JP2022049980A - Method for producing paste-like curable composition for denture base - Google Patents

Abstract

To provide methods for efficiently manufacturing a paste-like curable composition for denture base that has a cured body with high strength and toughness, as well as additionally has good operability of paste and can maintain good paste properties even when stored for a long period of time.SOLUTION: A method comprises: a first step of mixing component A consisting of a (meth) acrylic acid-based polymerizable monomer, which is liquid at normal temperature and pressure, with component B consisting of a (meth) acrylic acid-based non-crosslinked polymer, which can be dissolved in the component A, at a predetermined mixing temperature: TMIX(°C) to obtain a liquid composition in which the component B is dissolved in the component A; and a second step of mixing and kneading the obtained liquid composition and component C consisting of a porous organic crosslinked polymer, which can absorb the component A, to obtain a paste-like composition, a paste-like curable composition for denture base containing the components A, B, and C being produced by dissolving the component B while dispersing the powdery component B, which is less than the saturated dissolution amount for the component A at TMIX, in the component A, in the first step.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a curable composition for a denture base. More specifically, the present invention relates to a method for producing a paste-like curable composition suitable for a paste-type resin for a denture base, a hard lining material for a denture base, and a resin for repairing a denture base.

The curable composition for a denture base is a composition used for manufacturing or repairing a denture base, and as a material using the composition, a resin for a denture base used when newly producing a denture, Hard denture base dentures used to refurbish dentures that are no longer compatible with the patient's oral mucosa after long-term use and to re-use them, as well as denture linings, dentures and breaks. Known denture base repair resins and the like used for repairing broken dentures.

As the curable composition for a denture base, a polymerizable monomer containing a polymerizable monomer such as methyl methacrylate, a (meth) acrylic acid-based polymer such as polymethyl methacrylate and polyethyl methacrylate, and a polymerization curable composition containing a polymerization initiator is generally used. It is used. As the polymerization initiator, a chemical (redox) polymerization initiator, a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof is used, and the above-mentioned materials have different forms depending on the type of the polymerization initiator used. Provided.

For example, a combination of an oxidizing agent (sometimes referred to simply as a "radical initiator") and a reducing agent (sometimes referred to as a "polymerization accelerator") that can react immediately upon contact among the above materials. When a chemical polymerization initiator containing the above is used, it is necessary to store (package) the above-mentioned oxidizing agent and the above-mentioned reducing agent separately, and usually, the main component is a polymerizable monomer and a reducing agent. (See Patent Documents 1 and 2) composed of a liquid agent and a powder agent containing a (meth) acrylic acid-based polymer and an oxidizing agent as main components, or a single amount polymerizable with an oxidizing agent and a reducing agent, respectively. It is provided as a two-paste type (see Patent Document 3) in which a body and a (meth) acrylic acid-based polymer are blended to form a paste.

The two-paste type artificial toothbed material proposed in Patent Document 3 has a methacrylate having no urethane bond, a methacrylate having a urethane bond, a polyurethane powder having a radical bond, and a filler in each of the two. It is composed of components, one component containing an oxidizing agent (radical initiator) and the other component containing a reducing agent (polymerization accelerator). By preparing a composition composed of such two components, it is excellent in operability because it has a sufficient operation time to form a material for a denture base, and a cured product formed of the material has appropriate elasticity. It is known that it has a feature that there is little damage to the repaired part.

The two-paste type denture base material using such a chemical polymerization initiator has the advantage that polymerization is started by mixing the two pastes, so that a special device such as a polymer is not required. There was room for improvement in that the paste needs to be weighed and mixed, and the operation for producing the cured product is complicated.

On the other hand, various 1-paste type denture base materials using a photopolymerization initiator or a thermal polymerization initiator have also been proposed. For example, Patent Document 4 describes a polymerizable monomer and at least one weight selected from an alkyl (meth) acrylate homopolymer, an alkyl (meth) acrylate copolymer, and an alkyl (meth) acrylate / styrene copolymer. A resin material for artificial tooth beds has been proposed, which comprises a mixture of a coalescence and a thermal polymerization catalyst and / or a photopolymerization catalyst, and at least a part of the polymer components is dissolved in the polymerizable monomer. ing. Further, Patent Document 5 describes heat polymerization of a polymerizable monomer and / or an oligomer having a specific range of elasticity during polymerization, an organic filler and / or an organic-inorganic composite filler having a specific range of elasticity. A one-paste resin composition for artificial tooth beds has been proposed, which comprises a polymerization initiator composed of a type polymerization initiator and / or a photopolymerization type polymerization initiator.

1 The paste-type denture base material requires a device such as a polymerizer to cure it, but it does not need to be weighed or mixed, and the paste properties are maintained until heat or light is applied, at any time. Since the polymerization can be started, there is an advantage that the operability is excellent. Further, since the resin composition for a denture base described in Patent Document 5 uses a material having an appropriate elastic modulus, the obtained cured product has excellent bending strength and elastic energy characteristics, and has impact resistance. It is known to have the characteristic of being excellent in sex.

Japanese Unexamined Patent Publication No. 11-335222 Tokuhei 4-042364 Gazette Japanese Unexamined Patent Publication No. 2000-175941 Japanese Unexamined Patent Publication No. 2000-254152 JP-A-2002-104912

As described above, the 1-paste type and 2-paste type denture base materials are known to have appropriate elasticity, good bending strength and impact resistance, and excellent operability. There is. However, the strength and toughness are not always satisfactory, and depending on the filling material used, it is difficult to control the paste properties and the strength may be low, so there is still room for improvement.

Further, since the paste type denture base material is often handled by a gloved hand due to its morphological characteristics, it is necessary to suppress stickiness so as not to adhere to the glove. On the other hand, it is necessary to adhere to the plaster model when it is used for making a new denture, and to the denture when it is used for lining or repairing the denture base. That is, in the paste-type curable composition for a denture base, from the viewpoint of operability, a paste property having an appropriate viscosity such that it does not adhere to gloves but adheres to a plaster model or a denture is required.

As described above, in the paste-type curable composition for artificial dentition, the one-paste type has good paste operability and the cured product has high strength and toughness. As for the pastes, those having good operability of each paste and the kneaded paste of both pastes (kneaded paste) and having high strength and toughness of the cured kneaded paste are required.

The present inventors have (meth) acrylic acid-based as a paste-like curable composition for a 1-paste type curable composition for an artificial pelvic bed and a 2-paste type curable composition for an artificial pelvic bed that can meet the above requirements. A paste-like curable composition containing a polymerizable monomer, a porous organic crosslinked polymer capable of absorbing the (meth) acrylic acid-based polymerizable monomer, and a (meth) acrylic acid-based non-crosslinked polymer (hereinafter, "" It is also referred to as a "proposed paste-like curable composition") (Japanese Patent Application No. 2019-4801 and Japanese Patent Application No. 2019-48536). The "paste" generally means a non-precipitating non-Newtonian fluid, and the "paste" in the present specification is a high-viscosity paste having plastic deformability, particularly a non-aqueous high-viscosity paste. Means that.

