JP7367935B2 - Kit for preparing curable composition for denture base - Google Patents

Description

The present invention provides a curable composition for denture bases, specifically a curable composition for denture bases used as a denture base resin, a hard lining material for denture bases, a denture base repair resin, etc. Regarding the kit.

A curable composition for denture bases is a composition used for manufacturing and repairing denture bases, and materials using the composition include resins for denture bases used when newly manufacturing dentures, Hard lining materials for denture bases are used to line denture bases that no longer fit the patient's oral mucosa due to long-term use, and to improve the fit. Resins for repairing denture bases and the like used for repairing dentures and the like are known.

As a curable composition for a denture base, a curable composition containing a polymerizable monomer such as methyl methacrylate, a (meth)acrylic polymer such as polymethyl methacrylate or polyethyl methacrylate, and a polymerization initiator is generally used. . Such a curable composition is a powder-liquid type composed of (1) a liquid agent containing a polymerizable monomer as a main component and a powder agent containing a (meth)acrylic polymer and a radical initiator as main components. (See Patent Documents 1 and 2.) (2) A paste made by blending a polymerizable monomer, a filler such as a (meth)acrylate polymer, and a thermal polymerization catalyst and/or a photopolymerization catalyst. (see Patent Document 3), or (3) a polymerizable monomer, a (meth)acrylic polymer, and a radical polymerization initiator or polymerization accelerator (does not have polymerization activity within a single paste, but has two It is provided as a two-paste type (see Patent Documents 4 and 5) consisting of a combination of two pastes, each of which is blended so that polymerizable species are generated when the pastes are mixed.

One-paste denture base materials that use photopolymerization catalysts or thermal polymerization catalysts do not require measuring or mixing, and can maintain paste properties until heat or light is applied, and polymerization can begin at any time. Although it has excellent operability, it requires equipment such as a polymerization vessel for curing. On the other hand, two-paste denture base materials using chemical polymerization initiators are usually provided as a kit consisting of a combination of two pastes, and although measuring and mixing is required, Since polymerization is started by mixing, it has the advantage that equipment such as a polymerization vessel is not required.

As an example of a two-paste type denture base material, Patent Document 4 describes methacrylate having at least one unsaturated double bond and no urethane bond, and methacrylate having at least one unsaturated double bond and urethane bond. A first component consisting of a methacrylate having a bond, a polyurethane powder having a cross bond, a filler, and a chemical polymerization initiator; a methacrylate having at least one unsaturated double bond and no urethane bond; Disclosed is a denture base repair material composition comprising a second component consisting of a methacrylate having at least one unsaturated double bond and a urethane bond, a polyurethane powder having a cross bond, a filler, and a polymerization accelerator. has been done. The above-mentioned composition is said to have excellent operability because it has a sufficient operating margin, and furthermore, because the cured product has appropriate elasticity, there is less damage to the repaired area.

Further, Patent Document 5 describes a paste (i) containing a (meth)acrylic polymer and a fluorine-containing (meth)acrylic acid polymerizable monomer in which the solubility of the (meth)acrylic polymer is less than 20% by mass; A denture comprising a paste (ii) containing a (meth)acrylic polymerizable monomer having a solubility of the (meth)acrylic polymer of 20% by mass or more and a filler, and a polymerization initiator contained in at least one of the pastes. A floor covering material is disclosed. The above-mentioned denture base lining material can increase the viscosity over time to the same extent as the powder-liquid type when mixed with the paste, has excellent operability, and has excellent storage stability of the paste and color resistance of the cured product. It is said to be excellent. In addition, when renovating dentures by the direct method using a powder-liquid type, the change in paste properties over time after mixing the powder-liquid is effectively used to facilitate clinical or technical operations. The advantage is that you can. Specifically, it is possible to perform plating work during the high-flow period immediately after mixing, then perform shaping work when the mochi is in a state where it is plastically deformed, and then further adjustment work can be performed after that when the mochi is in a state where it is not plastically deformed. It is said to have benefits.

Japanese Patent Application Publication No. 11-335222 Special Publication No. 4-042364 Japanese Patent Application Publication No. 2002-104912 Japanese Patent Application Publication No. 2000-175941 WO2015/105103 Japanese Patent Application Publication No. 2013-87076 Japanese Patent Application Publication No. 2004-203773 Japanese Patent Application Publication No. 2009-179612

As mentioned above, some of the two-paste type denture base materials are known to have good operability and storage stability, and to have appropriate elasticity. However, the resulting cured product was not always satisfactory in terms of strength and toughness. Furthermore, depending on the filling material used, it may be difficult to control the paste properties, and the strength of the resulting cured product may be low.

In addition, regarding the paste properties, due to the characteristics of the two-paste type denture base hardening composition, it is often handled with gloved hands when mixing or building up, so be careful not to stick to the gloves. It is necessary to suppress stickiness. On the other hand, when used for making a new denture, it is necessary to adhere to a plaster model, and when used for lining or repairing a denture base, it is necessary to adhere to the denture. In other words, a two-paste type denture base curable composition is required to have paste properties that have appropriate viscosity so that it does not adhere to gloves but adheres to plaster models and dentures.

In view of these circumstances, an object of the present invention is to provide a two-paste type curable composition for denture bases, in which the obtained cured product has high strength and toughness, and furthermore, the paste has good operability. .

The cured product of the curable composition for denture bases is a composite material of a (meth)acrylic polymer used as a filler with a low elastic modulus and a cured product of a polymerizable monomer that serves as a matrix. It is thought that the interfacial state of the material affects the toughness. Therefore, the present inventors thought that by using a porous organic crosslinked polymer as an organic filler, it would be possible to increase the strength by crosslinking, and conducted extensive studies.

As a result, (1) it may be possible to obtain the desired effect by using a porous organic cross-linked polymer, and (2) the desired effect may not be obtained depending on the type of porous organic cross-linked polymer. , (3) It was found that when a large amount of non-porous organic crosslinked polymer coexists, the hardness of the paste tends to change during storage. As a result of further studies based on these findings, the bending strength (strength ) and breaking energy (toughness), and can also improve paste properties, and even when a porous organic crosslinked polymer is used for only one of the two pastes, it is possible to mix the two pastes. It has been found that the above effects can be obtained if the resulting curable composition for denture base contains a specific amount of monomer-absorbing porous organic crosslinked polymer. Furthermore, the present inventors have discovered that by suppressing the content of the non-porous organic crosslinked polymer to a specific amount or less, changes in paste hardness during storage are suppressed and storage stability is improved, and the present invention has been completed.

That is, the first aspect of the present invention is a kit for preparing a curable composition for a denture base by mixing these compositions, which comprises a combination of a first composition and a second composition. ,
The curable composition for denture base comprises a (meth)acrylic polymerizable monomer [A], monomer-absorbing porous organic crosslinked polymer particles (b1), non-porous organic crosslinked polymer particles (b2), and non-crosslinked polymer particles. (b3) an organic filler [B] comprising at least one selected from the group consisting of; and a polymerization initiator [C];
The first composition and the second composition both contain a (meth)acrylic polymerizable monomer [A] and an organic filler [B], and [A] and [B] contained in the first composition. ] and [A] and [B] contained in the second composition are respectively [A ¹ ] and [B ^{1 ] and [A 2 ]} and [B ² ], [A ¹ ] and [A ² ] may be different from each other, and [B ¹ ] and [B ² ] may be different from each other,
The [B ¹ ] includes monomer-absorbing porous organic crosslinked polymer particles (b1 ¹ ) capable of absorbing the [A ¹ ],
The polymerization initiator [C] is
(1) It is composed of a single component, and the single component is blended in either the first composition or the second composition, or (2) It is composed of a plurality of components, and the Each of the plurality of constituent components is blended into either the first composition or the second composition in such a manner that it does not exhibit polymerization activity in the first composition or the second composition. This is a kit for preparing a curable composition for denture base.

