, This is because it may cause pain again.

  Patent Document 1 discloses a mucosal conditioner comprising an acrylic or methacrylic (hereinafter abbreviated as “(meth) acrylic”) non-crosslinked polymer and a phthalic acid plasticizer. Patent Document 2 discloses a mucosal conditioner comprising a (meth) acrylic non-crosslinked polymer, a phthalic acid-based plasticizer, and an organic solvent. These mucosal conditioners dissolve plasticizers in a short period of time, lose viscoelasticity over time, become hard, and cannot be used for a long period of time.

  Patent Document 3 discloses a powder material containing a (meth) acrylic non-crosslinked polymer and a polymerization initiator, a liquid material containing a phthalic acid or sebacic acid plasticizer, a (meth) acrylic monomer, and an organic solvent. A mucosal conditioner comprising: Since this mucosal conditioner is partially polymerized after kneading, elution of the plasticizer is suppressed, but the mucosal conditioner after polymerization becomes hard and is difficult to use for a long period of time. Furthermore, when a (meth) acrylic monomer is added to the extent that sufficient strength is obtained for use over a long period of time, the ratio of the plasticizer is relatively reduced, and sufficient flexibility cannot be obtained. It is difficult to balance durability.

  Patent Documents 4 and 5 disclose a mucosal conditioner comprising a (meth) acrylic non-crosslinked polymer, a liquid polymer, and an organic solvent. By using a liquid polymer as a plasticizer, this mucosal conditioner suppresses the elution of the plasticizer from the mucosal conditioner, but has insufficient durability.

  On the other hand, (meth) acrylate-based polymerizable monomers are used in dental materials such as dental curable compositions and dental adhesives, and in particular, a cured product having 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 And 9 are known polymerizable monomers having a biphenyl skeleton.

  From the viewpoint of facilitating the handling of the polymerizable monomer, it is advantageous that the polymerizable monomer is a low-viscosity liquid or liquid substance at room temperature. For example, in many cases, a polymerizable monomer is generally used as a mixed composition mixed with other components according to various uses, rather than used alone. In such a case, if the polymerizable monomer is a low-viscosity liquid or liquid substance, blending with other components is extremely easy.

  However, Bis-GMA exemplified in Patent Documents 6 and 7 has an extremely high viscosity in a room temperature environment, and the polymerizable monomer exemplified in Patent Document 8 is solid in a room temperature environment. Poor mechanical strength. Further, the polymerizable monomer exemplified in Patent Document 9 has relatively low viscosity, but also has poor mechanical strength.

JP-A-03-020204 JP-A-02-297358 JP-A-2002-104913 JP 2006-225281 A JP 2009-294362 A JP 2007-126417 A JP-A-09-157124 JP-A-05-170705 JP-A-63-297344

  The problem to be solved by the present invention is to provide a mucosal conditioner for kneading a powder material and a liquid material, in which the operability and handleability immediately after kneading during kneading are high, and that the denture base has a sufficient thickness. An object of the present invention is to provide a mucosal conditioner that can be formed on a mucosal surface, maintains its thickness for a long period of time, has high tear strength, and can be used for a long period of time.

  The present inventors have conducted intensive studies on the above problems, and as a result, a specific polymerizable compound represented by the following general formula (1), which has excellent mechanical strength, low viscosity even at room temperature, and excellent handleability. The inventors have found that the above problems can be solved by blending a monomer and a polymerization initiator, and have completed the present invention.

〔前記一般式（１）中、Ｘは−Ｏ−を表し、Ａｒ^１およびＡｒ^２は、各々、２価〜４価から選択されるいずれかの価数を持つ非置換の芳香族基を表し、各々同一であっても異なっていてもよく、Ｌ^１およびＬ^２は、各々、主鎖の原子数が２〜６０の範囲内であり、かつ、２価〜４価から選択されるいずれかの価数を持つ炭化水素基を表し、各々同一であっても異なっていてもよく、Ｒ^１およびＲ^２は、各々、水素またはメチル基を表す。また、ｍ１、ｍ２、ｎ１およびｎ２は、各々、１〜３の範囲から選択される整数である。〕
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、及び下記一般式（１）で示されるラジカル重合性単量体を含む液材と、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、重合開始剤が前記ｉ）液材及び前記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。

[In the general formula (1), X represents —O— , and Ar ¹ and Ar ² each represent an unsubstituted aromatic group having any valence selected from divalent to tetravalent. May be the same or different, and L ¹ and L ² each have a main chain atom number in the range of 2 to 60 and are selected from divalent to tetravalent And each may be the same or different, and R ¹ and R ² each represent hydrogen or a methyl group. Further, m1, m2, n1 and n2 are each an integer selected from the range of 1-3. ]
The present invention that solves the above-mentioned problems is described below.
[1] i) a plasticizer, and a liquid material containing a radical polymerizable monomer which is shown by the following general formula (1), ii) (meth) divided into a powder material containing an acrylic non-crosslinked polymer packaging Te, are stored, both of the polymerization initiator is the i) a liquid material and the ii) powder material, or any included one, the dental tissue conditioner is used as a paste at the time of use with mixed both wood.

[In the general formula (1), X represents —O— , and Ar ¹ and Ar ² each represent an unsubstituted aromatic group having any valence selected from divalent to tetravalent. May be the same or different, and L ¹ and L ² each have a main chain atom number in the range of 2 to 60 and are selected from divalent to tetravalent And each may be the same or different, and R ¹ and R ² each represent hydrogen or a methyl group. Further, m1, m2, n1 and n2 are each an integer selected from the range of 1-3. ]
[2] Formula dental tissue conditioner according to the at least one of L ¹ and L ² is Nde contains a hydroxyl group in (1) [1].
[3] Formula (1) in the radically polymerizable monomer represented by the according to the above [1] or [2], which is a polymerizable monomer represented by the following general formula (2) Dental mucosal conditioner.

[In the general formula (2), X, L ¹ , L ² , R ¹ and R ² are the same as those in the general formula (1). ]
[4] The plasticizer, dental tissue conditioner according to any one of the weight-average molecular weight of liquid polymer in the range of 1,000 to 10,000 [1] to [3].
[ 5 ] The dental mucosal conditioner according to any one of [1] to [ 4 ], wherein the (meth) acrylic non-crosslinked polymer has a glass transition temperature of 0 to 60 ° C.
[ 6 ] The dental mucosal conditioner according to any one of [1] to [ 5 ], wherein the ii) powder material further contains an inorganic powder.
[7] the i) a liquid material, a dental tissue conditioner according to any one of which is characterized in that further contains a water-soluble organic solvent [1] to [6].

