JP2013087076A - Conditioning material for dental mucous membrane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mucous membrane conditioning material by kneading a powder material and a liquid material, with high operability and handling immediately after kneading, and capability in forming a sufficiently thick layer on the mucous membrane of a denture base, and maintaining the thickness for a long period, and further with high tearing strength, so that it can be used for a long period of time.SOLUTION: The mucous membrane conditioning material layer with a sufficient thickness can be formed by blending a porous organic crosslinking polymer with a (meth)acrylic non-crosslinking polymer particles and a plasticizer, thereby suppressing initial viscosity of the mucous membrane conditioning material resulting in the elevation of operability and a handling property immediately after kneading, and moderately increasing the viscosity of the mucous membrane conditioning material after serving on an artificial tooth. Furthermore, the high tearing strength is developed and the thickness is maintained over long period because the polymer component and the plasticizer component in the mucous membrane conditioning material are permeated and kept in the fine pores of the porous organic crosslinking polymer.

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, the elution of the plasticizer is suppressed, but the mucosa-adjusting material after polymerization becomes hard and difficult to use for a long time.

  In addition, all of the mucosa-adjusting materials disclosed in Patent Documents 1 to 3 have a high flow period for placing on the denture after kneading the powder material and the liquid material. When it is inserted into the oral cavity, it is pushed out from between the denture and the inner surface of the oral cavity due to the mounting pressure, and the mucous membrane adjusting material layer cannot be formed with a sufficient thickness.

  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.

  Furthermore, with the mucosa preparation material of Patent Document 4, it is possible to ensure a certain period of initial high flow after the kneading of the powder material and the liquid material so that the paste can be placed on the denture base mucosa surface with a sufficient margin. It has also been proposed to blend a powdered crosslinked polymer. That is, immediately after the powder material and the liquid material are kneaded and made into a uniform paste, the fluidity of the paste is high. Then, as the liquid material penetrates into the powder material, the (meth) acrylic type The non-crosslinked polymer powder begins to dissolve in the liquid material, and its viscoelasticity increases rapidly. Therefore, while maintaining the fluidity of the paste, it must be placed on the denture basement mucosal surface and inserted into the oral cavity for shaping, but only the (meth) acrylic non-crosslinked polymer powder is used. In this case, the dissolution rate in the liquid material was too high, and the high flow period required for the above-described preparation operation could not be secured sufficiently (in order to have sufficient margin for the operation in clinical practice, a uniform paste was formed. It is desirable that the viscosity be suppressed to 300 Pas (23 ° C.) or less until about 2 minutes later.

  However, since the mucosa preparation material blended with the above-mentioned cross-linked polymer does not dissolve at all, the cross-linked polymer is slow to swell, so that when the denture is inserted into the oral cavity, the mucosa preparation material layer has a sufficient thickness due to insufficient viscoelasticity. It was difficult to form, and when a strong occlusal pressure was applied during use of the denture, it was easily pushed out from the denture mucosa surface. In Patent Document 5, in order to solve these problems, a high flow period is ensured by blending (meth) acrylic non-crosslinked polymer particles having a glass transition temperature of 80 to 120 ° C. without using a crosslinked polymer. On the other hand, there has been proposed a mucosa-adjusting material that can form a layer with a sufficient thickness on the denture mucosa surface and is difficult to be pushed out even when the denture is used.

  Patent Document 6 discloses a dental adhesive containing an acidic group-containing polymerizable monomer, a polymerization initiator, and a porous organic filler. In this adhesive, a high adhesive force can be obtained when the monomer is polymerized in the pores of the porous organic filler.

  Patent Document 7 discloses a dental composition comprising a powder material containing a (meth) acrylic non-crosslinked polymer, porous particles supporting a catalyst, and a liquid material containing a radical polymerizable monomer and a catalyst. Has been. In this dental composition, the catalyst blended in the powder material is supported on the porous particles, so that the powder material is not sticky and the operability is improved. This composition is suitable as a dental resin cement and a dental adhesive.