The above-mentioned proposed paste-like curable composition solves the above-mentioned problems, but according to the subsequent study by the present inventor and the like, when each component is simply mixed and kneaded at the time of preparation, it takes time to prepare. It has been found that the obtained paste-like curable composition may not exhibit the desired paste properties, or the paste properties may change when stored for a long period of time.

Therefore, an object of the present invention is to provide a method capable of producing the proposed paste-like curable composition with high efficiency and high reproducibility in a state where it can exhibit its original characteristics. ..

The present invention solves the above-mentioned problems newly recognized by the present inventors, and one embodiment of the present invention is:
Component A: A component composed of a (meth) acrylic acid-based polymerizable monomer that is liquid at normal temperature and pressure, Component B: a component composed of a (meth) acrylic acid-based non-crosslinked polymer that can be dissolved in the component A, and C. Ingredients: A method for producing a paste-like curable composition for artificial dentition, which comprises a component made of a porous organic crosslinked polymer capable of absorbing the component A.
The first step of mixing the A component and the B component at a predetermined mixing temperature: _TMIX (° C.) to obtain a liquid composition in which the B component is dissolved in the A component.
Including the second step of mixing and kneading the liquid composition obtained in the first step and the C component to obtain a paste-like composition, in the first step, the component B of the A component in the temperature: T _MIX . It is a method for producing a paste-like curable composition for artificial dentition, which comprises dissolving the B component while dispersing the powdery B component in an amount equal to or less than the saturated dissolution amount in the A component. The "normal temperature and pressure" in the present invention means 25 ° C. and 1 atm (≈1013 hPa).

In the production method of the above embodiment (hereinafter, also referred to as “the production method of the present invention”), the component B is 5 to 40 (parts by mass) and the component A in _TMIX with respect to the component A 100 (parts by mass). The amount of component A (parts by mass) absorbed per unit amount (parts by mass) of component C, which is measured according to JIS K5101-13-1, is R (component A). It is preferable to produce a paste-like curable composition for an artificial tooth bed, which comprises an amount of 65 / R to 165 / R (parts by mass) when the content is (parts by mass / parts by mass of C component). ..

Further, in the first step, the A component or a part of the A component is used as a dispersion medium, and the saturated dissolution amount of the dispersion medium with respect to the B component is smaller than the saturated dissolution amount of the A component with respect to the component B in the temperature: _TMIX . Under such conditions, the dispersion medium and the powdery B component were mixed to obtain a dispersion liquid in which the powdery B component was dispersed in the dispersion medium, and the dispersion step was obtained. It is preferable that the dispersion liquid includes a total amount of the component A and a total amount of the powdery component B, and includes a dissolution step of dissolving the component B in a state where the temperature of the system is _TMIX .

In the above preferred embodiment, the (meth) acrylic acid-based polymerizable monomer component which has a predetermined composition and is liquid at normal temperature and pressure at a predetermined temperature: the maximum amount of the B component which is soluble in 100 parts by mass ( By mass), the solubility of the polymerizable monomer component in the B component at the predetermined temperature is defined as the solubility of the A component as a dispersion medium or a part of the A component in the B component in the dispersion step. It is preferable to mix the dispersion medium and the powdery B component at a temperature of 5 or less to obtain a dispersion liquid in which the powdery B component is dispersed in the dispersion medium.

Further, in the above preferred embodiment, as the A component, the A1 component composed of a (meth) acrylic acid-based polymerizable monomer having a solubility of the B component in T _MIX of 5 or less and the solubility of the B component in T _MIX of 5 are used. Dispersion in which a powdery B component is dispersed in the A1 component using a mixture of the A2 component composed of the (meth) acrylic acid-based polymerizable monomer and the A1 component as a dispersion medium in the dispersion step. A liquid is obtained, and in the dissolution step, the dispersion liquid and the A2 component are mixed to bring the total amount of the A component and the total amount of the powdery B component into a state, and then the B component is dissolved at temperature: _TMIX . , Is preferred.

According to the manufacturing method of the present invention, it is possible to give a cured product having high bending strength (strength) and breaking energy (toughness), and it does not adhere to the glove, but it adheres to a paste model or a denture. It is possible to efficiently produce a paste-like curable composition for a denture base which not only has a paste property having a high viscosity but also can maintain such a paste property even after long-term storage.

The object of the production method of the present invention is a component A: a (meth) acrylic acid-based polymerizable monomer that is liquid at normal temperature and pressure (hereinafter, the polymerizable monomer is simply a "monomer" and the component A is a "monomer". A component consisting of a "monomer component"); a component B: a (meth) acrylic acid-based non-crosslinked polymer (hereinafter, also referred to as a "soluble non-crosslinked polymer") that is soluble in the component A. Component; and component C: a component consisting of a porous organic crosslinked polymer capable of absorbing the component A (hereinafter, also referred to as "absorbent monomeric porous crosslinked polymer"); It is a paste-like curable composition, which can give a cured product having high bending strength (strength) and breaking energy (toughness), and does not adhere to gloves but adheres to plaster models and artificial teeth. It has a paste property with a moderate viscosity.

Although not bound by logic, the present inventors speculate that the mechanism by which the above-mentioned paste-like curable composition for denture base exerts such an excellent effect is as follows.

That is, it is considered that the reason why the bending strength (strength) of the cured product is high is that a crosslinked polymer having a high elastic modulus is used as the organic filler. Regarding the fact that the toughness is high despite the use of the crosslinked polymer, the anchor generated by the infiltration of the A component into the pores of the absorbent monomeric porous crosslinked polymer, which is the C component, and hardening. It is considered that the effect increased the interfacial bonding strength between the matrix and the organic filler in the cured product.

Regarding the paste properties, the effect of being able to adjust the paste properties by dissolving the B component in the A component, which is seen in the two-component system of the B component (soluble non-crosslinked polymer) and the A component (monomer), is obtained by the C component ( It is considered that this is because the absorbent monomer (porous crosslinked polymer) does not inhibit. For example, when a crosslinked polymer powder that is not a C component and does not have absorbent monomer properties (has no pores) is blended, it is difficult to uniformly disperse the powder because of its poor affinity. Is narrowed and may aggregate and settle in the paste during long-term storage, making the paste hard. On the other hand, when a absorbent monomeric porous crosslinked polymer (C component) powder is blended, the pores are formed. Since the monomer component infiltrates into the state, it becomes a state having an affinity with the monomer, so that uniform dispersion is easy and the dispersed state can be maintained for a long period of time, so that the effect of the C component is not easily impaired. Conceivable.

The paste-like curable composition for a denture base, which is the object of the production method of the present invention, has such excellent features, but as described above, it is produced by the subsequent study by the present inventor and the like. It was found that when each component was simply mixed and kneaded at times, it took time to prepare, and the desired paste properties and the desired storage stability regarding the paste properties could not be obtained.