In the kit for preparing a curable composition for denture base of the present invention, the monomer-absorbing porous organic crosslinked polymer particles ( Unit amount of b1): Amount of (meth)acrylic polymerizable monomer [A ¹ ] contained in the first composition absorbed per g-B (unit: g): g-A (unit: g) It is preferable that the absorption amount defined by: R _Ab = {(g-A)/(g-B)} is 1.5 or more.

In addition, the curable composition for denture bases, which is the object of preparation, contains 20 to 20 parts of monomer-absorbing porous organic crosslinked polymer particles (b1) per 100 parts by mass of the (meth)acrylic polymerizable monomer [A]. 80 parts by mass, the first composition contains 20 to 200 parts by mass of [B ¹ ] per 100 parts by mass of [A ¹ ], and the second composition contains 100 parts by mass of [A ² ]. On the other hand, it is preferable to contain 20 to 200 parts by mass of [B ² ].

Further, in the first composition, the amount of the non-porous organic crosslinked polymer particles (b2) based on 100 parts by mass of [A ¹ ] is 10 parts by mass or less; ² ] It is preferable that the amount of the non-porous organic crosslinked polymer particles (b2) added to 100 parts by mass is 10 parts by mass or less.

Furthermore, in the second composition, the organic filler [B ² ] includes the non-crosslinked polymer particles (b3), and the non-crosslinked polymer particles for the (meth)acrylic polymerizable monomer [A ² ]. The solubility of (b3) is less than 20% by mass, and in the first composition, the (meth)acrylic polymerizable monomer [A ¹ ] is the non-crosslinked polymer particles (b3) contained in the second composition. ) preferably contains a (meth)acrylic polymerizable monomer having a solubility of 20% by mass or more.

Regarding porous organic crosslinked polymers, there are examples in which they are blended as fillers in dental mucosa conditioners containing plasticizers and water-soluble organic solvents (Patent Document 6), and in dental adhesives as catalyst carriers. An example (Patent Document 7) and an example in which it is blended into a dental adhesive containing an acidic group-containing monomer and water (Patent Document 8) are known. However, to the best of the inventors' knowledge, there is no example in which it has been incorporated into a curable composition for a denture base consisting of a non-aqueous composition that does not substantially contain water.

Further, a second aspect of the present invention is a denture base lining or denture base repair comprising the denture base curable composition preparation kit according to the first aspect of the present invention, and a denture base adhesive. , wherein the denture base adhesive is a liquid adhesive containing a (meth)acrylic non-crosslinked polymer (PA), a (meth)acrylic polymerizable monomer (PB), and an organic solvent (PC). It is a kit for denture base lining or denture base repair.

According to the present invention, it is possible to provide a (two-paste type) kit for preparing a curable composition for a denture base, in which the resulting cured product has high strength and toughness, and the paste has good operability.

Further, each of the first composition and the second composition constituting the kit for preparing a curable composition for denture base of the present invention does not contain the non-porous organic crosslinked polymer particles (b2) at all, or even if it does contain the non-porous organic crosslinked polymer particles (b2). When the content is 10 parts by mass or less per 100 parts by mass of (meth)acrylic polymerizable monomer [A], the hardness of each paste is stable and does not change over time. Each also has the effect of being able to be stored stably for a long period of time.

Further, in the second composition, the organic filler [B ² ] includes the non-crosslinked polymer particles (b3), and the non-crosslinked polymer particles for the (meth)acrylic polymerizable monomer [A ² ]. The solubility of (b3) is less than 20% by mass, and in the first composition, the (meth)acrylic polymerizable monomer [A ¹ ] is the non-crosslinked polymer particles (b3) contained in the second composition. ) having a solubility of 20% by mass or more, the (meth)acrylic polymerizable monomer [A ¹ ] contained in the first composition after mixing both. By dissolving and swelling the non-crosslinked polymer particles (b3) contained in the second composition, similar to the powder-liquid type denture base material, the changes in paste properties over time after mixing can be effectively used, and clinical results can be improved. This has the advantage of facilitating manual or technical operations.

Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.

In this specification, unless otherwise specified, the expression "x to y" using numerical values x and y means "more than or equal to x and less than or equal to y." In such a notation, when a unit is attached only to the numerical value y, the unit shall also be applied to the numerical value x.

Further, in this specification, the term "(meth)acrylic" means both "acrylic" and "methacrylic". Similarly, the term "(meth)acrylate" refers to both "acrylate" and "methacrylate," and the term "(meth)acryloyl" refers to both "acryloyl" and "methacryloyl."

1. Kit for Preparing a Curable Composition for Denture Bases of the Present Invention The kit for preparing a curable composition for denture bases of the present invention consists of a combination of a first composition and a second composition, and the kit includes a combination of a first composition and a second composition. A kit for preparing a curable composition for a denture base, comprising:
The curable composition for denture bases contains (meth)acrylic polymerizable monomer [A] (hereinafter also referred to as "[A] component"), monomer-absorbing porous organic crosslinked polymer particles (b1) (hereinafter referred to as "[A] component"). ), non-porous organic crosslinked polymer particles (b2) (hereinafter also referred to as "component (b2)") and non-crosslinked polymer particles (b3) (hereinafter referred to as "component (b2)"). An organic filler [B] comprising at least one member selected from the group consisting of (b3) component (hereinafter also referred to as "component [B]"), and a polymerization initiator [C] (hereinafter also referred to as "[C] component" as appropriate),
The first composition and the second composition both contain a (meth)acrylic polymerizable monomer [A] and an organic filler [B], and [A] and [B] contained in the first composition. ] and [A] and [B] contained in the second composition are respectively [A ¹ ] and [B ^{1 ] and [A 2 ]} and [B ² ], [A ¹ ] and [A ² ] may be different from each other, and [B ¹ ] and [B ² ] may be different from each other,
The [B ¹ ] includes monomer-absorbing porous organic crosslinked polymer particles (b1) that have absorbency for the [A ¹ ],
The polymerization initiator [C] is
(1) It is composed of a single component, and the single component is blended in either the first composition or the second composition, or (2) It is composed of a plurality of components, and the Each of the plurality of constituent components is blended into either the first composition or the second composition in such a manner that it does not exhibit polymerization activity in the first composition or the second composition. It is characterized by becoming.

The first composition and the second composition constituting the denture base curable composition preparation kit of the present invention usually have a paste form in which each component is uniformly mixed (kneaded). Therefore, it can be said that the kit for preparing the curable composition for denture bases of the present invention is a two-paste type kit (or a two-paste type curable composition for denture bases itself). In addition, "paste" is a non-settling, non-Newtonian fluid, and "paste-like" in this specification means a high viscosity paste with plastic deformability, especially a non-aqueous high viscosity paste. do.

The curable composition for denture bases (paste composition) prepared using the curable composition preparation kit for denture bases of the present invention has a mixture of components [A] and [B] as a main component. Preferably. Moreover, it is preferable that the first composition and the second composition each have a mixture of the [A ¹ ] component and the [B ¹ ] component, and the [A ² ] component and the [B ² ] component as a main component. . In addition, "containing as a main component" means that the total mass of the components is 80 parts by mass or more, preferably 90 parts by mass or more, when the total mass of the composition is 100 parts by mass.