  The mucosal conditioner of the present invention has a low initial viscosity, is excellent in operability, and suppresses the dissolution of the plasticizer and improves durability (tear strength), so that it can be used for a long time while maintaining softness. it can.

  Hereinafter, the present invention will be described in detail.

The dental mucosal conditioner of the present invention (hereinafter, also referred to as "the present mucosal conditioner") comprises an i) liquid material and ii) a powder material described below. The present 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, and 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 is any valence selected from divalent to tetravalent. Represents a hydrocarbon group having a number, and may be the same or different, and R ¹ and R ² each represent a hydrogen or a methyl group. Further, 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, the use of a liquid polymer is particularly preferred. By using the liquid polymer, the flexibility of the dental mucosal conditioner after curing can be increased, and the flexibility can be maintained for a long time when used in the oral cavity. In addition, since the liquid polymer does not migrate to the denture base, it does not damage the denture base.

  The liquid polymer is preferably a water-insoluble liquid polymer having a mass average molecular weight of 1,000 to 10,000 and a proportion of oligomer having a molecular weight of 500 or less being 10% by mass or less.

  In the present invention, the term "liquid" means a liquid at room temperature to oral temperature, that is, 18 to 40 ° C. If it is not liquid within the above temperature range, kneading with the powder material cannot be performed, the mucous membrane adjusting material does not become a paste, or an appropriate viscoelasticity cannot be obtained.

  In the present invention, water-insoluble means that the solubility in water at 37 ° C., which is the 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, particularly preferably 1% by mass or less.

  When the mass average molecular weight of the liquid polymer is less than 1000 or when a water-soluble plasticizer is used, the plasticizer elutes in the oral cavity when the mucosal modifier is used, and the viscoelasticity and flexibility of the mucosal modifier are lost in a short time. May be asked. When the mass average molecular weight of the liquid polymer exceeds 10,000, appropriate flexibility cannot be imparted, and it may be difficult to use the liquid polymer as a mucosal conditioner. The mass average molecular weight of the liquid polymer having good kneadability is 1200 to 7000, and more preferably 1500 to 5000.

  In general, the higher the molecular weight of a liquid polymer, the lower the compatibility with other components tends to be. Therefore, the molecular weight distribution of the liquid polymer is preferably less than 10% by mass, and more preferably less than 5% by mass, for the portion having a molecular weight exceeding 10,000. In addition, a liquid polymer having a molecular weight of 500 or less easily elutes in the oral cavity and easily migrates to a denture base, so that it may be difficult to use it for a long period of time. Therefore, in the molecular weight distribution of the liquid polymer, the portion having a molecular weight of 500 or less is preferably less than 10% by mass, more preferably less than 7% by mass.

  The material of the liquid polymer is not particularly limited, but has a good affinity for the (meth) acrylic non-crosslinked polymer particles blended with the powder material, and is excellent in kneadability and various physical properties of the obtained paste. A (meth) acrylic liquid polymer is preferred. Among them, (meth) acrylate-based polymers (hereinafter, also referred to as “(meth) acrylate-based) polymers are particularly preferable because a liquid polymer having the above molecular weight is easily obtained.

  The (meth) acrylic liquid polymer blended in the powder material has the average molecular weight limited to the above range, and its properties are liquid. Different from non-crosslinked polymers.

  A liquid polymer having a mass average molecular weight of 1,000 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 mixing ratio of the monomer and the polymerization initiator. Ion polymerization or living radical polymerization, in which the average molecular weight can be easily controlled, is suitably used. In particular, according to the anionic polymerization, a polymer having a very sharp molecular weight distribution and a mass average molecular weight / number average molecular weight of 2 or less and close to monodispersion can be obtained. Further, 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 is polymerized with another monomer copolymerizable with the (meth) acrylic monomer so as to have a mass average molecular weight of 1,000 to 10,000. Just fine.

  Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth), which are esters 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 ( (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 selected from meth) acrylates or a copolymer obtained by polymerizing two or more 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.

  Other monomers copolymerizable with the (meth) acrylate-based monomer include vinyl acetate and styrene. In this case, it is possible to use a copolymer obtained by copolymerizing one or more (meth) acrylate monomers and one or more other copolymerizable monomers. From the viewpoint of solubility and swelling, the monomer unit derived from the (meth) acrylate-based monomer preferably contains at least 50 mol%, more preferably at least 80 mol%.

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

  As the liquid polymer, two or more polymers having different molecular weight distributions may be used in combination. Further, two or more liquid polymers having different types and ratios of the monomer units constituting the polymer may be used in combination.

  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, L ¹ and L ² may each 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 atoms in the main chain is in the range of 2 to 60. Represents a hydrocarbon group having a valence, and may be the same or different, and R ¹ and R ² each represent a hydrogen or a methyl group. Further, 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 a mixture of isomers containing two or more isomers.

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

In addition, the reason for exhibiting a low viscosity even in a room temperature environment is that the aromatic group Ar ¹ and the aromatic group Ar ² are directly linked via a σ bond, such as a biphenyl structure, at the center of the molecule. 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 employed. It is mentioned. Although the structure (Ar ¹ -Ar ² ) has high symmetry in molecular structure and is easily crystallized, the structure (Ar ¹ -X-Ar ² ) in which a divalent group X is further introduced into such a structure has a molecular structure. It is considered that the flexibility of the polymer is increased and the symmetry is reduced, and as a result, the crystallinity is reduced and the viscosity is reduced. 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 ) has a higher molecular flexibility than the structure (Ar ¹ -Ar ² ). For this reason, the polymerizable monomer of the present embodiment is less likely to become brittle and has excellent flexural strength as compared with a polymerizable monomer having a structure (Ar ¹ -Ar ² ) introduced at the molecular center. .

Next, the polymerizable monomer represented by the general formula (1) will be described in more 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. 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 tetravalent represented by the following structural formulas Ar-a4 to Ar-a6. Naphthalene, or divalent to tetravalent anthoselan represented by the following structural formulas Ar-a7 to Ar-a9. In these structural formulas, a bond is provided at an arbitrary carbon of a benzene ring constituting the aromatic groups Ar ¹ and Ar ² (excluding a carbon forming a condensed portion between the benzene ring and the benzene ring). Can be. For example, in the case of the structural formula Ar-a1 (divalent benzene), two bonds can be provided at any of the ortho, meta, and para positions.

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.