Japanese Patent No. 2905433 Japanese Patent No. 2755424 Japanese Patent No. 3479274 Japanese Patent No. 4693434 JP 2011-132189 A JP 2009-179612 A JP 2004-203773 A

  The problem to be solved by the present invention is a mucosal preparation material for kneading a powder material and a liquid material, which has high operability and handling properties immediately after kneading and has a sufficient thickness and is layered on the mucosal surface of the denture base. It is an object of the present invention to provide a mucosa-adjusting material that can be formed, maintains a thickness 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 present inventors have formulated a porous organic crosslinked polymer in addition to a specific non-crosslinked polymer and a plasticizer, so that the initial viscosity of the mucosa-adjusting material is suppressed and operability immediately after kneading. It was also found that the handling property was improved and the viscosity of the mucosa-adjusting material increased moderately after being placed on the denture, so that the layer of the mucosa-adjusting material could be formed with a sufficient thickness. Furthermore, since the polymer component and the plasticizer component in the mucosa-adjusting material penetrate and are retained in the pores of the porous organic crosslinked polymer, the interaction between the porous organic crosslinked polymer and the non-crosslinked polymer (so-called anchor) As a result of increasing the effect, the present inventors have found that the film has high tear strength and the thickness is maintained over a long period of time, and the present invention has been completed.

  The present invention for solving the above problems is described below.

[1] In a dental mucosa adjusting material comprising (1) a powder material and (2) a liquid material and kneading both materials at the time of use,
(1) The powder material comprises a) (meth) acrylic non-crosslinked polymer particles, and b) a porous organic crosslinked polymer,
(2) The liquid material comprises a plasticizer,
A mucosal conditioner for dental use characterized by the above.

  [2] b) The porous organic cross-linked polymer has an average particle size of 2 to 50 μm, an average pore size of 1 to 100 nm, and an oil absorption amount of purified sesame oil measured according to JIS K5101-13 of 0.8 ml / g or more. The dental mucosa preparation material according to [1].

  [3] (1) The powder material comprises 5 to 40 parts by mass of b) a porous organic crosslinked polymer with respect to 100 parts by mass of a) (meth) acrylic non-crosslinked polymer particles [1] or [2 ] The dental mucosa preparation material described in the above.

  [4] The dental mucosa adjusting material according to [1] to [3], wherein the plasticizer includes a liquid polymer having a mass average molecular weight of 1000 to 10,000.

  [5] The dental mucosa preparation material according to [1] to [4], in which a) (meth) acrylic non-crosslinked polymer particles have a glass transition temperature of 0 to 60 ° C. and an average particle diameter of 10 to 100 μm.

  [6] (2) The dental mucosa preparation material according to [1] to [5], wherein the liquid material contains a water-soluble organic solvent.

  In the initial stage after the kneading of the powder material and the liquid material, the mucosa preparation material of the present invention has a sufficient high flow period in which the paste can be easily placed on the denture base mucosa surface due to the presence of the porous organic crosslinked polymer that does not dissolve. Time can be secured and workability is good. Further, since the paste penetrates into the pores of the porous organic crosslinked polymer and suddenly develops viscoelasticity from the end of the high flow period, after the paste is placed on the denture basement mucosa, the denture is placed in the oral cavity at an early stage. Even if it is inserted, the layer can be formed with a sufficient thickness as a mucosa-adjusting material.

  Moreover, since the porous organic crosslinked polymer has an anchoring effect in the mucosa preparation material, the above mucosa preparation material layer is difficult to be pushed out between the denture and the mucosal surface even when a strong occlusal pressure is applied during use of the denture. While being held well on the mucosal surface over a period of time, high tear strength can be obtained and it can be used with good durability for a long time.

  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 (1) a powder material and (2) a liquid material, which will be described below. This mucosa-adjusting material is used by kneading (1) a powder material and (2) a liquid material at the time of use.