Although not bound by any particular logic, the mechanism by which the curable composition for denture bases prepared using the curable composition preparation kit for denture bases of the present invention achieves the above-described excellent effects. The present inventors conjecture that this is as follows.

That is, it is believed that the reason why the bending strength (strength) of the cured product is high is because a crosslinked polymer with a high elastic modulus is used as the organic filler. Furthermore, the reason why the toughness is increased despite the use of a crosslinked polymer is that the (meth)acrylic polymerizable monomer [A] is inside the pores of the monomer-absorbing porous organic crosslinked polymer particles (b1). It is thought that this is because the interfacial bonding strength between the matrix and the organic filler in the cured product was increased due to the anchor effect generated by the infiltration and curing.

Moreover, the following reasons can be considered as reasons why the good paste properties were achieved. In systems containing non-crosslinked polymer particles (b3), interaction with the (meth)acrylic polymerizable monomer [A], specifically, part of the component (b3) dissolves in the [A] component, Component (b3) swells with component [A] and becomes soft, making it possible to adjust it to a good state. However, cross-linked polymers are poor in this kind of interaction, so it is difficult to use a large amount of cross-linked polymer. It is thought that the adjustment range of such paste properties is usually narrowed when blending. However, when monomer-absorbing porous organic crosslinked polymer particles (b1) are used, an interaction similar to the above-mentioned interaction occurs due to the infiltration of component [A] into the pores, and the above-mentioned adjustment range is widened. It is thought that good paste properties were achieved because it was possible to maintain the paste as it was.

Finally, the storage stability of the paste (the property that the paste does not become hard even after long-term storage) is increased because crosslinked polymers that do not have pores generally have poor interaction with the matrix, so they aggregate and settle within the paste. However, the paste may become hard, whereas the monomer-absorbing porous organic cross-linked polymer particles (b1) do not aggregate within the paste because the matrix seeps into the pores, and the paste remains in the state immediately after production. This is thought to be due to the ability to maintain

Each component used in the denture base curable composition preparation kit of the present invention will be explained below.

<(meth)acrylic polymerizable monomer [A]>
As the (meth)acrylic polymerizable monomer, (meth)acrylic polymerizable monomers commonly used in dentistry can be used without particular limitation. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, hydroxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-methacryloxyethylpurpionate, acetoacetoxyethyl (meth)acrylate, per Monomers such as fluorooctylethyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 1H,1H,3H-hexafluorobutyl (meth)acrylate, etc. Functional (meth)acrylic polymerizable monomers, 1,6-bis(methacrylethyloxycarbonylamino)trimethylhexane, 2,2-bis(methacryloyloxyphenyl)propane, and acrylates corresponding to these methacrylates, 2-hydroxy Ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1, Difunctional (meth)acrylic polymerizable monomers such as 9-nonanediol di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, and polyoxytetramethylene glycol dimethacrylate, trimethylolpropane tri(meth)acrylate, and trimethylolpropane tri(meth)acrylate. Examples include trifunctional (meth)acrylic polymerizable monomers such as methylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and trimethylolmethane tri(meth)acrylate.

These (meth)acrylic polymerizable monomers can be used alone or in combination of two or more. In particular, when using a combination of a monofunctional and a difunctional or trifunctional or higher functional, the mechanical properties such as strength and durability of the resulting cured product can be improved by blending a large amount of the difunctional or trifunctional or higher functional. It is preferable because it can also be made good.

[A] The content of the component is 40 to 80 parts by mass when the total mass of the curable composition for denture bases prepared using the curable composition preparation kit for denture bases of the present invention is 100 parts by mass. It is preferably 50 to 70 parts by weight, more preferably 50 to 70 parts by weight.

<Organic filler [B]>
The organic filler is at least one selected from the group consisting of monomer-absorbing porous organic crosslinked polymer particles (b1), non-porous organic crosslinked polymer particles (b2), and non-crosslinked polymer particles (b3). Regarding these (b1), (b2), and (b3), those contained in the first composition are expressed as (b1 ¹ ), (b2 1 ), and (b3 1 ), respectively, and those contained in the second composition are expressed as (b1 1 ), (b2 ¹ ), and (b3 ¹ ), respectively. Those contained in the composition may be expressed as (b1 ² ), (b2 ² ), and (b3 ² ), respectively.

The monomer-absorbing porous organic crosslinked polymer particles (b1) are made of a crosslinked polymer made of an organic material in the form of granules or powder (aggregation of fine particles) in the air at room temperature. The particle may be used without particular limitation as long as it has pores communicating with the outside inside the particle and a large number of pores on the surface of the particle through which the (meth)acrylic polymerizable monomer [A] can permeate. In particular, in this embodiment, from the viewpoint of high strength effect, in accordance with the "refined linseed oil method" of JIS K5101-13-1:2004 (ISO 787-5:1980) (instead of refined linseed oil) The amount of the (meth) absorbed per g-B (unit: g) of the monomer-absorbing porous organic crosslinked polymer particles (b1) measured using the (meth)acrylic polymerizable monomer [A] ) Amount of acrylic polymerizable monomer [A]: Absorption amount defined as g-A (unit: g): R _Ab = {(g-A)/(g-B)} is 1.5 or more, It is preferable to use one having a value of 2.0 to 5.0.

The absorption amount R _Ab is determined by using the curable composition for denture base according to this embodiment instead of using purified linseed oil in the "refined linseed oil method" described in JIS K5101-13-1:2004. It is determined using the (meth)acrylic polymerizable monomer [A] used (if a mixture of two or more monomers is used, a mixture of monomers having the same composition) is used. Specifically, a predetermined amount [M _B (g)] of the monomer-absorbing porous organic crosslinked polymer particles (b1) are placed on a glass plate, and the monomer of the [A] component is added from a burette to 4 or 5 at a time. Gradually add drop by drop, using a palette knife to work the monomer into the polymer each time. These steps are repeated until a lump of monomer and polymer is formed, and then the monomer and polymer are added dropwise one drop at a time, and the process is repeated to ensure complete kneading. The end point is when the paste becomes smooth and hard, and the amount of monomer [A] used up to the end point [M _A (g)] is measured. At that time, the time required for the operation to reach the end point should be within 25 minutes. And the following formula:
R _Ab (g/g)=M _A (g)/M _B (g)
Accordingly, the absorption amount R _Ab is determined.

The absorption amount R _Ab determined as described above is determined at the critical point where the monomer of component [A] penetrates into the interior of the monomer-absorbing porous organic crosslinked polymer particles (b1) and begins to form a smooth paste state. Although it can be regarded as a parameter representing the quantitative ratio, as can be understood from the ease of operation, it does not mean a strict critical point, and the [ A] This is a measure of the absorbency of the component to the monomer. In fact, in the curable composition for denture bases according to the present embodiment, the amount of the (meth)acrylic polymerizable monomer [A] is absorbed by the amount of the monomer-absorbing porous organic crosslinked polymer particles (b1). It has been confirmed that even if the amount is less than the amount calculated as the product multiplied by the amount R _Ab (hereinafter also referred to as "calculated total absorption amount"), a paste-like composition can be obtained.