The aromatic groups Ar ¹ and Ar ² may each have a substituent. In this case, hydrogen of the benzene ring constituting the aromatic groups Ar ¹ and Ar ² is replaced with another substituent. Can be. The substituent of the aromatic groups Ar ¹ and Ar ² is not particularly limited as long as it does 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 its terminal. Those having a total number of atoms (number of atoms) constituting the substituent within the range of 1 to 60 can be appropriately selected. Specifically, mention may be made or a monovalent hydrocarbon group having 1 to 20 carbon atoms, -COOR ^3, -OR ^3, halogen group, an amino group, a nitro group, a carboxyl group or the like. Note that R ³ is the same as a 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 and an ethyl group; an alicyclic hydrocarbon group such as a cyclohexyl group; a phenyl group; And a heterocyclic group such as furan.

X represents a divalent group, and specifically, the number of atoms in the main chain bridging 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. Is preferred. Examples of the divalent groups X of such _{electron-donating, -O -, - CH 2 -} , - CH (R 5) - or -S-. 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 by the following resonance structural formula, so that the polarity at the center of the molecule is relatively high. For this reason, the affinity with the hydrophilic material with high polarity can be further improved, and as a result, the compatibility with the hydrophilic material can be improved, and the affinity and adhesion to the hydrophilic surface can be improved. It becomes easier. Note that the following resonance structural formula shows that the divalent group X is —O— and the aromatic groups Ar ¹ and Ar ² are phenylene groups (provided that two bonds are provided at the para position). FIG. 2 shows the center of the molecule of the polymerizable monomer of the present embodiment.

L ¹ and L ² each represent a hydrocarbon group in which the number of atoms in the main chain is in the range of 2 to 60, and which has any valence selected from divalent to tetravalent; 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, further 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.

  In addition, the atoms constituting the main chain are basically composed of carbon atoms, and all the atoms may be carbon atoms, but it is also possible to replace some of the carbon atoms constituting the main chain with hetero atoms. 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 hetero atoms 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 hetero atoms that can be introduced into the main chain is one. .

Further, a substituent may be bonded to at least one of the atoms constituting the main chain (usually a carbon atom). Examples of such substituents 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, a halogen, -COOR ^4, and -OR ^4. Note that R ⁴ is the same as the alkyl group having 1 to 3 carbon atoms. Further, the monovalent hydrocarbon group having a hydroxyl group preferably has 1 to 3 carbon atoms, and more preferably 1 to 2 carbon atoms. Specific examples of the monovalent hydrocarbon group having a hydroxyl _{group, -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 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 ^{1 In} at least one of ² , the substituent is preferably a hydroxyl group and / or a monovalent hydrocarbon group having a hydroxyl group. In addition, the number of hydroxyl groups contained in each of L ¹ and L ² may be at least one or more, but is usually preferably one. Further, hydroxyl groups, it is more preferable that contains one to each of L ¹ and L ^2, in this case, will include two hydroxyl groups in the molecule, if m1, m @ 2 = 1.

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, even 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 an ester bond directly bonded to the aromatic groups Ar ¹ and Ar ² , since the increase in viscosity can be 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 atoms in the chain means in the range of 2 to 10, and the number of atoms in the main chain is particularly preferably in the range of 2 to 3. The reason why the above-mentioned effect is obtained is not clear, but the present inventors have I speculate as follows.

When a hydroxyl group is present in the vicinity of an 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 converted to an aromatic group as shown in the following structural formula. It is expected that an intramolecular hydrogen bond is likely to be formed between the ester group and the oxygen of the carbonyl group of the ester bond directly bonded to Ar ¹ and Ar ² . In addition, the structural formula exemplified below is represented by the following formula in general formula (1): 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, the formation of an intermolecular hydrogen bond is suppressed. For this reason, in the polymerizable monomer of the present embodiment, when a hydroxyl group is not contained in the molecule, the viscosity increases when the molecule contains a hydroxyl group. The increase in the viscosity is suppressed to the same level as the viscosity of the polymerizable monomer having the formula (such as Bis-GMA).

In addition, when the intramolecular hydrogen bond is formed, the benzene ring forming the aromatic groups Ar ¹ and Ar ² and the benzene ring directly forming the aromatic group are compared with the case where the intermolecular hydrogen bond is not formed. Distortion occurs in the benzoate structure composed of the ester bond to be bonded, and the symmetry of the molecular structure at the molecular center decreases. Therefore, it is considered that the crystallinity of the molecule is reduced and the remarkable increase in the viscosity is further suppressed. In addition, the formation of intramolecular hydrogen bonds weakens the intermolecular bonds, which may cause a decrease in the mechanical strength of the cured product. However, when the polymerizable monomer of this embodiment has a hydroxyl group near the ester bond directly bonded to the aromatic groups Ar ¹ and Ar ² , the hydroxyl group is more precisely a molecule than an intermolecular hydrogen bond. It is considered that the degree of contribution to internal hydrogen bonding is relatively higher, and that it is also likely to contribute to the formation of a gentle hydrogen bonding network between molecules. Further, when a plurality of hydroxyl groups are contained in a molecule, such as when both L ¹ and L ² have a hydroxyl group, a high-density hydrogen bonding network is easily formed between the molecules. In this case, it is considered that the mechanical strength of the cured product can be higher than that of the polymerizable monomer of this embodiment having no hydroxyl group in the molecule.

Specific examples of L ^{1, L 2,} in the case of ^{n1, n2 = 1 (L 1} , if ^{L 2} is a divalent hydrocarbon group), is the following structural formulas L-b1~L-b14 it can. Note that, 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 L-b1 to L-b14, 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, d represents an integer selected from the range of 0 to 5, e represents an integer selected from the range of 2 to 5, f is selected from the range of 1 to 6 Represents an integer. The values of a to f are preferably selected in the structural formulas L-b1 to L-b14 so that the number of atoms in the main chain is 12 or less.

On the other hand, when n1 and n2 = 2 (when L ¹ and L ² are trivalent hydrocarbon groups), in the structural formulas L-b1 to L-b14, among the carbon atoms constituting the main chain, * The carbon atom farthest from the carbon atom having the attached bond has two bonds. When n1 and n2 = 3 (when L ¹ and L ² are tetravalent hydrocarbon groups), the structural formulas L-b1 to L-b2, L-b6 to L-b8, and L-b10 to L In -b14, among the carbon atoms constituting the main chain, the carbon atom farthest from the carbon atom having the 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). In general formula (2) are the compounds of formula (1), m1, m2, n1, n2 = 1, Ar 1, Ar 2 = -C 6 H 4 - ( structural formula Ar-a1) and to the case structure It is shown.