The present inventors presumed that the cause of such a problem is as follows, and examined a solution based on the following. That is, the problem that preparation takes time is that powder is usually used as the soluble non-crosslinked polymer (component B), and when dissolved in the monomer, the monomer permeates into the powder particles and swells, and gradually. It is thought that dissolution occurs, but when a large amount of powder and a large amount of monomer are mixed at once, the swollen powder adheres to each other to form a lump, and the contact area with the monomer is significantly reduced. .. In addition, the reason why the desired paste properties and the like cannot be obtained is that a part of the soluble non-crosslinked polymer (component B) exists in a state in which it is not dissolved in the monomer at the time of paste preparation. As a result, it becomes difficult to obtain the desired paste properties, and even if the desired paste properties can be adjusted, the residual polymer gradually dissolves and the paste properties are considered to be unstable.

The present invention has been made by studying such a new problem recognition and a study based on the above hypothesis regarding the cause thereof. The mixing / kneading process is divided into two stages, and the powdery B component is provided in the first stage. The above problem is solved by completely dissolving the B component while dispersing it in the A component.

That is, the production method of the present invention comprises the first step of mixing the A component and the B component at a predetermined mixing temperature: _TMIX (° C.) to obtain a liquid composition in which the B component is dissolved in the A component, and the first step. Including the second step of _mixing and kneading the liquid composition obtained in one step and the C component to obtain a paste-like composition, in the first step, a powder having a saturated dissolution amount or less with respect to the component A in TMIX. It is characterized in that the B component is dissolved while the B component is dispersed in the A component.

Hereinafter, various raw materials used in the production method of the present invention and each step in the production method of the present invention will be described in detail. In the present specification, unless otherwise specified, the notation "x to y" using the numerical values x and y means "x or more and y or less". When a unit is attached only to the numerical value y in such a notation, the unit shall be applied to the numerical value x as well. Further, in the present specification, the term "(meth) acrylic type" means both "acrylic type" and "methacrylic type". Similarly, the term "(meth) acrylate" means both "acrylate" and "methacrylate", and the term "(meth) acryloyl" means both "acryloyl" and "methacryloyl".

1. 1. Various raw materials used in the production method of the present invention First, each component used in the production method of the present invention and the curable composition for a paste-like denture base will be described.

1-1. Component A: Monomer As a (meth) acrylic acid-based polymerizable monomer that is liquid at room temperature and pressure and is used as the component A (monomer component) used in the production method of the present invention, it is generally used for dentistry. Among the (meth) acrylic acid-based polymerizable monomers, those which are liquid at normal temperature and pressure when used alone or when two or more kinds are mixed are used. As described above, the "normal temperature and pressure" in the present invention means 25 ° C. and 1 atm (≈1013 hPa).

Specific examples of such (meth) acrylic acid-based polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and 2-methacryloxyethyl. Monofunctional (meth) acrylic acid-based polymerizable monomers such as purpionate and acetoacetoxyethyl (meth) acrylate, 1,6-bis (methacryloxycarbonylamino) trimethylhexane, 2,2-bis (methacryloyl). Oxyphenyl) propane and the acrylates corresponding to these methacrylates, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, ethylene glycol di (meth) ) Bifunctional (meth) acrylic acid-based polymerizable single amount of acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, etc. Trifunctional (meth) acrylic acid-based polymerizable singles such as body, trimethylol propanetri (meth) acrylate, trimethylol ethanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylol methanetri (meth) acrylate. Acrylate and the like can be mentioned.

These (meth) acrylic acid-based polymerizable monomers can be used alone or in combination of two or more. In particular, when a monofunctional product and a bifunctional or trifunctional or higher product are used in combination, mechanical properties such as strength and durability of the obtained cured product can be obtained by blending a large amount of the bifunctional or trifunctional or higher product. Is also preferable because it can be good.

1-2. Component B: Soluble non-crosslinked polymer The component B used in the production method of the present invention has solubility in the component A and is generally used for dentistry in normal temperature air. Granular or powdery, non-crosslinkable (non-crosslinking) (meth) acrylic acid-based polymers can be used without particular limitation. Specifically, having solubility in the A component means that all the B components to be blended are dissolved in 100 parts by mass of the A component at 25 ° C., as judged visually.

Examples of suitable (meth) acrylic acid-based non-crosslinked polymers include methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, n-butyl (meth) acrylate, and 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-hydroxy Propyl (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) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate homopolymer or copolymer, poly (styrene-ethylmethacrylate) and other (meth) acrylic acid-based singles. Examples thereof include a copolymer of a weight and another polymerizable monomer. These may be used alone or in combination of two or more.

The average molecular weight of the component B is not particularly limited, but is preferably 50,000 or more and less than 1 million, preferably 100,000 or more, from the viewpoint of the ease of adjusting the solubility and the paste properties. 700,000 or less is more preferable. The particle size is not particularly limited, but if it is too large, it is slow to dissolve in the component A, it takes time to manufacture, and the work efficiency tends to decrease. Therefore, it is preferably 100 μm or less. ..

The blending amount of the B component is preferably 5 to 40 parts by mass, more preferably 15 to 30 parts by mass with respect to 100 parts by mass of the A component.

1-3. Component C: Absorbing Monomer Porous Crosslinked Polymer The C component (absorbing monomeric porous crosslinked polymer) used in the production method of the present invention is a granular or powdery (aggregate of fine particles) in a room temperature atmosphere composed of an organic material. ), Which is composed of a crosslinked polymer composed of the organic material of), and is a pore that communicates with the outside inside the particles, and the above (meth) acrylic acid-based polymerizable monomer can penetrate into the inside of the pores. It can be used without particular limitation as long as it has a large number of holes on the surface, but from the viewpoint of high strength effect, it conforms to the "refined monomer oil method" of JIS K5101-13-1 (for refined monomer oil). It is defined by the amount (g) of the A component absorbed per unit amount of the absorbent monomeric porous organic cross-linked polymer, which is measured (using the (meth) acrylic acid-based polymerizable monomer instead). It is preferable to use a polymer having an absorption amount preferably in the range of 1.5 g / g or more, more preferably 2.0 g / g or more, and 5.0 g / g or less.

The material of the absorbent monomeric porous organic crosslinked polymer is not particularly limited as long as it is a crosslinked polymer, but from the viewpoint of compatibility with the (meth) acrylic acid-based polymerizable monomer, the crosslinked polymethylmethacrylate, Cross-linked polyalkyl (meth) acrylates such as cross-linked polyethyl methacrylate and cross-linked polymethyl acrylate, polystyrene, polyvinyl chloride and the like are preferable. Further, as such a porous crosslinked polymer, the polymers described in Japanese Patent Application Laid-Open No. 4-51522, Japanese Patent Application Laid-Open No. 2002-265529 and the like can be used. Further, as such a porous crosslinked polymer, a commercially available "Technopolymer MBP-8" (Sekisui Plastics Co., Ltd.) or the like can be used.