Although the details of the reason why the mixture becomes pasty even when component [A] is used in an amount less than the calculated total absorption amount are unknown, it is thought that this is due to differences in kneading conditions and kneading time. In other words, when measuring the amount of absorption, kneading is performed using a palette knife and the measurement is carried out in a short time (within 25 minutes), so component (b1), which remains partially aggregated, is retained between the polymer particles. It is thought that there are also monomers that have been used for this purpose, and the absorption amount may be overestimated. On the other hand, when preparing the curable composition for denture bases according to the present embodiment, it may be kneaded using a mortar or a mechanical kneading device such as a planetary mixer or a kneader. In many cases, strong shearing force is applied during kneading, making it possible to achieve a high degree of homogenization.Also, the extrusion effect caused by the shearing force and the expansion of the pore diameter due to heat generation or swelling reduce the amount of monomer that has been absorbed into the pores. It is thought that some of it is released and becomes a paste.

The material of the monomer-absorbing porous organic crosslinked polymer particles (b1) is not particularly limited as long as it is a crosslinked polymer, but from the viewpoint of affinity with the (meth)acrylic polymerizable monomer [A], Preferred are crosslinked polyalkyl (meth)acrylates such as methyl methacrylate, crosslinked polyethyl methacrylate, and crosslinked polymethylacrylate, polystyrene, polyvinyl chloride, and the like. Further, porous organic crosslinked polymers described in Japanese Patent Publication No. 4-51522, Japanese Patent Application Laid-Open No. 2002-265529, etc. can be used. Furthermore, commercially available products such as "Techpolymer MBP-8" (Sekisui Plastics Co., Ltd.) can also be used.

The average pore diameter of the monomer-absorbing porous organic crosslinked polymer particles (b1) is preferably from 1 to 100 nm, particularly preferably from 5 to 50 nm. The average pore diameter refers to the average diameter of pores formed on the surface of primary particles, not the agglomerated pores of secondary particles formed by aggregation of particles. The average pore diameter can be determined by calculation from the pore distribution of particles measured using a mercury porosimetry pore distribution measuring device. When the average pore diameter of the monomer-absorbing porous organic crosslinked polymer particles is smaller than 1 nm, the anchoring effect in the cured product decreases as the amount of (meth)acrylic polymerizable monomer [A] permeates into the pores decreases. Therefore, it tends to be difficult to obtain sufficient strength. When the average pore diameter is larger than 100 nm, although the amount of seepage is large, the anchoring effect is rather reduced, and it tends to be difficult to obtain sufficient strength.

The particle size of the monomer-absorbing porous organic crosslinked polymer particles (b1) is not particularly limited, but the average particle size is preferably 1 to 50 μm, particularly preferably 3 to 30 μm. Note that the average particle diameter refers to the average particle diameter of primary particles of porous organic crosslinked polymer particles, and is measured using a particle size distribution measuring device using a laser diffraction/scattering method. If the average particle size of the monomer-absorbing porous organic crosslinked polymer particles is smaller than 1 μm, the paste before curing tends to become more sticky and the operability decreases, and if the average particle size is larger than 50 μm, the specific surface area Because of the small size, it tends to be difficult to obtain sufficient strength and toughness in the cured product. Note that the particle shape is not particularly limited, and both pulverized particles and spherical particles can be used.

The preferred blending amount of the monomer-absorbing porous organic crosslinked polymer particles (b1) in the curable composition for denture bases prepared using the curable composition preparation kit for denture bases of the present invention is as follows: (meth)acrylic polymerizable monomer [A ¹ ] contained in the product and (meth)acrylic polymerizable monomer [A ² ] contained in the second component; Based on the total mass of [A], the amount is 20 to 80 parts by mass per 100 parts by mass of component [A]. If the amount of component (b1) exceeds 80 parts by mass, not only will the cured product become hard and brittle, but the paste will also tend to be hard and difficult to shape. Moreover, when the blending amount of component (b1) is less than 20 parts by mass, the anchoring effect tends to decrease and it becomes difficult to obtain sufficient strength. From the viewpoint of effectiveness, the blending amount of component (b1) is preferably 30 to 70 parts by weight, particularly 40 to 60 parts by weight.

In addition, in the denture base curable composition preparation kit according to the present embodiment, in addition to the composition of the preparation target having the above-mentioned composition, in each paste of the first composition and the second composition, Product of content (unit: g) of monomer-absorbing porous organic crosslinked polymer particles (b1) per unit amount (unit: g) of (meth)acrylic polymerizable monomer [A] and absorption amount R _Ab It is further preferable that the condition that is 0.65 to 1.65 be satisfied.

Non-porous organic crosslinked polymer particles (b2) are particles that do not have pores on their surface or have a small number of pores, and have an absorption amount R _Ab of less than 1.5 as determined as above. , preferably 1.0 or less. Non-porous organic crosslinked polymer particles are difficult to dissolve and swell in the (meth)acrylic polymerizable monomer [A] and have poor interaction with the matrix, so they may aggregate and settle within the paste, making the paste hard. Therefore, if a large amount of this is blended, the properties of the paste may change during storage (specifically, it becomes hard), which may reduce the operability of the paste. Therefore, when blending non-porous organic crosslinked polymer particles (b2 ¹ ) or (b2 ² ), the blending amount should be adjusted to [A ¹ ] or [ ^A2 ] It is preferable that the amount of each component is 10 parts by mass or less per 100 parts by mass of the component, and it is more preferable that they are not added at all.

The material of the non-porous organic crosslinked polymer particles (b2) is not particularly limited as long as it is a crosslinked polymer, but from the viewpoint of affinity with the (meth)acrylic polymerizable monomer [A], crosslinked polymethyl methacrylate , crosslinked polyalkyl (meth)acrylates such as crosslinked polyethyl methacrylate, crosslinked polymethyl acrylate, polystyrene, polyvinyl chloride, etc. are preferred.

The particle size of the non-porous organic crosslinked polymer particles (b2) is not particularly limited, but from the viewpoint of paste properties, the average particle size is preferably 1 to 50 μm, particularly preferably 3 to 30 μm. Note that the particle shape is not particularly limited, and both pulverized particles and spherical particles can be used.

The non-crosslinked polymer particles (b3) are particularly limited to non-crosslinkable (non-crosslinked) (meth)acrylic polymers that are generally used in dentistry and are granular or powdery in the atmosphere at room temperature. Can be used without any problem. Examples of those that can be preferably used include methyl (meth)acrylate, ethyl (meth)acrylate, t-butyl (meth)acrylate, n-butyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, Stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobonyl (meth)acrylate, isopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2- Hydroxy-1,3-dimethacryloxypropane, isobutyl (meth)acrylate, butoxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2-methoxyethyl ( (meth)acrylic polymerizable monomers such as meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate homopolymer or copolymer, poly(styrene-ethyl methacrylate) and other polymerizable monomers Examples include copolymers of. These may be used alone or in combination of two or more.

The average molecular weight of the non-crosslinked polymer particles (b3) is not particularly limited, but from the viewpoint of ease of adjusting paste properties, the mass average molecular weight is preferably 50,000 to 1,000,000, and 10,000 to 1,000,000. More preferably, it is between 70,000 and 700,000. In addition, the mass average molecular weight in this specification means the standard polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC).

The average particle size of the non-crosslinked polymer particles (b3) is not particularly limited, but if the average particle size is too large, it will dissolve slowly in the (meth)acrylic polymerizable monomer [A], making it difficult to manufacture. The thickness is preferably 100 μm or less because it takes time and reduces work efficiency.

The amount of the non-crosslinked polymer particles (b3) in the curable composition for denture bases prepared using the curable composition preparation kit for denture bases of the present invention is determined by the amount of (meth)acrylic polymerizable monomer [A ] It is preferably 5 to 40 parts by weight, more preferably 15 to 30 parts by weight, per 100 parts by weight.