Further, the polymerizable monomer of the present embodiment is preferably a polymerizable monomer represented by the 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 same general formula (1) except that the valence can take only two valences. And L ³ and L ⁴ each represent a divalent hydrocarbon group having a main chain atom number in the range of 1 to 8; R ³ and R ⁴ each represent hydrogen or a methyl group. Also, 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} (Bifunctional structure). Further, in the general formula (3), the groups shown in parentheses on both the left and right sides can be bonded to any of the two bonding hands 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 parenthesis on the left side in the general formula (3) may be bonded to both sides of the group shown in the center, or the group shown on the right side in the general formula (3). Groups shown in parentheses may be attached 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 the atoms may be carbon atoms, but a part of the carbon atoms constituting the main chain may be used. 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, but is preferably 1 to 5, 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 a 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. A group in which a part or the whole is substituted by 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). (1, 1) and (0, 2) are more preferable from the viewpoint that suppression of decomposition of body molecules can be expected.

  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). Preferably, it contains any two or more structural isomers selected from the group consisting of: When the polymerizable monomer contains two or more types of structural isomers for 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 is easy to improve. In this case, the average value of the value k in all the 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 more than 0 and 1.95 or less). Is preferred. Further, the lower limit of the average value k is preferably 0.1 or more, and the upper limit of the average value k is more preferably 1.7 or less, and further preferably 1.5 or less. , 0.4 or less. In addition, in order to improve the mechanical strength of the cured product and the storage stability in a well-balanced manner, the average value k is also 0.05 or more and 2. It is suitable similarly to 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 structural isomers than in the value k = 2 (in the state not containing structural isomers). be able to. In this regard, it is more advantageous that the average value of the value k is small as long as the average value of the value k is not less than 0.05.

  The polymerizable monomer of the present embodiment can be synthesized by appropriately combining known starting materials and known synthesis reaction methods, and the production method 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 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 is a main chain having 1 to 7 atoms. Represents a divalent hydrocarbon group. P is 0 or 1. Here, the average value of the value 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, if necessary, by performing a purification treatment after the synthesis, the average value k (the abundance ratio of the structural isomers represented by the general formulas (6) to (8)) is adjusted so as to be closer to a desired value. You may.

In L ⁵ shown in the general formula (4) to (8), atoms composing the main chain is basically composed of carbon atoms, but all the atoms may be carbon atoms, constituting the main chain Some of the carbon atoms may be replaced by 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.

The atomic number of the main chain in ^{L 5} represents, but may be a 1-7, preferably 1-4, 1-2 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; A group in which a part or the whole is substituted by 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. This is the same in 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. Also, p is preferably 0.

  If necessary, a polymerizable monomer containing two or more structural isomers is obtained by the above-described production method, and then a polymerizable monomer substantially free of structural isomers (for example, a compound represented by the general formula: Only the polymerizable monomer shown in (6)) may be isolated and purified. However, the polymerizable monomer obtained by isolation and purification has a higher mechanical strength and storage stability than the polymerizable monomer containing two or more structural isomers before the isolation and purification treatment. It tends to be inferior in terms of compatibility with sex. In addition, the production and production of the polymerizable monomer requires an additional isolation and purification treatment, which is disadvantageous in terms of cost. Therefore, from these viewpoints, the isolation and purification treatment is preferably omitted.

  The mixing amount of the radical polymerizable monomer is preferably at least 1 part by mass with respect to 100 parts by mass of the plasticizer from the viewpoint of improving tear strength, and the handleability of the composition and the flexibility as a mucosal conditioner are preferred. From the viewpoint of application, the amount is preferably within 30 parts by mass, and particularly preferably 3 to 20 parts by mass, which can provide particularly good operation feeling and durability.

  The liquid material in the mucosal conditioner of the present invention may contain a radical polymerizable monomer other than the polymerizable monomer represented by the general formula (1) as long as the effects of the present invention are not impaired. As the radical polymerizable monomer, a known monomer that can be generally used for a dental material can be used. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, and β-methacryloyloxyethyl 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 Acrylate corresponding to acrylate, 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 Difunctional (meth) acrylic polymerizable monomers such as 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol Examples include trifunctional (meth) acrylic polymerizable monomers such as ethanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylolmethanetri (meth) acrylate.

  The amount of the polymerizable monomer is such that the total amount of the polymerizable monomer represented by the general formula (1) is 30 parts by mass with respect to 100 parts by mass of the plasticizer from the viewpoint of imparting flexibility as a mucosal conditioner. Parts or less. From the viewpoint of improving the tear strength, the ratio of the polymerizable monomer represented by the general formula (1) to the other polymerizable monomer is preferably 8/2 to 10/0.

  It is preferable that the liquid material in the mucous membrane adjusting material of the present invention further contains a water-soluble organic solvent. By blending the water-soluble organic solvent, the fluidity of the liquid material is improved and the liquid material is easy to handle. Further, the operability in mixing and kneading the powder material and the liquid material is improved. 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 easily penetrates the plasticizer when dissolving or swelling the (meth) acrylic non-crosslinked polymer blended in the powder material, It is considered that this is to improve the familiarity and the like. In addition, since the mucosal conditioner of the present invention is used in the oral cavity for a relatively long period of time, a water-insoluble organic solvent which 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 from the viewpoint of harm to living organisms and odor, and ethanol is particularly preferable.

The blending amount of the water-soluble organic solvent is not particularly limited as long as the effect of the present invention is not impaired. From the viewpoint of the handleability of the composition and the change in the physical properties of the composition after the organic solvent is eluted from the composition, the content is preferably 30 parts by mass or less, and particularly preferably 3 to 20 parts by mass, which can provide a good operational feeling. It is particularly preferred that there is.
ii) Powder The powder 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, (meth) acrylic monomer), 2 Copolymers obtained by copolymerizing different kinds of (meth) acrylic monomers, and copolymerization of (meth) acrylic monomers and polymerizable monomers other than (meth) acrylic monomers And a copolymer obtained by the above method (provided that the proportion of the monomer unit based on the (meth) acrylic monomer is 50 mol% or more). (Meth) acrylic polymers are well compatible with (meth) acrylic denture bases and can easily obtain appropriate viscoelasticity.

  In addition, it is necessary that the composition obtained by kneading a powder material and a liquid material into the present mucosal conditioner be a paste having an appropriate viscosity. Therefore, the (meth) acrylic non-crosslinked polymer needs to be a non-crosslinked polymer that is soluble in the liquid component.

  Homopolymers obtained by homopolymerizing (meth) acrylic monomers include poly (methyl methacrylate), poly (iso-propyl methacrylate), poly (t-butyl methacrylate), poly (phenyl methacrylate), and 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 (II) 3-chloro-2,2-bis (chloromethyl) propyl acrylate}, poly (2-chlorophenyl acrylate), poly (4-chlorophenyl acrylate), poly (4-methoxyphenyl acrylate), poly (2,4-di (Lorophenyl 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 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.