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

When the average pore diameter is smaller than 1 nm, the anchoring effect in the cured product also decreases as the amount of the (meth) acrylic acid-based polymerizable monomer infiltrated into the pores decreases, and it is difficult to obtain sufficient strength. Tend to be. Even when the average pore diameter is larger than 100 nm, the anchoring effect is rather lowered although the amount of infiltration is large, and it tends to be difficult to obtain sufficient strength.

The particle size of the absorbent monomer-like porous organic crosslinked polymer is not particularly limited, but the average particle size is preferably 1 to 50 μm, and particularly preferably 3 to 30 μm. The average particle size means the average particle size of the primary particles of the porous crosslinked polymer particles, and is measured by using a particle size distribution measuring device by a laser diffraction / scattering method. When the average particle size is smaller than 1 μm, the stickiness of the paste before curing tends to increase and the operability tends to decrease. When the average particle size is larger than 50 μm, the specific surface area becomes small, so that the cured product has sufficient strength and sufficient strength. It tends to be difficult to obtain toughness. The particle shape is not particularly limited, and either pulverized particles or spherical particles can be used.

The optimum amount of the absorbent monomeric porous organic crosslinked polymer is determined by the absorbed amount. For example, a porous organic crosslinked polymer having a large absorption amount absorbs a large amount of monomers, so that the apparent amount of monomers is small, and the desired paste properties can be obtained with a relatively small blending amount. On the other hand, a relatively large amount of the porous organic crosslinked polymer having a small absorption amount can be blended. Specifically, the amount (mass part) of the A component absorbed per unit amount (mass part) of the C component measured according to the above JIS K5101-13-1 is R (A component mass part / C component). The amount is preferably 65 / R to 165 / R (parts by mass). When the C component exceeds 165 / R, the cured product tends to be hard and brittle, and the paste tends to be hard. If it is less than 65 / R, the anchor effect tends to decrease and the hardness tends to decrease. From the viewpoint of curing, the amount of the C component is preferably 80 / R to 150 / R, particularly preferably 100 / R to 140 / R.

Even if it is an organic crosslinked polymer, the non-porous organic crosslinked polymer having no pores on the surface is difficult to dissolve and swell in the above (meth) acrylic acid-based polymerizable monomer and has little interaction with the matrix. Therefore, the paste may aggregate and settle in the paste, and the paste may become hard. If a large amount of this is added, the properties of the paste change during storage (specifically, it becomes hard), and the operability of the paste deteriorates. I may end up doing it. Therefore, when a non-porous organic crosslinked polymer is blended, the blending amount is preferably 10 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic acid-based polymerizable monomer, and the blending amount is completely. It is more preferable not to do so.

1-4. Other Ingredients In the production method of the present invention, a polymerization initiator used as a dental material can be preferably used. Examples of the polymerization initiator include a chemical (redox) polymerization initiator, a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

When the curable composition for artificial dentition produced by the present invention is a one-paste type, a photopolymerization initiator and / or a thermal polymerization initiator is used as the polymerization initiator, and the chemical polymerization initiator is completely or substantially. It is preferable not to include it in. Here, "substantially not contained" means that it is permissible to contain a very small amount within a range that does not adversely affect the storage stability and does not affect the effect of the present invention.

On the other hand, in the case of the 2-paste type, any known polymerization initiator can be used as long as it can polymerize and cure the component A. For example, radical polymerization initiators used in the dental field include chemical polymerization initiators (normal temperature redox initiators), photopolymerization initiators, thermal polymerization initiators, etc., which may be used alone. It may be used together. In the case of the two-paste type, it is preferable to distribute the polymerization initiator so that the polymerization starts when the two pastes are mixed, from the viewpoint of storage stability.

The chemical polymerization initiator is a polymerization initiator which is composed of two or more components and produces a polymerization active species at around room temperature by mixing all the components immediately before use. Typical examples of such a chemical polymerization initiator are organic peroxide / amine compound compounds.

Typical organic peroxides used as such chemical polymerization initiators include ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, peroxyesters, diacyl peroxides, and peroxydi. There are carbonates and the like, and specifically, methyl ethyl ketone peroxide, cyclohexano peroxide, P-methane hydroperoxide, diisopropylbenzene peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, benzoyl peroxide, di- Examples thereof include n-propyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate and the like.

The suitable amount of these organic peroxides to be used varies depending on the type of the organic peroxide used and cannot be unconditionally limited, but it should be used in the range of 0.05 to 5 parts by mass with respect to 100 parts by mass of the A component. Is preferable, and it is more preferable to use it in the range of 0.1 to 3 parts by mass. When the component A is divided into two compositions in a two-paste type, the amount of the component A is 100% by mass of the total amount of the (meth) acrylic acid-based polymerizable monomers contained in the two compositions. As a part, the amount of the organic peroxide used may be appropriately determined. Hereinafter, the same applies to the case where the amount of each composition used is specified with respect to the mass of the component A.

Further, as the tertiary amine for generating a radical in contact with these organic peroxides, a known compound is not particularly limited and is used. Specific examples of commonly used tertiary amine compounds include N, N-dimethylaniline, N, N-diethylaniline, N, N-dipropylaniline, N, N-dibutylaniline, N-methyl, Anilines such as N-β-hydroxyethylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dipropyl-p-toluidine, N, N-dibutyl-p- Toluidines such as toluidine, p-tolyldiethanolamine, p-tolyldipropanolamine, N, N-dimethyl-anisidine, N, N-diethyl-p-anisidine, N, N-dipropyl-p-anisidine, N, N- Anisidines such as dibutyl-p-anisidine, morpholins such as N-phenylmorpholine and N-toluidine morpholine, bis (N, N-dimethylaminophenyl) methane, bis (N, N-dimethylaminophenyl) ether And so on. 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. -Toluidine propanolamine is preferably used.

The amount of the tertiary amine compound used is 0. It is preferably used in the range of 05 to 5 parts by mass, and more preferably used in the range of 0.1 to 3 parts by mass.

Specific examples of the photopolymerization initiator 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. Classes; α-diketones such as diacetyl, benzyl, camphorquinone, 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) -Bisacylphosphinoxides such as phenylphosphine oxide can be mentioned. These can be used alone or in admixture of different types.

The photopolymerization initiator is preferably used in combination with a reducing compound. Suitable reducing compounds include tertiary amines such as 2- (dimethylamino) ethyl methacrylate, p-N, N-dimethylaminobenzoate ethyl, N-methyldiethanolamine, dimethylaminobenzaldehyde, terephthalaldehyde; Sulfur-containing compounds such as 2-mercaptobenzoxazole, 1-decanthyl, thiosartyl acid, and thiobenzoic acid; N-phenylalanine and the like can be mentioned.

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

Examples of the thermal polymerization initiator include peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxydicarbonate, and diisopropylperoxydicarbonate. Examples thereof include azo compounds such as azobisisobutyronitrile.