When mixing the first composition and the second composition, in order to obtain a viscosity increase over time to the same degree as that of a powder-liquid denture base material, in the second composition, non-organic filler [B ² ] must be used. It is preferable that the crosslinked polymer particles (b3 ² ) are included, and that the solubility of the (b3 ² ) in the (meth)acrylic polymerizable monomer [A ² ] is less than 20% by mass. Further, in the first composition, the (meth)acrylic polymerizable monomer [A ¹ ] may include a (meth)acrylic polymerizable monomer in which the solubility of the (b3 ² ) is 20% by mass or more. Preferably, the solubility of the (b3 ² ) in the (meth)acrylic polymerizable monomer [A ¹ ] is particularly preferably 20% by mass or more. Here, solubility is the upper limit of the concentration at which a polymer can be dissolved in a polymerizable monomer, and simply refers to whether the polymer is dissolved at 23°C by adding a predetermined amount of the polymer to the polymerizable monomer. It can be evaluated visually. For example, when adding polymers in increasing amounts such as 5% by mass, 20% by mass, and 50% by mass, and visually evaluating whether or not each added amount dissolves at 23°C, it was found that 5% by mass of polymer If a part remains undissolved, the solubility will be less than 5% by mass, and if all of it is dissolved, the solubility will be 5% by mass or more. Similarly, if part of the 20% by mass of the polymer remains undissolved, the solubility will be less than 20% by mass, if all of it is dissolved, the solubility will be 20% by mass or more, and furthermore, a part of the 50% by mass of the polymer will not dissolve. If it remains, the solubility will be less than 50% by mass, and if all of it is dissolved, the solubility will be 50% by mass or more.

The non-crosslinked polymer particles (b3 ² ), a (meth)acrylic polymerizable monomer in which the solubility of (b3 ² ) is 20% by mass or more, and the solubility of (b3 ² ) in less than 20% by mass (meth) The acrylic polymerizable monomers listed above can be used as long as the combination satisfies the above requirements.

When the solubility of the (b3 ² ) in the (meth)acrylic polymerizable monomer [A ¹ ] is 20% by mass or more, a denture prepared using the denture base curable composition preparation kit of the present invention The blending ratio ((b3 ² )/[A ^{1 ]) of the non-crosslinked polymer particles (b3 2 ) and the [A 1 ] in} the curable composition for floors may be 0.9 to 3.0. It is preferably 1.2 to 2.5, more preferably 1.4 to 2.0. When the blending ratio ((b3 ² )/[A ¹ ]) is set within the range of 0.9 to 3.0, when the (b3 ² ) is dissolved when the first composition and the second composition are mixed, In addition, it becomes easier to set the dissolution rate to a more appropriate level within a range that is neither too low nor too high. That is, it becomes easier to ensure that the mixture of the first composition and the second composition has properties suitable for being taken out and trimmed after being shaped in the oral cavity.

<Polymerization initiator [C]>
As the polymerization initiator [C] used in the present invention, any one that can polymerize and cure the (meth)acrylic polymerizable monomer [A] can be used without any restriction, and any known polymerization initiator can be used. agents are available. For example, radical polymerization initiators used in the dental field include chemical polymerization initiators (room-temperature redox initiators), photopolymerization initiators, thermal polymerization initiators, etc., and each of these may be used alone or May be used together. However, the polymerization initiator [C] is (1) composed of a single component, and the single component is blended into either the first composition or the second composition, or ( 2) It is composed of a plurality of components, and each of the plurality of components does not exhibit polymerization activity in the first composition and the second composition. It needs to be added to either one of the compositions.

A chemical polymerization initiator is a polymerization initiator that is composed of two or more components and generates polymerization active species at around room temperature when all the components are mixed immediately before use. Typical examples of such chemical polymerization initiators include those based on organic peroxides/amine compounds.

Typical organic peroxides used as such chemical polymerization initiators include ketone peroxide, peroxyketal, hydroperoxide, diaryl peroxide, peroxy ester, diacyl peroxide, and peroxydi Carbonates, etc., specifically methyl ethyl ketone peroxide, cyclohexanoperoxide, P-methane hydroperoxide, diisopropylbenzene peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, benzoyl peroxide, di- Examples include n-propyl peroxydicarbonate and 1,1,3,3-tetramethylbutyl peroxyneodecanoate.

The preferable amount of these organic peroxides to be used varies depending on the type of organic peroxide used, so it cannot be absolutely limited, but the (meth)acrylic polymerizable monomer [A ¹ ] contained in the first composition, Preferably 0.05 to 5 parts by mass based on 100 parts by mass of the (meth)acrylic polymerizable monomer [A] combined with the (meth)acrylic polymerizable monomer [A ² ] contained in the second component. , more preferably in the range of 0.1 to 3 parts by mass.

Further, as the tertiary amine for generating radicals by contacting with these organic peroxides, known compounds can be used without particular limitation. Specific examples of tertiary amine compounds that are preferably used 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,N-dimethylaminophenyl)methane, bis(N,N-dimethylaminophenyl)ether etc. 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, - Tolyldipropanolamine is preferably used.

The amount of the tertiary amine compound used is preferably 0.00 parts by mass based on 100 parts by mass of the (meth)acrylic polymerizable monomer [A] including [A ¹ ] and [A ² ]. The amount ranges from 0.05 to 5 parts by weight, more preferably from 0.1 to 3 parts by weight.

Among the above combinations of organic peroxide and tertiary amine compound, specific examples of suitable combinations include BPO/N,N-diethyl-p-toluidine, BPO/N,N-dipropyl-p-toluidine , BPO/p-tolyldiethanolamine, and BPO/p-tolyldipropanolamine. Among them, when a tertiary amine compound mixed with a radically polymerizable monomer needs to be stored for a long period of time, BPO/N, N-diethyl-p-toluidine, BPO/N, N Most preferred is the combination -dipropyl-p-toluidine.

In addition to such a chemical polymerization initiator consisting of an organic peroxide and an amine compound, a sulfinic acid such as benzenesulfinic acid, p-toluenesulfinic acid and its salts, or a barbituric acid initiator such as 5-butylbarbituric acid is used. It can be used without any problems even if it is mixed with other agents.
Examples of photopolymerization initiators include benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, benzyl ketals such as benzyl dimethyl ketal and benzyl diethyl ketal, diaryl ketones such as benzophenone, anthraquinone, and thioxanthone, and diacetyl. , benzyl, camphorquinone, α-diketones such as 9,10-phenanthraquinone, bis-(2,6-dichlorobenzoyl) phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5- Dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,4,6-trimethylbenzoyl) )--phenylphosphine oxide and other bisacylphosphine oxides. These can be used alone or in a mixture of different types.

Note that the photopolymerization initiator is preferably used in combination with a reducing compound. Reducing compounds that can be suitably used include tertiary amines such as 2-(dimethylamino)ethyl methacrylate, p-N,N-ethyl p-N,N-dimethylaminobenzoate, N-methyldiethanolamine, dimethylaminobenzaldehyde, and terephthalaldehyde; Examples include sulfur-containing compounds such as 2-mercaptobenzoxazole, 1-decanethiol, thiosalcylic acid, and thiobenzoic acid, and N-phenylalanine.

Furthermore, in order to further enhance the activity of the photopolymerization initiator, it is also a preferred embodiment to add a photoacid generator. Examples of the photoacid generator include diaryliodonium salt compounds, sulfonium salt compounds, sulfonic acid ester compounds, halomethyl-substituted -S-triazine conductors, and pyridinium salt compounds. When using a photoacid generator, the photopolymerization initiator is preferably α-diketones such as camphorquinone, and it is more preferable to use a reducing compound such as ethyl p-N,N-dimethylaminobenzoate.