  Examples of copolymers for copolymerizing (meth) acrylic monomers and other polymerizable monomers include poly (styrene-methyl methacrylate) and poly (styrene-ethyl methacrylate) poly (styrene-n-butyl methacrylate). Is exemplified.

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

  Among the above (meth) acrylic non-crosslinked polymers, in terms of solubility, ease of handling, etc., they are composed of (meth) acrylate-based monomer units such as ethyl methacrylate and n-butyl methacrylate. 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. In the case of a polymer having a Tg of less than 0 ° C., the non-crosslinked polymer particles are extremely strongly aggregated during storage of the powder at room temperature (about 18 to 35 ° C., which is the environmental temperature at which the mucosal conditioner is stored before use). Therefore, the composition obtained by kneading with the liquid material may not form a paste. When the polymer has a Tg of higher than 60 ° C., the composition obtained by kneading with the liquid material becomes hard, and it may not be possible to impart appropriate flexibility to the mucosal conditioner. In the present invention, “appropriate flexibility” means that the Shore A hardness is 20 or less.

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

  The above (meth) acrylic non-crosslinked polymer is not particularly limited in its average molecular weight and molecular weight distribution 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 light 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 addition, in this specification, the mass average molecular weight means a standard polystyrene equivalent molecular weight measured by gel permeation chromatography (hereinafter, may be abbreviated as "GPC").

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

  Further, in addition to the above-mentioned components, an inorganic powder may be added to the powder material ii) in the dental mucosal preparation material of the present invention, as long as the effects of the present invention are not impaired. By adding the inorganic powder, the viscoelasticity and the like 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 mucosal conditioner becomes too soft, an appropriate desired hardness can be obtained by adding an inorganic powder. In general, the amount of the inorganic powder is desirably 5 parts by mass or less, more preferably 2 parts by mass or less, based on 100 parts by mass of the (meth) acrylic non-crosslinked polymer.

  The type of the inorganic powder is not particularly limited, and can be selected from reinforcing materials and fillers added to a general resin composition. Specific examples include calcium carbonate, calcium sulfate, magnesium oxide, barium carbonate, barium sulfate, titanium oxide, potassium titanate, barium titanate, aluminum hydroxide, magnesium hydroxide, silica 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 viewpoint of ease of handling, compatibility with liquid materials, and solubility (elution) in saliva.

  The particle size of these inorganic powders is not particularly limited, but from the viewpoint of storage stability, kneadability and the like, the volume average particle size is preferably 1 μm or less, more preferably 0.1 μm or less. Considering the availability of inorganic particles having such a particle size, fumed silica is most preferable. Of course, two or more kinds of inorganic powders having different materials and average particle diameters may be used in combination. It should be noted that the crosslinked polymer may be added to the powder material in a small amount that does not affect the effects of the present invention.

  As the polymerization initiator contained in i) the liquid material and / or ii) the powder material, i) polymerizes and cures the polymerizable monomer represented by the general formula (1) contained in the liquid material. As long as it can be used, it can be used without any limitation, and a known polymerization initiator can be used. For example, radical polymerization initiators used in the dental field include chemical polymerization initiators (room temperature redox initiators), photopolymerization initiators, and thermal polymerization initiators. Polymerization initiators and / or photopolymerization initiators are preferred.

  The chemical polymerization initiator is a polymerization initiator which is composed of two or more components and which generates a polymerization active species near room temperature by mixing all components immediately before use. As such a chemical polymerization initiator, an organic peroxide / amine compound-based one is representative.

  Representative organic peroxides used as such a chemical polymerization initiator include ketone peroxide, peroxyketal, hydroperoxide, diaryl peroxide, peroxyester, diacyl peroxide, and peroxydioxide. Carbonate and the like, specifically, methyl ethyl ketone peroxide, cyclohexano peroxide, P-methane hydroperoxide, diisopropylbenzene peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, benzoyl peroxide, di- Examples thereof include n-propylperoxydicarbonate and 1,1,3,3-tetramethylbutylperoxyneodecanoate.

  The preferred amount of these organic peroxides varies depending on the type of the organic peroxide used and 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 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.

  As the tertiary amine for generating a radical upon contact with these organic peroxides, known compounds are used without particular limitation. 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-tolyldiethanolamine, from the viewpoint of high polymerization activity, low irritation and low odor -Tolyldipropanolamine is preferably used.

  The amount of the tertiary amine compound is preferably 0.1 to 100 parts by mass of the polymerizable monomer represented by the general formula (1). The range is from 0.5 to 5 parts by mass, and more preferably from 0.1 to 3 parts by mass.

  Among the above-mentioned combinations of organic peroxides and tertiary amine compounds, preferred ones are specifically exemplified by 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, from the viewpoint of storage stability, BPO / N, N-diethyl-p-toluidine, BPO / N , N-Dipropyl-p-toluidine is most preferred.

  In addition to such a chemical polymerization initiator comprising an organic peroxide and an amine compound, a sulfinic acid such as benzenesulfinic acid or p-toluenesulfinic acid and a salt thereof, or a barbituric acid-based initiator such as 5-butyl barbituric acid is used. Even if the agent is blended, it can be used without any problem.

  As the photopolymerization initiator, known initiator systems such as an α-diketone-reducing agent, a ketal-reducing agent, and a thioxanthone-reducing agent are preferably used. Examples of the A-diketone 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. Reducing agents as one component of the photopolymerization initiator include tertiary amines such as 2- (dimethylamino) ethyl methacrylate, ethyl 4-dimethylaminobenzoate, N-methyldiethanolamine, lauraldehyde, dimethylaminobenzaldehyde, and terephthalic acid. Aldehydes such as aldehyde, 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid, thiobenzoic acid and the like can be mentioned.

  Suitable amounts of these photopolymerization initiators vary depending on the type of photopolymerization initiator used, and thus cannot be unconditionally limited, but are preferably based on 100 parts by mass of the polymerizable monomer represented by the general formula (1). Is in the range of 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.

  The above-mentioned organic peroxide and tertiary amine compound are used separately in i) liquid material and ii) powder material. Either one of them may be used. 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 mucosal preparation material of the present invention, the mixing ratio of the powder material and the liquid material is not particularly limited, but the mixing ratio of the plastic material to be mixed with the liquid material is 100 parts by mass of the (meth) acrylic non-crosslinked polymer. The range where the amount of the agent is 50 to 300 parts by mass is preferable. Also, if there is a large difference in the ratio between the powder material and the liquid material, a paste may not be formed even when both are mixed. Therefore, the powder material and the liquid material preferably have a powder / liquid ratio of 0.5 to 2.5 in terms of mass ratio. From the viewpoint of easy measurement and mixing at the time of use, the powder / liquid = More preferably, it is about 0.8 to 2.0. The mixing of the powder material and the liquid material may be carried out until both become a uniform paste, but are usually made uniform within a range of 5 to 100 seconds.