(1) Powder material The powder material comprises a) (meth) acrylic non-crosslinked polymer particles, and b) a porous organic crosslinked polymer.

  a) (Meth) acrylic non-crosslinked polymer particles are homopolymers obtained by homopolymerizing a polymerizable monomer having an acrylic group or a methacrylic group as a polymerizable group (hereinafter referred to as (meth) acrylic monomer). Polymers, copolymers obtained by copolymerizing two or more different (meth) acrylic monomers, and (meth) acrylic monomers and polymerizable monomers other than (meth) acrylic monomers, The copolymer obtained by copolymerizing (however, 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, a) (meth) acrylic non-crosslinked polymer particles need 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 particles preferably have a glass transition temperature (hereinafter also referred to as Tg) 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 5 to 60 μm, and particularly preferably 30 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, those having 50,000 to 1,000,000 are more preferable, and those having 200,000 to 600,000 are most 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.

  b) As the porous organic crosslinked polymer, any crosslinked polymer can be used without any limitation as long as it is a crosslinked organic polymer having a large number of pores on the surface. Even if porous inorganic particles such as silica are used instead of the porous organic crosslinked polymer, high mechanical strength cannot be obtained because of low affinity with the (meth) acrylic non-crosslinked polymer. In addition, the organic crosslinked polymer that is not porous does not exhibit the anchor effect between the pores and the non-crosslinked polymer, so that high mechanical strength cannot be obtained.

  The material of the porous organic crosslinked polymer is not particularly limited as long as it is a crosslinked organic polymer. From the viewpoint of affinity with the (meth) acrylic non-crosslinked polymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, crosslinked Cross-linked polyalkyl (meth) acrylates such as polymethyl acrylate, polystyrene, polyvinyl chloride and the like are preferable. Moreover, as such a porous organic crosslinked polymer, polymers described in JP-A No. 2002-256005 and JP-A No. 2002-265529 can be used. Furthermore, as such a porous organic crosslinked polymer, commercially available “Technopolymer MBP-8” (Sekisui Plastics Co., Ltd.) and the like can be used.

  The average pore diameter of the porous organic crosslinked polymer is preferably 1 to 100 nm, particularly preferably 5 to 50 nm, and most preferably 10 to 30 nm. The average pore diameter represents the average diameter of the pores formed on the surface of the primary particles of the porous organic crosslinked polymer, not the aggregated pores of the secondary particles formed by aggregation of the porous organic crosslinked polymer particles. . The average pore diameter can be obtained by calculation from the pore distribution of particles measured using a mercury intrusion method pore distribution measuring apparatus.

  When the average pore size is smaller than 1 nm, the amount of (meth) acrylic non-crosslinked polymer and plasticizer (hereinafter also referred to as “matrix”) intruded into the pores is reduced, and appropriate viscoelasticity is obtained. However, there is a tendency that a sufficient thickness of the mucosa-adjusting material cannot be formed, the anchoring effect between the crosslinked polymer and the matrix is lowered, and the tear strength of the mucosa-adjusting material is lowered. Even when the average pore diameter is larger than 100 nm, the anchor effect with the matrix is lowered, and the tear strength of the mucosa-adjusting material tends to be lowered.

  The particle diameter of the porous organic crosslinked polymer is not particularly limited, but the average particle diameter is preferably 1 to 50 μm, particularly preferably 3 to 30 μm, and most preferably 5 to 15 μm. In addition, this average particle diameter represents the average particle diameter of the primary particle of a porous organic crosslinked polymer particle. The average particle diameter is measured using a particle size distribution measuring apparatus by a laser diffraction / scattering method.

  When the average particle size is smaller than 1 μm, the initial viscosity of the mucosa-adjusting material becomes high, and the fluidity necessary for placing on the denture cannot be obtained and the operability is lowered. Even when the average particle size is larger than 50 μm, the initial viscosity of the mucosa-adjusting material is increased, and the fluidity necessary for placing on the denture cannot be obtained, resulting in a decrease in operability. The particle shape is not particularly limited, and either pulverized particles or spherical particles can be used.

  The oil absorption amount of the porous organic crosslinked polymer is preferably 0.8 ml / g or more, more preferably 1.3 to 5.0 ml / g. The oil absorption is measured by the refined linseed oil method described in JIS K5101-13-1.

  When the amount of oil absorption is less than 0.8 ml / g, the amount of (meth) acrylic non-crosslinked polymer and plasticizer penetrating into the pores is reduced, and adequate viscoelasticity cannot be obtained, resulting in a sufficiently thick mucosa. There is a tendency that the adjustment material cannot be formed, the anchor effect between the crosslinked polymer and the matrix is lowered, and the tear strength of the mucosa adjustment material is lowered.

  These porous organic crosslinked polymers may be used in combination with a plurality of different materials, average particle diameters, average pore diameters, and the like as necessary.