As a thermal polymerization initiator, peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, Azo compounds such as azobisisobutyronitrile can be mentioned. These can be used alone or in a mixture of different types.

The amount of the photopolymerization initiator and thermal polymerization initiator may be catalytic (that is, the amount that can function as a polymerization initiator and perform sufficient polymerization), and the specific amount is as follows: Although it cannot be definitively limited as it varies depending on the type of polymerization initiator used, usually, based on 100 parts by mass of (meth)acrylic polymerizable monomer [A], which is a combination of [A ¹ ] and [A ² ], The amount is 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight.

The above chemical polymerization catalyst is used separately, for example by adding an organic peroxide to the first composition and a tertiary amine compound to the second composition, so as to satisfy the above condition (2). be done. Even when a photopolymerization initiator and a thermal polymerization catalyst are used, they need to be blended into the first composition and/or second composition so as to satisfy the above condition (1) or (2). Moreover, a chemical polymerization catalyst, a photopolymerization catalyst, and a thermal polymerization catalyst may be used in combination.

<Other ingredients>
The first composition and/or the second composition constituting the denture base curable composition preparation kit of the present invention may contain calcium carbonate, magnesium oxide, barium sulfate, etc., within a range that does not impede the effects of the present invention. , titanium oxide, potassium titanate, aluminum hydroxide, silica powder, glass powder, diatomaceous earth, silica, calcium silicate, talc, alumina, mica, silica glass, and other inorganic fillers and inorganic particles with a polymerizable monomer added in advance to form a paste. granular organic-inorganic composite filler obtained by polymerizing and pulverizing, polymerization inhibitors such as butylated hydroxytoluene and methoxyhydroquinone, 4-methoxy-2-hydroxybenzophenone, 2-(2-benzotriazole)- Ultraviolet absorbers such as p-cresol, polymerization regulators such as α-methylstyrene dimer, dyes, pigments, fragrances, etc. can be added.

<Manufacturing method>
The method for producing each paste (the first composition and the second composition) in the denture base curable composition preparation kit of the present invention is not particularly limited. Bye. When non-crosslinked polymer particles (b3) are included, from the viewpoint of storage stability, it is preferable to swell and dissolve them in the (meth)acrylic polymerizable monomer [A] in advance.

In order to prevent deterioration during storage, the manufactured paste is preferably stored in a light-shielding container, especially when a photopolymerization initiator is used. The form of the paste is not particularly limited, but it may be molded into a stick, horseshoe shape, sheet, sphere, prism, etc. and stored in a container, or it may be stored in a tube, bottle, etc. without being molded. good.

Furthermore, in the kit for preparing a curable composition for denture bases of the present invention, the mixing ratio of the first composition and the second composition is not particularly limited; If there is a large difference in the ratio, it may be difficult to mix uniformly. Therefore, the mixing ratio of the two pastes is preferably 10/1 to 1/1, more preferably 5/1 to 1/1, with the smaller paste being 1.

<How to use>
When the denture base curable composition preparation kit of the present invention is used as a denture base resin, hard lining material, or repair resin, it can be used in a known manner. For example, when creating a new denture, an impression of the patient's oral cavity is taken and a plaster model is created, and the first composition and the second composition of the present invention are mixed on the plaster model to form a denture base. After forming a denture base using a curable composition, setting it in an articulator and arranging the artificial teeth, if a photopolymerization catalyst or a thermal polymerization catalyst is used, it is polymerized and hardened by light irradiation or heating, The shape is corrected and polished, and the denture is made.

When repairing a poorly fitting denture, apply an adhesive/separator as necessary to the denture that no longer fits in the patient's mouth, and apply a paste (for denture bases) containing a mixture of the first composition and the second composition. After applying the curable composition and adjusting it to the patient's oral cavity, if a photopolymerization catalyst or thermal polymerization catalyst is used, it is polymerized and cured by light irradiation or heating, and the shape is corrected and polished to improve the fit of the denture. Ru. When lining the mucous membrane surface, apply a thin paste of the first composition and the second composition, and when extending the bed, mix the first composition and the second composition and apply the stick-shaped paste so as to wrap it around the area. Good too.

2. Kit for denture base lining or denture base repair of the present invention The curable composition for denture base, which is the preparation object of the curable composition preparation kit for denture base of the present invention, is suitable for use as a hard lining material for denture base. In the case of a curable composition or a curable composition for a denture base repair resin, the first composition and the second composition according to the present embodiment are usually applied after applying an adhesive to the denture base. A mixed paste (curable composition for denture base) is applied, and if a photopolymerization catalyst or a thermal polymerization catalyst is used, it is polymerized and cured by irradiation or heating. Therefore, when used for such purposes, it is preferable to use a kit in which the denture base curable composition preparation kit of the present invention is combined with a denture base adhesive.

<Adhesive for denture base>
The adhesive for denture bases is (meth)acrylic non-crosslinked polymer (PA) (hereinafter also referred to as the "(PA) component" as appropriate), which is generally used as an adhesive for bonding denture bases in the dental field. ), (meth)acrylic polymerizable monomer (PB) (hereinafter also referred to as "(PB) component" as appropriate), and organic solvent (PC) (hereinafter also referred to as "(PC) component" as appropriate). An adhesive that further contains a polymerization initiator (PD) (hereinafter also referred to as "(PD) component" as appropriate) if necessary can be used without particular limitation. Such denture base adhesives are usually liquid, and after being applied to the denture base to be bonded, a hard denture base adhesive prepared using the above-mentioned kit for preparing a curable composition for denture bases of the present invention is applied. By applying a curable composition for lining material or a curable composition for denture base repair resin and curing it, the cured product can be firmly adhered to the denture base.

As the (PA) component, (PB) component, and (PD) component, the components described above as the (b3) component, [A] component, and [C] component, respectively, can be used without particular limitation. (PC) component: Organic solvents include hydrocarbon compounds such as hexane, heptane, and pentane; aromatic hydrocarbon compounds such as toluene and xylene; ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, etc. Alcohol compounds; ether compounds such as diethyl ether, tetrahydrofuran, tert-butyl methyl ether; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone; ester compounds such as ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate; Non-halogenated organic solvents such as the following can be suitably used. These organic solvents may be used alone or in combination of two or more.

The denture base to be bonded is not particularly limited, but (meth)acrylic denture bases can be suitably employed. (Meth)acrylic denture bases generally have polymethyl methacrylate as the main component, and a portion may be copolymerized with ethyl methacrylate, styrene, etc., or cross-linked with a cross-linking agent such as ethylene glycol dimethacrylate. You may do so.

EXAMPLES Hereinafter, in order to specifically explain the present invention, Examples and Comparative Examples will be given and explained, but the present invention is not limited by these in any way.
First, the names, characteristics, abbreviations (if abbreviations are used), etc. of various compounds used in each example and comparative example are shown.

<(meth)acrylic polymerizable monomer [A] (PB)>
(Monofunctional polymerizable monomer)
・HPr: 2-methacryloyloxyethylpurpionate ・FMA1: 1H, 1H, 3H-hexafluorobutyl methacrylate ・FMA2: Perfluorooctylethyl methacrylate (bifunctional polymerizable monomer)
・ND: Nonamethylene diol dimethacrylate ・UDMA: 1,6-bis(methacrylethyloxycarbonylamino)trimethylhexane (trifunctional polymerizable monomer)
- TT: Trimethylolpropane trimethacrylate.