  The dental mucosa conditioner of the present invention may contain, as necessary, coloring materials such as dyes and pigments, fragrances, antibacterial agents, antifungal agents, and the like, in addition to the above components.

  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 of Examples and Comparative Examples are as follows.

(1) Measurement method of glass transition point (Tg) Tg was measured using a differential scanning calorimeter (DSC6200 / Seiko). The initial temperature was raised at a rate of 10 ° C./min to a temperature about 30 ° C. higher than the approximate Tg. Then, the temperature at the intersection of the three tangent lines obtained from the signal obtained by immediately raising the temperature was determined, and the intermediate temperature between them was defined as Tg.

(2) Method of measuring kneading time To a rubber cup from which a liquid material has been measured in advance, add 1.1 mass times of powder material to start kneading, and the added powder material is uniform with the liquid material. Kneading was continued with a spatula until it became a paste. The time from the start of mixing until a uniform paste was obtained was measured and defined as the mixing time.

(3) Initial Viscosity Measurement Method at the Time of Kneading It was measured using a dynamic viscoelasticity measuring device CS rheometer “CVO120HR” (manufactured by Bolin Corporation). The 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 ° diameter, 1 ° cone. The mixture was kneaded by the method described in the above (3) Method of measuring kneading time, and the viscosity was measured 30 seconds after the uniform paste was obtained (kneading time). In order to allow a sufficient margin for the operation, it is desirable that the initial viscosity can be suppressed to 300 Pas or less.

(4) Method of measuring consistency
It measured based on JIS-T6519 (short term elastic lining material for denture base). The measurement was carried out by kneading according to the method described in (3) Method of measuring kneading time, 2 ml of the sample was weighed, and placed on one glass plate. Thirty 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. After 120 seconds from the end of mixing, a 1000 g weight was gently placed vertically on the cover glass plate, and the weight was removed 60 seconds later. Eight minutes after the end of the mixing, the lengths of the maximum part and the minimum part between the parallel tangents of the sample spread were measured, and the average value was determined to be the consistency. The fact that the consistency at the time of this measurement is small (approximately 60 or less) means that the paste obtained by kneading the powder material and the liquid material on the adhesive surface of the denture base is inserted into the oral cavity when the paste is viscoelastic. Means that it is difficult to be pushed out even when mounting pressure is applied.

(5) Method of measuring hardness Shore A hardness, which is an index of flexibility, was measured based on JIS-K7215 (durometer type A). The measurement was performed at the time of standing overnight at 37 ° C. after kneading and at the time of immersing in water at 37 ° C. for one month (hereinafter, “initial hardness” and “hardness after one month” respectively). Say).

(6) Thickness change rate measuring method 30 × 30 × 2 mm on a square acrylic plate having a side of about 30 mm and a thickness of about 2 mm produced using a denture base resin material (“Akron” (GC)). And a kneading method as described in (2) Method of measuring kneading time, pour the paste 10 seconds after the uniform paste was obtained, and pour another paste from above. It was pressed with two acrylic plates. Thirty minutes after the start of mixing, the mold was removed, immersed in water at 37 ° C. for one day, and the thickness of the test piece was measured using a micrometer. The thickness of the test piece minus the thickness of the two acrylic plates was taken as the pre-test thickness of the mucosal conditioner layer. After the thickness measurement, a load test was repeatedly performed under the following conditions using a fatigue tester “Electro Pulse” (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 thickness of the test piece minus the thickness of the two acrylic plates was taken as the post-test thickness of the mucosal conditioner layer, and the rate of change was determined by the following equation.
Thickness change rate [%] of mucosal conditioner layer = (thickness before test−thickness after test) [mm] / 2 [mm] × 100
(7) Tear strength A test was conducted based on JIS K6252 "Vulcanized rubber and thermoplastic rubber-Determination of tear strength". An angle-shaped (2 mm thick) test piece was prepared, immersed in water at 37 ° C. overnight, and then broken using an autograph (AG-1 manufactured by Shimadzu Corporation) at 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.

  Various compounds used in each of Examples and Comparative Examples are as follows.

1. Liquid Material Components The 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 of tri (n-butyl) aluminum (1.0 mol / l) was mixed with 40 ml of toluene, and cooled to -78 ° C. To this, 7.4 ml (7.4 mmol) of a toluene solution of t-butyl lithium (1.0 mol / l) was added, and after stirring for several minutes, 16.1 g (126 mmol) of butyl acrylate was added at a temperature in the reaction system. Carefully added so as not to go up. This reaction was performed in a standard Schlenk tube under a nitrogen atmosphere, and the transfer of the reagent was performed using a syringe. After the toluene was refluxed over sodium, it was distilled under a nitrogen atmosphere. Butyl acrylate was purified through a basic alumina column and a column of Molecular Sieves 4A. After stirring for 24 hours, methanol was added to stop the reaction. After washing with a 50% aqueous methanol solution using a separatory funnel, vacuum drying was performed at 120 ° C. to obtain 11.6 g of a colorless and transparent liquid compound (yield: 72%). According to GPC measurement, the mass average molecular weight was 2,000 (in terms of polystyrene), Mw / Mn = 1.15, and those having a molecular weight of less than 500 were contained in 5% by mass.

(Production Example 2)
PBA-2: 1.0 ml (1.0 mmol) of a toluene solution of tri (n-butyl) aluminum (1.0 mol / l), 2.5 ml of a toluene solution of t-butyllithium (1.0 mol / l) (2. (5 mmol) to obtain 10.1 g of a colorless and transparent liquid compound (yield: 63%). According to GPC measurement, the mass average molecular weight was 6000 (in terms of polystyrene), Mw / Mn = 1.12, and those having a molecular weight of less than 500 were less than 1% by mass.

(Production Example 3)
PPA: 3.0 ml (3.0 mmol) of a toluene solution of tri (n-butyl) aluminum (1.0 mol / l) was mixed with 40 ml of toluene, and cooled to -78 ° C. To this, 7.4 ml (7.4 mmol) of a toluene solution of t-butyl lithium (1.0 mol / l) was added, and after stirring for several minutes, 14.8 g (130 mmol) of propyl acrylate was added at a temperature in the reaction system. Carefully added so as not to go up. This reaction was performed in a standard Schlenk tube under a nitrogen atmosphere, and the transfer of the reagent was performed using a syringe. After the toluene was refluxed over sodium, it was distilled under a nitrogen atmosphere. Propyl acrylate was purified through a basic alumina column and a column of Molecular Sieves 4A. After stirring for 24 hours, methanol was added to stop the reaction. After washing with a 50% aqueous methanol solution using a separatory funnel, vacuum drying was performed at 120 ° C. to obtain 10.2 g of a colorless and transparent liquid compound (yield: 69%). According to GPC measurement, the mass average molecular weight was 2,000 (in terms of polystyrene), Mw / Mn = 1.15, and those having a molecular weight of less than 500 were contained in 5% by mass.