The blending amount of the photopolymerization initiator and the thermal polymerization initiator is the amount of the polymerization initiator used when the photopolymerization initiator or the thermal polymerization initiator is used alone, and the photopolymerization initiator and the thermal polymerization initiator are used. When used in combination, the total amount of the polymerization initiator may be as long as it is a catalytic amount (that is, an amount capable of exhibiting a function as a polymerization initiator and sufficiently polymerizing). The specific amount thereof varies depending on the type of polymerization initiator used and cannot be unconditionally limited, but it is preferably used in the range of 0.05 to 5 parts by mass with respect to 100 parts by mass of the A component, and is preferably 0.1. It is more preferable to use it in the range of about 3 parts by mass.

The amount of the reducing agent or photoacid generator used is preferably in the range of 0.05 to 5 parts by mass, and further preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the A component. preferable.

Further, in the production method of the present invention, calcium carbonate, magnesium oxide, barium sulfate, titanium oxide, potassium titanate, aluminum hydroxide, silica stone powder, glass powder, diatomaceous earth, silica, as long as the effects of the present invention are not impaired. Inorganic fillers such as calcium silicate, talc, alumina, mica, and quartz glass, granular organic-inorganic composite fillers obtained by preliminarily adding a polymerizable monomer to inorganic particles to form a paste, polymerizing, and pulverizing. Polymerization inhibitors such as butyl hydroxytoluene and methoxyhydroquinone, UV absorbers such as 4-methoxy-2-hydroxybenzophenone and 2- (2-benzotriazole) -p-cresol, polymerization modifiers such as α-methylstyrene dimer, Dyes, pigments, fragrances and the like can be added.

2. 2. Manufacturing Method of the Present Invention As described above, the manufacturing method of the present invention
The first step of mixing the component A (monomer) and the component B (soluble non-crosslinked polymer) at a predetermined mixing temperature: _TMIX (° C.) to obtain a liquid composition in which the component B is dissolved in the component A.
The present invention comprises a second step of mixing and kneading the liquid composition obtained in the first step with the C component (absorbent monomeric porous crosslinked polymer) to obtain a paste-like composition.

2-1. First step In the first step, a liquid composition in which component A (monomer) and component B (soluble non-bridged polymer) are mixed at a predetermined mixing temperature: _TMIX (° C.) and component B is dissolved in component A. However, in order to prevent the undissolved B component from remaining in the paste-like curable composition for artificial dentition, which is the target product, and the desired paste properties and the like cannot be obtained, the temperature is adjusted to _TMIX . The powdery B component in an amount equal to or less than the saturated dissolution amount of the A component with respect to the component B is dissolved in the A component while the B component is dissolved.

The mixing temperature is usually a temperature of room temperature or higher, but it is preferably 45 to 60 ° C. when the B component is difficult to dissolve when the B component is dissolved. If it is determined that stirring is difficult due to an increase in the viscosity of the mixed solution, the component B may be dissolved by stopping the stirring and keeping the mixed solution warm. The temperature at the time of heat retention is preferably about the same as the temperature at which the B component is stirred and dissolved. When the dissolution is carried out at such a temperature, if the dissolution is completely completed, the B component does not usually precipitate even when cooled to room temperature. After heat insulation, visually confirm that there is no undissolved residue at 25 ° C., and if there is any undissolved residue, insulate until all of the undissolved residue is dissolved. Even when the dissolution of the component A is confirmed only by stirring, it is preferable to keep the heat for a certain period of time.

The first step preferably includes the following dispersion step and dissolution step because the component B can be efficiently dissolved in the component A.

Dispersion step: A condition in which the A component or a part of the A component is used as a dispersion medium, and the saturated dissolution amount of the dispersion medium with respect to the B component is smaller than the saturated dissolution amount of the A component with respect to the component B in the temperature: _TMIX . A step of mixing the dispersion medium and the powdery B component to obtain a dispersion liquid in which the powdery B component is dispersed in the dispersion medium.

Dissolution step: A step of dissolving the B component in a state in which the dispersion liquid obtained in the dispersion step contains the entire amount of the A component and the total amount of the powdery B component, and the temperature of the system is _TMIX .

Further, (meth) acrylic which is a liquid at normal temperature and pressure having a predetermined composition at a predetermined temperature because it is highly efficient and a liquid composition in which the component B is dissolved in the component A can be obtained in a short time. Acid-based polymerizable monomer component: When the maximum amount (part by mass) of the B component soluble in 100 parts by mass is defined as the solubility of the polymerizable monomer component in the B component at the predetermined temperature, the above. In the dispersion step, the dispersion medium and the powdery B component are mixed at a temperature at which the solubility of the A component as the dispersion medium or a part of the A component in the B component is 5 or less, and the dispersion medium is in the form of a powder. It is preferable to obtain a dispersion liquid in which the B component of the above is dispersed.

Specifically, it is preferable to adopt the method shown in the following (1) or (2).

(1) After mixing the A component and the powdery B component at a temperature such that the solubility of the A component in the B component is 5 or less to disperse the powdery B component, the temperature of the mixed solution is set to _TMIX . A method of dissolving the B component while dispersing the powdery B component in the A component.

(2) As the A component, the A1 component composed of a (meth) acrylic acid-based polymerizable monomer having a solubility of the B component in T _MIX of 5 or less and the solubility of the B component in T _MIX exceeding 5 (meth). After preparing a dispersion liquid in which a powdery B component is dispersed in the A1 component using a mixture of the A2 component composed of an acrylic acid-based polymerizable monomer, the dispersion liquid and the A2 component are mixed under stirring. A method of dissolving the B component while dispersing the powdery B component in the A component by mixing with T _MIX .

The liquid composition obtained by the first step usually has a loss tangent at 23 ° C.: tanδ ₍₂₃₎ is in the range of 1.0 to 3.0, preferably 1.5 to 3.0. The curable composition for a denture base obtained by using the liquid composition has good paste properties. The loss tangent tan δ is the ratio of the storage elastic modulus to the loss elastic modulus. Become. The value of tan δ ₍₂₃₎ of the liquid composition can be measured using a modular compact rheometer MCR302 (manufactured by Anton Pearl).

When the above-mentioned polymerization initiator, polymerization inhibitor, ultraviolet absorber, etc. are used as other components, these components may be added at any stage, but are the components A and B in the first step. It is preferable to dissolve it in the component A before mixing.

2-2. Second Step In the second step, the liquid composition obtained in the first step and the C component (absorbent monomeric porous crosslinked polymer) are mixed and kneaded to obtain a paste-like composition.

When the liquid composition obtained in the first step and the C component are stirred and mixed at normal temperature and pressure, the whole becomes rice cake-like and cohesive, but the time required until then is the monomer to be used and It varies depending on the combination of the absorbent monomeric porous crosslinked polymer. In order to reduce the unevenness of the paste as much as possible, it is preferable to visually confirm that the paste is uniform and then continue kneading for 10 minutes or more. If the properties of the obtained paste are too hard or too soft, the properties of the paste can be controlled by appropriately adding a liquid composition or the C component. Since the paste after kneading contains air bubbles, it is preferable to perform defoaming under vacuum conditions. By the above method, a one-paste type curable composition for a denture base can be produced.

When the above-mentioned filler is used as the other component, the filler may be added at any stage, but it is preferable to add the filler at the same timing when mixing the liquid composition and the C component in the second step. ..