  The blending ratio of a) (meth) acrylic non-crosslinked polymer particles and b) porous organic crosslinked polymer in the powder material is not particularly limited and may be set as appropriate. A) (meth) acrylic The b) porous organic crosslinked polymer is preferably 5 to 40 parts by mass and particularly preferably 10 to 30 parts by mass with respect to 100 parts by mass of the non-crosslinked polymer particles. When the amount is less than 5 parts by mass, it is difficult to obtain an anchor effect with the matrix. When it exceeds 40 parts by mass, the viscosity of the composition increases during kneading and the operability decreases.

(2) Liquid material The liquid material contains a plasticizer.

  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 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. Moreover, since the liquid polymer with a molecular weight of 500 or less is easily eluted in the oral cavity and easily moves to the denture base, it is difficult to sufficiently obtain the effects of the present invention. 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. It differs from polymer-based non-crosslinked polymer particles.

  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 particles used in 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.

  In addition to the plasticizer, the liquid material in the mucosa preparation 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 the plasticizer is easy to penetrate when the (meth) acrylic powder polymer blended in the powder material is dissolved or swollen by blending a water-soluble organic solvent. 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 to 30 parts by mass, and 3 to 20 parts by mass with respect to 100 parts by mass of the plasticizer. Part is particularly preferred. When the amount is less than 1 part by mass, the above operability cannot be improved. When it exceeds 30 mass parts, the handleability and odor of a composition may deteriorate, or the physical property change of a composition after an organic solvent elutes from a composition may become large. When the amount is 3 to 20 parts by mass, particularly good operational feeling can be obtained.

  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 of glass transition point (Tg) Tg was measured using a differential scanning calorimeter (DSC6200 / Seiko). The initial temperature increase was continued at a rate of 10 ° C./min up to about 30 ° C. above the approximate Tg, where it was held for 5 minutes and then decreased at 50 ° C./min. Next, the DSC curve obtained immediately after reheating was used. A base line extension line and an extension line at a steep descending position of the endothermic region due to the glass transition were drawn, and the temperature at the intersection of the 1/2 straight line between these extension lines and the DSC curve was determined as Tg.

(2) 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 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).

(3) Kneading time measurement method Add 1.1 parts by mass of powder material to a rubber cup in which the liquid material has been measured in advance, and start 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.

(4) Initial viscosity measurement method at the time of kneading It measured using the dynamic viscoelasticity measuring apparatus CS rheometer "CVO120HR" (made 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 was measured 30 seconds and 90 seconds after the time (kneading time) when a uniform paste was obtained. In the mucous membrane adjusting material, the viscosity after 90 seconds is preferably 100 to 300 Pas in order to ensure good operability for providing good dentures after kneading the powder material and the liquid material. Is more preferably 170 to 250 Pas.

(5) Volume average particle diameter It measured using Beckman Coulter LS230. The measurement was carried out using water as a dispersion medium, treated with ultrasonic waves for 3 minutes or more before measurement, and then immediately measured.

(6) Oil absorption amount It measured based on JISK5101-13-1 (oil absorption amount). At 23 ° C., the sample was placed on a measuring plate, and oil was gradually added to the refined sesame from the burette four or five times at a time, and each time the oil was kneaded into the refined sesame with a pallet knife. Repeat these steps until the oil and sample lumps are formed in the refined sesame, and then repeat by dropping one drop at a time and kneading completely until the paste becomes smooth and the end point is reached. . The amount of oil used in the refined sesame used up to the end point was measured to calculate the oil absorption.

(7) 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.

(8) 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.

(9) 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 (3) Method of measuring kneading time, pouring a paste after 10 seconds from the time when a uniform paste was obtained, and another one from above 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

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

1. Powder Material Components The a) (meth) acrylic non-crosslinked polymer particles in the powder materials used in Examples and Comparative Examples are as shown in Table 1 below.

The b) porous organic crosslinked polymer in the powder materials used in Examples and Comparative Examples is as shown in Table 2 below.
Table 3 shows nonporous crosslinked polymers. This was used in the comparative example.

2. Liquid Material Components The plasticizers as the main components in the liquid materials used in Examples and Comparative Examples are as shown in Table 4 below. 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.