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

In addition, 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 formulas are average values of the mixture of the compounds (a), (b) and (c). The values g and h shown together with the above structural formulas and the structural formulas shown below mean average values. In each molecule, the values of g and h can take an integer of 0, 1, or 2. . Except when the average of the values g and h is 0 or 2, the structural formula indicating the average of the values g and h has two or three 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 parentheses.

(Production Example 4)
<Synthesis of acid chloride (A)>
A first mixture of 2,5.3 g (0.096 mol) of 4,4'-diphenyletherdicarboxylic acid, 0.85 g (0.012 mol) of dimethylformamide and 80 ml of toluene was prepared. To the stirred first mixture, a second mixture consisting of 58.4 g (0.46 mol) of thionyl chloride and 20 ml of toluene was gradually added dropwise at room temperature. After completion of the dropwise addition, the obtained liquid was heated to 95 ° C. and refluxed for 3 hours. Then, by allowing the yellow transparent liquid obtained after heating and reflux to cool, the 4,4′-diphenyl ether dicarboxylic acid chloride having the molecular structure shown below (hereinafter sometimes referred to as “acid chloride (A)”) Was obtained. Further, this toluene solution was applied 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′-diphenyletherdicarboxylic acid chloride solid. Was.
<Synthesis of 4-DPEHE>
120 ml of methylene chloride was added to 15.3 g (0.052 mol) of the acid chloride (A) to obtain a dispersion containing the acid chloride (A). A mixed solution obtained by mixing 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 at −78 ° C. to the dispersion of the acid chloride (A) using a dropping funnel, and the mixture was further stirred for 5 hours. Water was added to the liquid obtained after the dropwise addition and stirring, and the solvent was removed using a rotary evaporator. The residue obtained after removing the solvent was dissolved in 100 ml of toluene, washed with a 0.5 N hydrochloric acid solution, washed with a saturated saline solution, dried over magnesium sulfate, and filtered. After concentrating the obtained filtrate with a rotary evaporator, the concentrate was further dried under vacuum to obtain 4-DPEHE (19.0 g, yield 76%, HPLC purity 97%). The ¹ H NMR spectrum data 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 that 25.3 g (0.096 mol) of 2,2'-diphenyletherdicarboxylic acid was used instead of 25.3 g of 4,4'-diphenyletherdicarboxylic acid, a method similar to that for synthesizing the acid chloride (A) was used. There was obtained 27.8 g (0.094 mol, 98% yield) of 2,2'-diphenyletherdicarboxylic acid chloride.

A method similar to that for synthesizing 4-DPEHE except that 15.3 g (0.052 mol) of 2,2′-diphenyletherdicarboxylic acid chloride was used instead of 15.3 g (0.052 mol) of acid chloride (A). Thus, 2-DPEHE (19.5 g, yield 78%, HPLC purity 97%) was obtained. The ¹ H NMR spectrum data of the obtained 2-DPEHE was 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 The mixture was placed in a glass container, heated to 85 ° C., and stirred. Next, the pressure in the reaction system in the heated and stirred state was reduced, and stirring was continued for 5 hours while removing water from the reaction system. Thereafter, the obtained liquid was cooled, purified using silica gel column chromatography, and concentrated to obtain 19.7 g (yield 53%) of 16.0 g (yield 53%) of 6-hydroxyhexyl methacrylate.
-Process 2-
Next, a solution containing 3.0 g (0.01 mol) of the acid chloride (A), 70 ml of methylene chloride, and 0.001 g of di-tertbutylmethylphenol was added to another glass container while stirring the solution. A solution obtained by dissolving 4.1 g (0.022 mol) of the above-mentioned 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 used. The solution was slowly dropped over 1 hour. After 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 removing the solvent was dissolved in 100 ml of toluene, washed with a 0.5 N hydrochloric acid solution, washed with a saturated saline solution, dried over magnesium sulfate, and filtered. The obtained filtrate was again concentrated by a rotary evaporator, and the concentrated solution was further dried in vacuo to obtain 4-DPEHH (4.6 g, 78%, 98% HPLC purity). The ¹ H NMR spectrum data of the obtained 4-DPEHH was 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, And cooled to 0 ° C. Next, a solution of 44.8 g (0.2 mol) of the acid chloride (A) dissolved in methylene chloride (200 ml) was slowly added dropwise to the solution over 2 hours. After the solution obtained after the dropwise addition was stirred for another 1 hour, water was added, and the solvent was removed using a rotary evaporator. The residue obtained after removing the solvent was dissolved in 100 ml of toluene, washed with a 0.5 N hydrochloric acid solution, washed with a saturated saline solution, dried over magnesium sulfate, and filtered. The obtained filtrate was again concentrated by a rotary evaporator, and the concentrated solution was purified by silica gel column chromatography to obtain 41.6 g of 4,4'-bis (2-hydroxyethoxycarbonyl) diphenyl ether (yield: 60%). .

In a solution obtained by dissolving 34.6 g (0.1 mol) of the obtained 4,4′-bis (2-hydroxyethoxycarbonyl) diphenyl ether and 3.2 g (5 mmol) of dibutyltin dilaurate in 100 ml of anhydrous dimethylformamide. And 39.8 g (0.2 mol) of 2- (2-methacryloyloxyethyloxy) ethyl isocyanate were further added, and the mixture was stirred at room temperature for 3 hours. 100 ml of methylene chloride was added to the solution after stirring, and the mixture was washed three times with distilled water using a separating funnel, and the methylene chloride layer was dried using magnesium sulfate. After drying, magnesium sulfate was filtered off, the filtrate was concentrated by a rotary evaporator, and the concentrate was further dried in vacuum to obtain 4-DPEUE (yield: 70.3 g, 95%, HPLC purity: 96%). . The ¹ H NMR spectrum data of the obtained 4-DPEUE was 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>
To 12.8 g of glycidyl methacrylate (0.09 mol), 12.9 g (0.05 mol) of 4,4'-diphenyletherdicarboxylic 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 form a uniform solution. Next, this solution was transferred to a separating funnel, washed three times with 40 ml of a 10 wt% aqueous solution of potassium carbonate, and further three times with distilled water, and then an ethyl acetate layer was recovered. Thereafter, magnesium sulfate was added to the collected 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 with a rotary evaporator to obtain a concentrate. The concentrate was further dried in vacuo to give 4-DPEGMA (22.8 g, 84% yield, 95% HPLC purity). The ¹ H NMR spectrum data of the obtained 4-DPEGMA was as follows.
^{1 H NMR δ1.93 (s, 6H} ), 3.90 (d, 0.8H), 4.30~4.70 (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 is added. 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, after stirring the reaction solution for 5 hours, the reaction solution was acidified using a 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and the precipitated solid was washed with water. The solid (compound) obtained after the washing was vacuum dried to obtain 4,4′-dicarboxydiphenyl sulfide (45.5 g, 83% yield).