<Organic filler [B]>
<Monomer-absorbing porous organic crosslinked polymer particles (b1)>
Table 1 shows the abbreviations, components, average particle diameters, and average pore diameters of the polymers used.

<Non-porous organic crosslinked polymer particles (b2)>
- PMMA-X: Polymethyl methacrylate (average particle size 8 μm, manufactured by Sekisui Plastics) - AC-X: Polyacrylic acid ester (average particle size 8 μm, manufactured by Sekisui Plastics).

<Non-crosslinked polymer particles (b3) or (PA)>
・PEMA: Polyethyl methacrylate (average particle size 35 μm, weight average molecular weight 500,000) ・P (EMA-MMA): Polyethyl methacrylate-methyl methacrylate copolymer (ethyl methacrylate/methyl methacrylate = 50/50, average particle size 40 μm) , weight average molecular weight 1 million).

<Polymerization initiator [C] or (PD)>
・BPO: Benzoyl peroxide ・DEPT: N,N-diethyl-p-toluidine ・CQ: Camphorquinone ・DMBE: Ethyl 4-(N,N-dimethylamino)benzoate.

<Organic solvent (PC)>
・Acetone ・Ethyl acetate.

<Other ingredients>
- Silica: Spherical silica (3-methacryloxypropyltrimethoxysilane treatment, average particle size 1 μm).

Next, methods for measuring each evaluation item in each example and comparative example are shown below.
(1) Monomer absorption amount Monomer absorption amount R _Ab is used in each example or comparative example instead of using purified linseed oil in the purified linseed oil method described in JIS K5101-13-1:2004 ( Measurement was performed using meth)acrylic polymerizable monomer [A] (if a mixture of two or more monomers is used, a mixture of monomers having the same composition) was used. Specifically, a predetermined amount [M _b (g)] of monomer-absorbing porous organic crosslinked polymer particles (b1) are placed on a glass plate, and the monomer of the [A] component is added from a burette to 4 to 5 g at a time. The monomer was added drop by drop, working the monomer into the polymer with a palette knife each time. Repeat these steps and continue dropping until a lump of monomer and polymer is formed.After that, drop one drop at a time and repeat until completely kneaded.The end point is when the paste becomes smooth and hard. The amount of the monomer [A] component used [M _A (g)] was measured. The time required for the operation to reach the end point was set to within 25 minutes. And the following formula:
R _Ab (g/g)=M _A (g)/M _b (g)
The monomer absorption amount R _Ab was calculated according to the following.

(2) Method for measuring bending strength, elastic modulus, and breaking energy A paste obtained by mixing predetermined amounts of the first composition and the second composition until uniform was mixed into a 30 x 30 x 2 mm It is filled into a polytetrafluoroethylene mold, and when a chemical polymerization catalyst is used, it is cured with polyethylene films pressed together on both sides, and when a photopolymerization catalyst is used, both sides are pressed together with polyethylene films and then cured. It is cured by irradiation with light for 5 minutes using a technical photopolymerization device α Light V (manufactured by MORITA), and when a thermal polymerization catalyst is used, it is immersed in water with both sides pressed together with polyethylene film and boiled. After that, it was heated for 1 hour to be cured to produce a cured product. Next, the cured product was polished with #800 and #1500 water-resistant abrasive paper, and then cut into a prismatic shape of 4 x 30 x 2 mm. The obtained cured product was immersed in water and left at 37° C. for 24 hours. This test piece was attached to a testing machine (manufactured by Shimadzu Corporation, Autograph AG-1), and a three-point bending test was performed at a distance between fulcrums of 20 mm and a crosshead speed of 1 mm/min to determine the bending strength, elastic modulus, and fracture energy. It was measured.

(3) Paste Adhesion Gloves were worn and the paste was evaluated according to the following criteria.
A: It does not adhere to gloves, but it does adhere to dentures and plaster.
B: It adheres to gloves, but can be peeled off from gloves when adhered to dentures and plaster.
C: Adheres to gloves and does not adhere to dentures and plaster.

(4) Paste properties after one month The paste was stored at 45°C for one month and evaluated according to the following criteria.
A: No change from immediately after paste preparation B: Slight viscosity change from immediately after paste preparation C: Significant viscosity change from immediately after paste preparation.

(5) Method for measuring solubility Non-crosslinked polymer particles (b3) are added to the polymerizable monomer in amounts of 5% by mass, 20% by mass, and 50% by mass, and visually evaluated to see if they dissolve at 23°C. Judgment was made based on the following criteria.
Less than 5% by mass: 5% by mass of the polymer does not dissolve 5% by mass or more, less than 20% by mass: All 5% by mass of the polymer dissolves, but 20% by mass of the polymer does not dissolve 20% by mass or more, less than 50% by mass: Polymer All 20% by mass is dissolved, but 50% by mass of the polymer is not dissolved. 50% by mass or more: All 50% by mass of the polymer is dissolved.

(6) Method for measuring complex elastic modulus maintenance time Changes in complex elastic modulus over time were measured using a dynamic viscoelasticity measuring device CS rheometer "CVO120HR" (manufactured by Bolin Co., Ltd.). The measurement was performed in oscillation mode using a parallel plate with a diameter of 20 mm at a frequency of 1 Hz and a measurement temperature of 37°C. Predetermined amounts of the first composition and the second composition were mixed until uniform, and measurement was started 1 minute after the start of mixing. The time required for the complex modulus of elasticity to change from 10 ³ Pa to 10 ⁴ Pa and the time required for the complex modulus to change from 10 ⁴ Pa to 10 ⁶ Pa were determined and defined as the complex modulus maintenance time.

In addition, clinically, a state in which the complex modulus of the paste obtained by mixing powder/liquid or paste/paste is about 10 ³ Pa to 10 ⁴ Pa is suitable for inserting into the oral cavity and shaping. A state of about 10 ⁴ Pa to 10 ⁶ Pa is suitable for removing the material from the oral cavity and trimming it. In order to perform each task with sufficient time, it takes at least 30 seconds for the complex modulus to change from 10 ³ Pa to 10 ⁴ Pa, and at least 2 minutes to change from 10 ⁴ Pa to 10 ⁶ Pa. A pattern of viscosity increase that requires this is preferred.

(6) Adhesive strength A 15 mm x 15 mm x 2 mm square plate-shaped cured body was prepared using denture base resin (Akron, manufactured by GC Corporation), and the plate-shaped cured body was polished with waterproof abrasive paper #800. This was used as the adherend. Apply the adhesive to the adherend using a brush, leave it to dry until the solvent component in the adhesive evaporates, then stick double-sided tape with a hole of 3 mm in diameter, and then apply the adhesive with a hole of 8 mm in diameter. A paraffin wax containing the same material was pasted onto the hole so that the same center was formed. A paste obtained by mixing predetermined amounts of the first composition and the second composition until uniform is filled into the holes, and when a chemical polymerization catalyst is used, the paste is cured while being pressed with a polyethylene film. When a photopolymerization catalyst is used, it is cured by irradiating it with light for 5 minutes using a dental laboratory photopolymerization device α Light V (manufactured by MORITA) while being pressed with a polyethylene film, and when a thermal polymerization catalyst is used. was immersed in water, brought to a boil, heated for 1 hour, and cured to prepare an adhesive test piece.
After immersing the above adhesive test piece in water at 37°C for 24 hours, a metal attachment was attached to the cured body (of the mixed paste) and a tensile tester (Autograph, manufactured by Shimadzu Corporation) was used to test the crosshead speed. Tensile strength was measured at 2 mm/min. The average value of the five test pieces was taken as the adhesive strength (initial).
A test piece prepared in the same manner as above was immersed in 5°C water for 30 seconds and 55°C warm water for 30 seconds using a thermal shock tester (manufactured by Tokyo Giken Co., Ltd.) for 1 cycle. A thermal shock test was conducted by repeating 000 cycles. The adhesive strength of the test piece after the thermal shock test was measured in the same manner as above, and the average value of the five test pieces was taken as the adhesive strength (after the durability test).