The production method of the present invention is not limited to the production of a 1-paste type curable composition for a denture base, but is a 2-paste type curable composition for a denture base, and two pastes are used, respectively. It can also be applied to the case of producing a composition in which the A component, the B component, and the C component are contained in both compositions when the first composition and the second composition are prepared, and only one of them is A to C. It can be applied as a method for producing one of the compositions when the three components are contained.

3. 3. Curable composition for denture base obtained by the method of the present invention 3-1. Preservation method The paste-like curable composition for denture bases produced by the production method of the present invention is stored in a light-shielding container in order to prevent deterioration during storage, especially when a photopolymerization initiator is used. Is preferable. The form of the paste is not particularly limited, but a rod, a horseshoe, a sheet, a sphere, a prism, or the like may be molded into a container, or may be stored in a tube, a bottle, or the like without being molded. good.

3-2. About the method of use When the curable composition for a denture base obtained by the production method of the present invention is used as a resin for a denture base, a rigid backing material, or a resin for repair, it can be used by a known method.

1 When a new denture is prepared with a paste mold, an impression in the oral cavity of the patient is obtained to prepare a gypsum model, and the manufactured denture base curable composition manufactured by the present invention is used on the gypsum model. The denture base is formed using the denture, set in an articulator, and the artificial teeth are arranged. Then, the denture is polymerized and cured by light irradiation or heating, and the denture is corrected and polished to produce a denture.

2 When a new denture is prepared with a paste mold, an impression in the oral cavity of the patient is obtained to prepare a gypsum model, and the first composition and / or the second composition produced according to the present invention on the gypsum model. A denture base is formed using a curable composition for a denture base, which is a mixture of both compositions containing a substance, and the denture base is set in an articulator to arrange artificial teeth, and then a photopolymerization catalyst or a thermal polymerization catalyst is used. When is used, the denture is produced by polymerizing and curing it by irradiation with light or heating to correct the shape and polish it.

When repairing a denture that is incompatible, apply an adhesive / separating material to the denture that is no longer compatible with the patient's oral cavity, and paste (in the case of a 2-paste type, the first composition and the second composition). After arranging the paste) in the patient's oral cavity, if a photopolymerization catalyst or a thermal polymerization catalyst is used, the denture is polymerized and cured by light irradiation or heating to correct the shape and polish, and the fit of the denture is improved. To. When lining the mucosal surface, the paste may be spread thinly, and when the floor is extended, the paste may be wrapped in a stick shape.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples in order to specifically explain the present invention, but the present invention is not limited thereto.

1. 1. The names, characteristics, abbreviations (when abbreviations are used), etc. of the various compounds used in each Example and Comparative Example are shown for the various compounds used in each Example and Comparative Example.

1-1. Component A: (meth) acrylic acid-based polymerizable monomer ・ HPr: 2-methacryloyloxyethyl purpionate (monofunctional polymerizable monomer)
ND: Nonamethylenediol dimethacrylate (bifunctional polymerizable monomer)
-UDM: 1,6-bis (methacrylethyloxycarbonylamino) trimethylhexane-TT: trimethylolpropane trimethacrylate (trifunctional polymerizable monomer).

1-2. Component B: Soluble non-crosslinked polymer powder ・ PMMA: Polymethylmethacrylate (average particle size (d): 20 μm, weight average molecular weight (Mw): 250,000)
-PEMA: Polyethyl methacrylate (d: 35 μm, Mw 500,000)
P (EMA-MMA): Polyethyl methacrylate-methyl methacrylate copolymer (ethyl methacrylate / methyl methacrylate = 50/50, d: 40 μm, Mw: 1 million)
-PBMA: Polybutylmethacrylate (d: 60 μm, Mw: 150,000).

1-3. Component C: Absorbent monomeric porous organic crosslinked polymer powder Table 1 shows the abbreviations, components, average particle size and average pore diameter of the polymers used (all manufactured by Sekisui Plastics Co., Ltd.).

1-4. Polymerization Initiator ・ CQ: Camphorquinone ・ BPO: Benzoyl Peroxide ・ DMBE: 4- (N, N-dimethylamino) Ethyl Benzoate ・ DEPT: N, N-diethyl-p-toluidine.

1-4. Non-porous organic crosslinked polymer-PMMA-X: Polymethylmethacrylate (d: 8 μm, manufactured by Sekisui Plastics Co., Ltd.).

2. 2. Example and Comparative Example Example 1
(1) Raw material A mixture of 50 parts by mass of HPr and 50 parts by mass of ND was used as the A component, PEMA was used as the B component, and PMMA-P8 was used as the C component. Moreover, CQ and DMBE were used as a polymerization initiator. Table 2 summarizes the compositions of the curable composition for denture bases, which is the product to be manufactured.

For convenience, the solubility of component A in the component B at the mixing temperature was evaluated based on whether it was at least a certain value or less than a certain value. Specifically, a predetermined amount: X parts by mass of B component is used for 100 parts by mass of A component, and the mixture is stirred at a mixing temperature for 3 hours using a stirrer, and the presence or absence of undissolved residue is visually confirmed. If there is no undissolved residue and it is completely dissolved, the solubility is X or more, and if the undissolved residue is confirmed, the solubility is less than X, and the former (X or more) is described as "X <". , The latter (less than X) is expressed as "<X". When a visual check was performed at X = 25 parts by mass according to this method, it can be said that the solubility of the A component in the B component is 25 or more (25 <) because there was no undissolved residue.

Further, the monomer absorption amount R of PMMA-P8, which is a C component, with respect to the A component was measured by the following method and found to be 2.4. The blending amount of the C component is 50 parts by mass, which is in the range of 65 / R = 27.1 to 165 / R = 68.8.

[Measurement method of monomer absorption amount]
In the refined flax oil method described in JIS K5101-13-1, the place where oil is used for refined flax is used in each Example or Comparative Example. It was measured by replacing it with a mixture). Specifically, a predetermined amount (g) [MB (g)] of _C component is placed on a glass plate, and 4 or 5 drops of the A component monomer are gradually added from the burette at a time, each time. The monomer was kneaded into the polymer with a palette knife. Repeat these steps until a lump of monomer and polymer is formed, then drop one drop at a time and repeat until the paste is completely kneaded. The amount (g) [MA (g)] of the _A component monomer used was measured. The time required for the operation to the end point was set to be within 25 minutes.

Based on the above MB (g) and _MA (g), the following formula Monomer absorption amount _R = _MA (g) / _MB (g)
The monomer absorption amount was calculated according to the above.