  Next, 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′-diphenylsulfidedicarboxylic acid chloride was synthesized in the same manner as in the synthesis method of (2).

Next, a method similar to that for synthesizing 4-DPEHE was used, except that 16.1 g (0.052 mol) of 4,4′-diphenylsulfidedicarboxylic acid chloride was used instead of 15.3 g of the acid chloride (A). -DPSHE (18.9 g, 73% yield, 91% HPLC purity) was obtained. The ¹ H NMR spectrum data 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>
Except for using 27.2 g (0.096 mol) of 2,2-bis (4-carboxyphenyl) propane synthesized by a synthesis method described in British Patent GB 753384 instead of 25.3 g of 4,4′-diphenyl ether dicarboxylic acid. In the same manner as in the method for synthesizing the acid chloride (A), 29.6 g (96% yield) of 2,2-bis (4-chlorocarbonylphenyl) propane was obtained.

Next, the same method as in the synthesis method 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 the acid chloride (A). By the method, 4-DPAHE (19.3 g, 73% yield, 92% HPLC purity) was obtained. The data of the obtained ¹ H NMR spectrum of 4-DPAHE was as follows.
¹ H NMR δ 1.64 (s, 6H), 1.93 (s, 6H), 4.53-4.64 (m, 8H), 5.59 (s, 2H), 6.12 (s, 2H) ), 7.22 (d, 4H), 7.90 (d, 4H)

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

3. Polymerization initiator The polymerization initiator used in Examples and Comparative Examples is 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 comprising 100 parts by mass of PBA-1, 10 parts by mass of M1, and 0.1 part by mass of DEPT;
A powder material comprising 100 parts by mass of PBMA and 0.1 parts by mass of BPO;
Was mixed to obtain a mucosal conditioner. The kneading time is 80 seconds, the initial viscosity (30 seconds) is 80 Pas, the initial viscosity (90 seconds) is 460 Pas, the consistency is 35, both the initial hardness and the hardness after one month are 11, the thickness change rate is 35%, and the tearing strength. Is 6.2 N / mm. Preferred physical properties of the dental mucosal conditioner of the present invention include a kneading time of 100 seconds or less, an initial viscosity of 300 Pas or less, a consistency of 60 or less, a hardness of 20 or less, a change rate of 50% or less, and a tear strength of 4. Since it is 5 N / m or more, and the initial viscosity of the mucosal conditioner of Example 1 is low, 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.

(Examples 2 to 9)
A mucosal conditioner was prepared and evaluated in the same manner as in Example 1 except that the type and the 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 mucosal conditioner was prepared and evaluated in the same manner as in Example 1 except that the type of the plasticizer was changed as shown in Table 4. The evaluation results are shown in Table 5.

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

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

(Examples 18 to 20)
A mucosal conditioner 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 mucosal conditioner was prepared and evaluated in the same manner as in Example 1 except that the polymerization initiator was changed as shown in Table 4. The evaluation results are shown in Table 5.

  Since the mucosal conditioners of Examples 2 to 21 have a low initial viscosity, they have good initial fluidity and good operability. Furthermore, since the tear strength is high and the rate of change in thickness is small, the durability is excellent.

(Comparative Example 1)
A mucosal conditioner was prepared and evaluated in the same manner as in Example 1 except that no radical polymerizable monomer was added. The compositions and evaluation results are shown in Tables 6 and 7.

(Comparative Example 2)
A mucosal conditioner 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 and 4)
A mucosal conditioner was prepared and evaluated in the same manner as in Example 1 except that the radical polymerizable monomer was changed as shown in Table 6. The evaluation results are shown in Table 7.

  Since the mucosal conditioners of Comparative Examples 1 and 2 do not contain a radical polymerizable monomer, they have low tear strength and poor durability. Furthermore, the mucosal conditioner of Comparative Example 2 has a large change in hardness one month after the initial hardness due to the elution of the plasticizer over time, and the softness is not maintained. The mucosal conditioner of Comparative Example 3 uses a conventional radically polymerizable monomer. Since the radical polymerizable monomer has low viscosity, it has good initial fluidity and good operability. On the other hand, since it has poor mechanical strength, it has low tear strength and poor durability. The mucosal conditioner of Comparative Example 4 uses a conventional radically polymerizable monomer. The radical polymerizable monomer has excellent mechanical strength, low tear strength and excellent durability, while high viscosity has poor initial fluidity and poor operability.

Claims (7)

i) plasticizer and a liquid material containing a radical polymerizable monomer which is shown by the following general formula (1), ii) (meth) packaging is divided into a powder material containing an acrylic non-crosslinked polymer, Has been saved,
Both polymerization initiator wherein i) the liquid material and the ii) powder material, or be included in either,
A dental mucosal conditioner used as a paste in which both materials are mixed when used.

[In the general formula (1), X represents —O— , and Ar ¹ and Ar ² each represent an unsubstituted aromatic group having any valence selected from divalent to tetravalent. May be the same or different, and L ¹ and L ² each have a main chain atom number in the range of 2 to 60 and are selected from divalent to tetravalent And each may be the same or different, and R ¹ and R ² each represent hydrogen or a methyl group. Further, m1, m2, n1 and n2 are each an integer selected from the range of 1-3. ] Dental tissue conditioner according to claim 1, wherein at least one of L ¹ and L ² in the general formula (1) is Nde contains a hydroxyl group. Dental tissue conditioner according to claim 1 or 2, wherein the radical polymerizable monomer represented by the general formula (1) is a polymerizable monomer 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 in the general formula (1). ] The dental plasticizer according to any one of claims 1 to 3, wherein the plasticizer is a liquid polymer having a mass average molecular weight in a range of 1,000 to 10,000. The (meth) dental tissue conditioner according to any one of claims 1 to 4 glass transition temperature of the acrylic-based non-crosslinked polymer is in the range of 0 to 60 ° C.. The dental mucosa conditioner according to any one of claims 1 to 5, wherein the ii) powder material further includes an inorganic powder. Wherein i) the liquid material, a dental tissue conditioner according to any one of claims 1 to 6, characterized in that further comprising a water-soluble organic solvent.