Example 1
Pastes were prepared with the compositions shown in Tables 2 and 3, and adhesives were prepared with the compositions shown in Table 4, and the above-mentioned physical properties were evaluated. The results are shown in Table 5.

As shown in Table 5, the cured product obtained by curing the paste of Example 1 has a high bending strength of 80 [MPa] and a breaking energy of 93 [N mm], both of which are high, and has high strength and toughness. are doing. In addition, the paste of Example 1 slightly adheres to the glove, but once it adheres to the denture and plaster, it can be easily peeled off from the glove, indicating good paste operability, and the paste properties after one month showed no change from immediately after preparation. It also had excellent storage stability. Furthermore, the paste of Example 1 could be firmly adhered to an adherend using an adhesive and had excellent adhesive durability.

Examples 2 to 24
Evaluation was performed in the same manner as in Example 1, except that the composition of the paste was changed as shown in Tables 2 and 3, and the composition of the adhesive was changed as shown in Table 4. The results are shown in Table 5.
In all of Examples 2 to 24, each component was blended so as to satisfy the configuration shown in the present invention, and in any case, the cured product had high strength and toughness, The paste had excellent operability and storage stability. Further, the pastes of Examples 2 to 24 could be firmly adhered to an adherend using an adhesive and had excellent adhesive durability.

Examples 25-27
Evaluation was performed in the same manner as in Example 1, except that the composition of the paste was changed as shown in Tables 2 and 3, and the composition of the adhesive was changed as shown in Table 4. The results are shown in Table 6.

In Examples 25 to 27, each component was blended so as to satisfy the configuration shown in the present invention, and in any case, the cured product had high strength and toughness, The paste had excellent operability and storage stability. Furthermore, the complex elastic modulus maintenance time was sufficiently maintained, and a moderate increase in viscosity was confirmed to be around the same level as conventional denture base materials composed of powder and liquid. Further, the pastes of Examples 25 to 27 could be firmly adhered to an adherend using an adhesive and had excellent adhesive durability.

Comparative examples 1 to 4
The monomer-absorbing porous organic crosslinked polymer particles (b1) were not used as the organic filler [B], but the fillers were changed to those shown in Tables 7 and 8, and the composition of the adhesive was changed as shown in Table 9. Evaluation was performed in the same manner as in Example 1 except for the changes. The results are shown in Table 10.

Comparative Examples 1, 2, and 4 contain non-porous organic crosslinked polymer particles (b2) as a filler instead of monomer-absorbing porous organic crosslinked polymer particles (b1), and the strength of the cured product is low; The paste properties after several months had changed significantly from immediately after preparation. Moreover, the pastes of Comparative Examples 1, 2, and 4 had low adhesive strength when adhered to an adherend using an adhesive, and were also inferior in adhesive durability.

Comparative Example 3 contains silica as a filler instead of monomer-absorbing porous organic crosslinked polymer particles (b1), and although the strength of the cured product is high, the toughness is low, and the paste adheres to gloves, making it difficult to operate. Also, the paste properties were poor. Further, the paste of Comparative Example 3 had low adhesive strength when adhered to an adherend using an adhesive, and was also poor in adhesive durability.

Claims (7)

A kit consisting of a combination of a first composition and a second composition, for preparing a curable composition for a denture base by mixing these compositions,
The curable composition for denture base comprises a (meth)acrylic polymerizable monomer [A], monomer-absorbing porous organic crosslinked polymer particles (b1), non-porous organic crosslinked polymer particles (b2), and non-crosslinked polymer particles. (b3) an organic filler [B] comprising at least one selected from the group consisting of; and a polymerization initiator [C];
The first composition and the second composition both contain a (meth)acrylic polymerizable monomer [A] and an organic filler [B], and [A] and [B] contained in the first composition. ] and [A] and [B] contained in the second composition are respectively [A ¹ ] and [B ^{1 ] and [A 2 ]} and [B ² ], [A ¹ ] and [A ² ] may be different from each other, and [B ¹ ] and [B ² ] may be different from each other,
The [B ¹ ] includes monomer-absorbing porous organic crosslinked polymer particles (b1) capable of absorbing the [A ¹ ],
The polymerization initiator [C] is
(1) It is composed of a single component, and the single component is blended in either the first composition or the second composition, or (2) It is composed of a plurality of components, and the Each of the plurality of constituent components is blended into either the first composition or the second composition in such a manner that it does not exhibit polymerization activity in the first composition or the second composition. A kit for preparing a curable composition for denture base, characterized by: JIS K5101-13-1: per unit amount of the monomer-absorbing porous organic crosslinked polymer particles (b1) contained in the first composition: g-B (unit: g), measured according to 2004. Amount of (meth)acrylic polymerizable monomer [A ¹ ] contained in the first composition absorbed: Absorption amount defined as g-A (unit: g): R _Ab = {(g-A) /(g-B)} is 1.5 or more, the kit for preparing a curable composition for denture base according to claim 1. The curable composition for denture base contains 20 to 80 parts by mass of monomer-absorbing porous organic crosslinked polymer particles (b1) based on 100 parts by mass of the (meth)acrylic polymerizable monomer [A],
The first composition contains 20 to 200 parts by mass of the [B ¹ ] based on 100 parts by mass of the [A ¹ ],
The kit for preparing a curable composition for a denture base according to claim 1 or 2, wherein the second composition contains 20 to 200 parts by mass of the [B ² ] based on 100 parts by mass of the [A ² ]. In the first composition, the content (unit: g) of the monomer-absorbing porous organic crosslinked polymer particles (b1) per unit amount (unit: g) of the (meth)acrylic polymerizable monomer [A ¹ ] ) and the absorption amount R _Ab is 0.65 to 1.65, the kit for preparing a curable composition for a denture base according to any one of claims 1 to 3. In the first composition, the amount of the non-porous organic crosslinked polymer particles (b2) based on 100 parts by mass of [A ¹ ] is 10 parts by mass or less,
The denture according to any one of claims 1 to 4, wherein in the second composition, the amount of the non-porous organic crosslinked polymer particles (b2) based on 100 parts by mass of [A ² ] is 10 parts by mass or less. Kit for preparing curable composition for floors. In the second composition, the organic filler [B ² ] includes the non-crosslinked polymer particles (b3) and the non-crosslinked polymer particles (b3) for the (meth)acrylic polymerizable monomer [A ² ]. ) has a solubility of less than 20% by mass,
In the first composition, the (meth)acrylic polymerizable monomer [A ¹ ] has a solubility of the non-crosslinked polymer particles (b3) contained in the second composition of 20% by mass or more (meth) The kit for preparing a curable composition for a denture base according to any one of claims 1 to 5, comprising an acrylic polymerizable monomer. A kit for denture base lining or denture base repair comprising the denture base curable composition preparation kit according to any one of claims 1 to 6 and a denture base adhesive,
The denture base adhesive is a liquid adhesive containing a (meth)acrylic non-crosslinked polymer (PA), a (meth)acrylic polymerizable monomer (PB), and an organic solvent (PC). Kit for wearing or denture base repair.