(2) First Step The _mixing temperature (TMIX) was set to 25 ° C., which is a normal temperature, and a liquid composition in which the B component was dissolved in the A component was prepared as follows.
That is, in a screw tube bottle (25 ml) containing a stirrer, 8 g of HPr and 8 g of ND as the A component, 80 mg of CQ (0.5 part by mass with respect to 100 parts by mass of the A component) and 80 mg of DMBE as the polymerization initiator ( 0.5 part by mass with respect to 100 parts by mass of A component), and while stirring these under normal temperature and normal pressure {25 ° C., 1 atm (≈1013 hPa)}, 4 g of PEMA, which is B component (100 mass by mass of A component). 25 parts by mass with respect to the portion) was added little by little so as not to agglomerate, and the entire amount of the B component was added, and stirring was continued until the post-solution became uniform. Then, the obtained mixed solution was kept warm in an incubator at 45 ° C. for 2 hours, naturally cooled to 25 ° C., and then visually confirmed that there was no undissolved residue.
Since the solubility of the A component in the B component is 25 or more, it can be said that the saturated dissolution amount of the B component in 16 g of the A component is 4 g or more.

(3) Loss of liquid composition Direct contact: tanδ measurement For the liquid composition thus obtained, a modular compact rheometer MCR302 (manufactured by Anton Pearl) was used, a cone plate with a diameter of 20 mm and 1 ° was used, and a frequency of 1 Hz was used. The measurement was performed under the conditions of a measurement temperature of 23 ° C. and a shear strain (vibration) of 0.1%, and the tan δ was evaluated to be 1.7. The average value after 60 seconds from the start of measurement when measured for 5 minutes under the above conditions was defined as the loss tangent of the liquid composition: tan δ.

(4) Second step Transfer 19 g of the liquid composition obtained in the first step onto a mortar, and add 7.5 g of PMMA-P8 as a C component (50 parts by mass with respect to 100 parts by mass of the A component). Then, using a pestle, the mixture was mixed at 25 ° C. for 10 minutes. After mixing, it was visually confirmed that a uniform paste was obtained, and after further mixing for 10 minutes, the obtained paste was defoamed under vacuum conditions to obtain a paste-like curable composition for a denture base.

(5) Manufacturing time The time required for the first step is 3 hours and 30 minutes, and the time required for the second step (time until the paste is finally defoamed) is 30 minutes, which is the total of both. One production time was 4.0 hours.

(6) Evaluation of Curable Composition for Paste-like Prosthesis With respect to the curable composition for artificial dentition obtained in the second step, paste hardness, paste adhesiveness, and paste properties after 1 month are evaluated and cured. Bending strength, elastic modulus, and breaking energy were evaluated for the body. The evaluation method is shown below.

[Evaluation method of paste hardness]
A paste (curable composition for denture base) was filled into a SUS nut-shaped mold to flatten the surface, and the mixture was left under shading for 2 minutes to keep the temperature constant at 23 ° C. A SUS rod with a diameter (Φ) of 5 mm is attached to the Sun Leometer CR-150 (manufactured by Sun Kagaku Co., Ltd.) as a pressure-sensitive shaft, and the maximum load [g] when compressed to a depth of 2 mm at a speed of 240 mm / min. Was the paste hardness.

[Paste adhesiveness evaluation method]
Gloves were attached, and the paste (curable composition for denture base) was evaluated by ⊚ to × according to the following criteria.
⊚: Does not adhere to gloves but adheres to dentures and plaster Δ: Adheres to gloves but can be peeled off from gloves when adhered to dentures and plaster ×: Adheres to gloves and does not adhere to dentures and plaster. It does not adhere to gloves and does not adhere to plaster.

[Method for evaluating paste properties after 1 month]
The paste (curable composition for denture base) was stored at 23 ° C. for 1 month, and evaluated as ⊚ to × according to the following criteria.
⊚: No change from immediately after paste preparation Δ: Slight viscosity change immediately after paste preparation ×: Significant viscosity change immediately after paste preparation.

[Evaluation method of bending strength, elastic modulus, and breaking energy of cured product]
When a 30 x 30 x 2 mm polytetrafluoroethylene mold is filled with a paste (curable composition for artificial dentition) and a photopolymerization catalyst is used, photopolymerization for dental technology is performed with both sides pressed with a polyethylene film. A cured product was prepared by irradiating with light for 5 minutes using the device α-light V (manufactured by MORITA). A cured product was prepared by heating for 1 hour from the above, and when a chemical polymerization catalyst was used, both sides were pressed with a polyethylene film and cured to prepare a cured product. Then, the cured product was polished with # 800 and # 1500 water-resistant abrasive paper, and then cut into 4 × 30 × 2 mm prisms. The obtained cured product was immersed in water and left at 37 ° C. for 24 hours. This test piece is mounted on a testing machine (manufactured by Shimadzu Corporation, Autograph AG-1), and a 3-point bending test is performed at a distance between fulcrums of 20 mm and a crosshead speed of 1 mm / min to determine bending strength, elastic modulus, and breaking energy. It was measured.

The evaluation results are shown in Tables 3 and 4. As shown in Tables 3 and 4, the paste properties are good, do not adhere to the gloves, adhere to the denture and plaster, the paste properties after 1 month do not change immediately after preparation, and the storage stability is excellent. rice field. Further, it was confirmed that the cured product had a high bending strength of 78 [MPa] and a breaking energy of 90 [N · mm], both of which had high strength and toughness.

Examples 2-7, 9-16
A curable composition for a denture base was produced in the same manner as in Example 1 except that the composition of the paste was changed as shown in Table 2. In any of the examples, the B component is completely dissolved at the mixing temperature. In addition, "↑" in Table 2 means "same as above", and the number in parentheses () represents the mass part.
The obtained curable composition for denture base was evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4.

Examples 2 to 7 and 9 to 16 all had high strength and toughness, and the operability and storage stability of the paste were also excellent.

Example 8
The composition of the paste was changed as shown in Table 2, and the A component, the B component, and the polymerization initiator were stirred in the production method of Example 1 by heating the temperature to 55 ° C. ( _TMIX = 55 ° C.). A curable composition for a denture base was produced and evaluated in the same manner as in Example 1 except that the obtained mixed solution was kept warm in an incubator at 55 ° C. for 2 hours. The results are shown in Tables 3 and 4.

Although the B component used in Example 8 was difficult to dissolve in the A component at room temperature, it could be completely dissolved by mixing while heating, and the dissolved state was maintained even at room temperature (25 ° C.). A paste having excellent paste operability and storage stability was obtained, and also had high strength and toughness.

Example 17
As shown in Table 2, the two pastes were used as the first composition (a) and the second composition (b), respectively, and each composition was produced in the same manner as in Example 1 and evaluated. The bending strength, elastic modulus and breaking energy are the physical characteristics of the cured product obtained by mixing Examples 17 (a) and (b). The results are shown in Tables 3 and 4.

Example 17 was a two-paste type denture base curable composition, which had high strength and toughness as in the one-paste type, and was also excellent in paste operability and storage stability.

Example 18
The composition of the paste is the same as that of Example 1. In the process of preparing the liquid composition, the component A and the polymerization initiator are added to the screw tube bottle (25 ml), the mixture is stirred under normal temperature and pressure, and then the mixed solution is added. The mixture was cooled to 2 ° C., component B was added while maintaining the temperature at 2 ° C., and the mixture was stirred until the component B was uniformly dispersed. At this time, the solubility of component B in component A at 2 ° C. was less than 5. Then, the mixture was manufactured and evaluated in the same manner as in Example 1 except that the mixture was stirred again at normal temperature and pressure until the mixture became uniform. The results are shown in Tables 3 and 4.