Example 1
A powder material consisting of 100 parts by mass of PBMA and 5 parts by mass of MBP;
A liquid material comprising only 100 parts by mass of PBA-1,
To obtain a mucosa-adjusting material. Kneading time is 90 seconds, initial viscosity (30 seconds) is 53 Pas, initial viscosity (90 seconds) is 225 Pas, consistency is 34, initial hardness and hardness after 1 month are both 11, thickness change rate is 41%, tear strength Was 4.9 N / mm.

(Example 2-12)
A mucosa-adjusting material was prepared in the same manner as in Example 1 except that the type and blending amount of the plasticizer, (meth) acrylic non-crosslinked polymer particles and porous organic crosslinked polymer were changed as shown in Table 5. evaluated. The evaluation results are shown in Table 7.

(Comparative Example 1-2)
Comparative Example 1 was prepared and evaluated in the same manner as Example 1 except that MBP was not blended. In Comparative Example 2, a mucosal preparation was prepared and evaluated in the same manner as in Example 1 except that 25 parts by mass of PMMA-X was used instead of 5 parts by mass of MBP. The compositions and evaluation results are shown in Tables 6 and 8.

(Example 13)
A powder material consisting of 100 parts by mass of PBMA and 25 parts by mass of MBP;
A liquid material composed of 100 parts by mass of PBA-1 and 2 parts by mass of ethanol;
To obtain a mucosa-adjusting material. These compositions and evaluation results are shown in Tables 5 and 7.

(Examples 14-15)
A mucosa-adjusting material was prepared and evaluated in the same manner as in Example 13 except that the blending amount of ethanol was changed as shown in Table 5. The evaluation results are shown in Table 7.

(Comparative Example 3)
In Comparative Example 3, a mucosal preparation was prepared and evaluated in the same manner as Example 14 except that MBP was not blended. The compositions and evaluation results are shown in Tables 6 and 8.

  Since the mucosa-adjusting material of Example 1-12 has a low initial viscosity, the initial fluidity is good and the operability is good. Moreover, even if the initial viscosity is low, the consistency is small, so that the mucosa-adjusting material can be formed with a sufficient thickness. Furthermore, these mucosa-adjusting materials are excellent in durability because they have high tear strength and a small rate of change in thickness.

  Since the mucosa-adjusting materials of Comparative Examples 1 and 3 do not contain a porous organic cross-linked polymer, the initial viscosity is high and the operability is poor. In addition, the tear strength is low and the durability is poor. Since the mucosa-adjusting material of Comparative Example 2 contains a non-porous cross-linked polymer in place of the porous organic cross-linked polymer, the initial viscosity is low but the consistency is large, and the mucosa-adjusting material can be formed with a sufficient thickness. Can not. In addition, the tear strength is low and the durability is poor.

  In the mucosa-adjusting material of Examples 13-15, since the water-soluble organic solvent is blended in the liquid material, the kneading time is shortened.

Claims (6)

(1) powder material, and (2) liquid material,
In the dental mucosa adjusting material used by kneading both materials at the time of use,
(1) The powder material comprises a) (meth) acrylic non-crosslinked polymer particles, and b) a porous organic crosslinked polymer,
(2) The liquid material comprises a plasticizer,
A mucosal conditioner for dental use characterized by the above.   b) The porous organic crosslinked polymer has an average particle size of 2 to 50 μm, an average pore size of 1 to 100 nm, and an oil absorption of the purified sesame oil measured according to JIS K5101-13 of 0.8 ml / g or more. The dental mucosa preparation material described in 1.   The dental material according to claim 1 or 2, wherein (1) the powder material comprises 5 to 40 parts by mass of b) a porous organic crosslinked polymer with respect to 100 parts by mass of a) (meth) acrylic non-crosslinked polymer particles. Mucosa adjustment material.   The dental mucosa-adjusting material according to claim 1, wherein the plasticizer contains a liquid polymer having a mass average molecular weight of 1000 to 10,000.   5. The dental mucosa-adjusting material according to claim 1, wherein the (meth) acrylic non-crosslinked polymer particles have a glass transition temperature of 0 to 60 ° C. and an average particle diameter of 10 to 100 μm.   (2) The dental mucosa-adjusting material according to any one of claims 1 to 5, wherein the liquid material contains a water-soluble organic solvent.