In Example 18, the component A was cooled and mixed under the condition that the solubility of the component B was less than 5, so that the component B was quickly and uniformly dispersed in the component A, and the time required for the first step was 2 hours and 30 minutes. It was greatly shortened, which led to a reduction in manufacturing time.

Example 19
The composition of the paste was the same as that of Example 1, and in the step of preparing the liquid composition, ND of the B component, the CQ, and the A component were added to the screw tube bottle, and the mixture was stirred until the B component was uniformly dispersed. Then, HPr, which is the other component A, was added, and the mixture was stirred until the mixture became uniform. Other than that, the mixture was produced in the same manner as in Example 1 and evaluated. The results are shown in Tables 3 and 4. The solubility of component B in ND at 25 ° C. was less than 5, and the solubility in HPr was 25 or more.

In Example 19, by adding the B component to the ND in which the solubility of the B component at 25 ° C. among the A components is less than 5, the B component is quickly and uniformly dispersed in the A component, and the time required for the first step. Was greatly reduced to 2 hours and 30 minutes, which led to a reduction in manufacturing time.

Comparative Example 1
In a screw tube bottle (25 ml) containing a stirrer, HPr 8 g and ND 8 g as A component, PEMA 4 g as B component (25 parts by mass with respect to 100 parts by mass of A component), and PMMA-P8 8 g as C component (25 parts by mass). 50 parts by mass with respect to 100 parts by mass of A component), 80 mg of CQ as a polymerization initiator (0.5 parts by mass with respect to 100 parts by mass of A component), 80 mg of DMBE (0.5 parts by mass with respect to 100 parts by mass of A component). Part), were added in sequence, and the mixture was stirred at normal temperature and pressure for 30 minutes. Since the viscosity of the mixture increased and it became difficult to stir, the mixture was added on a mortar and mixed with a pestle under normal temperature and pressure for 10 minutes to obtain a paste-like curable composition for a denture base. Evaluation was performed in the same manner as in Example 1. The results are shown in Tables 3 and 4.

In Comparative Example 1, since the paste was produced in one step, the B component remained, and the paste properties changed significantly when stored for a long period of time.

Comparative Example 2
In a screw tube bottle (25 ml) containing a stirrer, HPr 8 g, ND 8 g as A component, CQ 80 mg (0.5 part by mass with respect to 100 parts by mass of A component), DMBE 80 mg (A component 100) as a polymerization initiator. 0.5 parts by mass with respect to 100 parts by mass), and while stirring these under normal temperature and pressure, 4 g of PEMA (25 parts by mass with respect to 100 parts by mass of A component), which is the B component, was added in full at one time. Produced and evaluated a curable composition for a prosthesis bed in the same manner as in Example 1. The results are shown in Tables 3 and 4.

In Comparative Example 2, since the non-crosslinked polymer which is the B component was added in the entire amount at one time, the B component was aggregated without being dispersed in the A component, so that it took a long time to dissolve. In addition, the B component remained, and the paste properties changed significantly when stored for a long period of time.

Comparative Example 3
A curable composition for a denture base was produced and evaluated in the same manner as in Example 1 except that the composition of the paste was changed as shown in Table 2. The results are shown in Tables 3 and 4.

In Comparative Example 3, since the non-porous organic crosslinked polymer is used instead of the porous organic crosslinked polymer which is the C component, the strength of the cured product is low and the paste properties after one month are significantly changed immediately after the preparation. Was.

Claims (5)

Component A: A component consisting of a (meth) acrylic acid-based polymerizable monomer that is liquid at normal temperature and pressure.
Component B: A component made of a (meth) acrylic acid-based non-crosslinked polymer that can be dissolved in the component A, and component C: a component made of a porous organic crosslinked polymer that can absorb the component A.
A method for producing a paste-like curable composition for a denture base comprising.
The first step of mixing the A component and the B component at a predetermined mixing temperature: _TMIX (° C.) to obtain a liquid composition in which the B component is dissolved in the A component.
The second step of mixing and kneading the liquid composition obtained in the first step and the C component to obtain a paste-like composition, and the second step.
In the first step, the B component is dissolved while dispersing the powdery B component in an amount equal to or less than the saturated dissolution amount of the A component with respect to the component B in the temperature: _TMIX . A method for producing a paste-like curable composition for a denture base. The component B was measured at 5 to 40 (parts by mass) with respect to the component A 100 (parts by mass) and less than or equal to the saturated dissolution amount of the component A in TMIX, and the component C was measured according to JIS _K5101-13-1 . When the amount of A component (mass part) absorbed per unit amount (mass part) of C component is the absorption amount R (A component mass part / C component mass part), 65 / R to 165 / The method for producing a paste-like curable composition for an artificial dentition according to claim 1, wherein the paste-like curable composition for an artificial dentition comprising an amount of R (part by mass) is produced. The first step is
The dispersion is carried out under the condition that the A component or a part of the A component is used as a dispersion medium and the saturated dissolution amount of the dispersion medium with respect to the B component is smaller than the saturated dissolution amount of the A component with respect to the component B in the temperature: _TMIX . The dispersion step of mixing the medium and the powdery B component to obtain a dispersion liquid in which the powdery B component is dispersed in the dispersion medium, and the dispersion liquid obtained in the dispersion step are the total amount of the A component. A dissolution step in which the B component is dissolved in a state where the temperature of the system is _TMIX , and the total amount of the B component in the form of a sol is contained.
The method for producing a paste-like curable composition for a denture base according to claim 1 or 2. A (meth) acrylic acid-based polymerizable monomer component that has a predetermined composition and is liquid at normal temperature and pressure at a predetermined temperature: The maximum amount (parts by mass) of the B component that is soluble in 100 parts by mass. When the solubility of the polymerizable monomer component in the B component at the temperature of
In the dispersion step, the dispersion medium and the powdery B component are mixed at a temperature at which the solubility of the A component as the dispersion medium or a part of the A component in the B component is 5 or less, and the powder is mixed with the dispersion medium. To obtain a dispersion liquid in which the sol B component is dispersed,
The method for producing a paste-like curable composition for a denture base according to claim 3. As the A component, the A1 component composed of a (meth) acrylic acid-based polymerizable monomer having a solubility of the B component in T _MIX of 5 or less and the (meth) acrylic acid system having a solubility of the B component in T _MIX exceeding 5. Using a mixture of A2 component composed of polymerizable monomer,
In the dispersion step, an A1 component was used as a dispersion medium to obtain a dispersion liquid in which the powdery B component was dispersed in the A1 component.
In the dissolution step, the dispersion liquid and the A2 component are mixed to bring the total amount of the A component and the total amount of the powdery B component into a state, and then the B component is dissolved by temperature: T _MIX .
The method for producing a paste-like curable composition for a denture base according to claim 4.