WO2015046100A1 - Composition and method for producing same - Google Patents

Abstract

This composition contains a polymer (A), a monomer (B) and a polymerization initiator (C). This composition contains 100-280 parts by mass of the polymer (A) per 100 parts by mass of the monomer (B), and the polymer (A) contains 70% by mass or more of a methyl methacrylate unit. The monomer (B) contains 70-99.5% by mass of at least one compound that is selected from among compounds (b1) represented by formula (1) and methyl methacrylate (b2), and 0.5-30% by mass of 1,4-pentadien-3-ol (b3). A molded article that has excellent toughness and low water absorption, while exhibiting high strength and high elastic modulus can be obtained using this composition. (In the formula, each of R₁ and R₂ independently represents a hydrogen atom or a methyl group, and at least one of R₁ and R₂ is a hydrogen atom.)

Description

Composition and method for producing the same

The present invention relates to a polymer containing a methyl methacrylate unit, a composition containing a plurality of monomers and a polymerization initiator, and a method for producing the same. Moreover, it is related with the medical composition which consists of such a composition, especially a dental composition. Furthermore, the present invention relates to a molded product obtained by curing the composition and a kit for producing the composition.

A composition containing a polymer, a monomer, and a polymerization initiator is used as a material for a molded article. Such a composition is usually produced by mixing a polymer powder and a monomer liquid. And, as a method for producing a molded article, usually, a polymer powder and a monomer liquid are mixed, and the mixture is shaped after waiting until the mixture becomes cocoon-like, and then polymerized and cured. The method of obtaining the thing of this shape is used. If such a manufacturing method is used, manufacture of a composition and subsequent shaping are possible by simple operation. Until now, as such a composition, what is obtained by mixing a powder of polymethyl methacrylate (PMMA) and a liquid of methyl methacrylate (MMA) is known, and the composition is used in the medical field and the like. Has been. For example, the composition is used as a material such as a denture base material and a mouthpiece material in the dental field, and is also used as a bone cement material and the like in the orthopedic field.

However, a cured product obtained by polymerizing a composition containing polymethyl methacrylate, methyl methacrylate and a polymerization initiator has high hardness and high strength, but may have insufficient toughness. Therefore, depending on the application, there is a risk of breakage due to stress or impact during use, and the improvement has been demanded. Further, when the cured product is used for a long time in a moist state, the mechanical properties may deteriorate due to water absorption of the molded product. In particular, denture bases and mouthpieces may be colored with coffee or tea or used for a long period of time, which may cause bad odors, and a reduction in water absorption rate has been demanded.

In Patent Document 1, a polymerizable monomer having an unsaturated double bond, a polyalkyl (meth) acrylate, and a polymerization catalyst are mixed, and at least a part of the polyalkyl (meth) acrylate is polymerizable. A denture base resin material characterized by being dissolved in a monomer is described. This makes it possible to obtain a cured body that is paste-like in advance and can be simplified in operation, and has a large elastic energy and appropriate hardness and tenacity. In the examples, examples using 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate and ethylene glycol dimethacrylate as polymerizable monomers are described, but their strength was insufficient. .

In Patent Document 2, a polyalkyl (meth) acrylate powder and a vinyl ester monomer solution having 6 or more carbon atoms are mixed and thickened in the presence of a polymerization initiator, and then shaped. Then, a method for producing a molded article is described in which the polymerization reaction is allowed to proceed and then cured. However, when a vinyl ester monomer is used as the liquid agent, the elastic modulus of the obtained molded product is low, and it may be insufficient for use in applications requiring high elastic modulus.

In Patent Document 3, polymethylmethacrylate powder and polyethylene glycol di (meth) acrylate solution are mixed in the presence of a polymerization initiator to increase the viscosity, and then the polymerization reaction is allowed to proceed. A method for producing a molded product to be cured is described. However, polyethylene glycol di (meth) acrylate has a slow rate of swelling the powder of polymethyl methacrylate, and the mixing operation requires 24 hours or more, so that the operability is insufficient. In some applications, the balance of strength, elastic modulus, and toughness may be insufficient.

JP 2000-254152 A WO2006 / 077944 WO2011 / 090078

The present invention has been made to solve the above problems, and provides a composition capable of obtaining a molded product having high strength and high elastic modulus, excellent toughness, and low water absorption. It is the purpose. Moreover, it aims at providing the method which can prepare such a resin composition simply.

The said subject is a composition containing a polymer (A), a monomer (B), and a polymerization initiator (C);
Containing 100 to 280 parts by mass of the polymer (A) with respect to 100 parts by mass of the monomer (B),
The polymer (A) contains 70% by mass or more of methyl methacrylate units,
The monomer (B) is represented by the following formula (1)

[Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and at least one of R ₁ and R ₂ is a hydrogen atom. ]
70 to 99.5% by mass of at least one compound selected from the compound (b1) and methyl methacrylate (b2) represented by formula (2):

It is solved by providing a composition characterized by containing 0.5 to 30% by mass of 1,4-pentadien-3-ol (b3) represented by the formula:

At this time, it is preferable that the composition has a heterogeneous structure derived from the particles of the polymer (A).

The above composition wherein the monomer (B) contains 70 to 99.5% by mass of the compound (b1) and 0.5 to 30% by mass of 1,4-pentadien-3-ol (b3) is preferable. It is an aspect. Further, the composition wherein the monomer (B) contains 70 to 99.5% by mass of methyl methacrylate (b2) and 0.5 to 30% by mass of 1,4-pentadien-3-ol (b3) is also provided. Is a preferred embodiment.

A medical composition comprising the above composition is a preferred embodiment of the present invention, and a dental composition comprising the medical composition, particularly a dental adhesive, is a more preferred embodiment. Specifically, a bone cement made of the medical composition is a preferred embodiment. A molded product obtained by curing the composition is also a preferred embodiment of the present invention. Specifically, a denture base or mouthpiece obtained by curing the dental composition is a preferred embodiment.

Further, the above-mentioned problem is that the powder of the polymer (A) and the liquid agent of the monomer (B) are mixed and thickened in the presence of the polymerization initiator (C). It is also solved by providing a manufacturing method. At this time, it is preferable that the polymer (A) contains a polymerization initiator (C) in advance.

Furthermore, the above-mentioned subject is a powder of polymer (A) containing 70% by mass or more of a methyl methacrylate unit,
Following formula (1)

[Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and at least one of R ₁ and R ₂ is a hydrogen atom. ]
70 to 99.5% by mass of at least one compound selected from the compound (b1) and methyl methacrylate (b2) represented by formula (2):

And a solution of monomer (B) containing 0.5 to 30% by mass of 1,4-pentadien-3-ol (b3) represented by the formula: wherein at least one of the powder or the solution is polymerized It is also solved by providing a kit containing the initiator (C).

The composition of the present invention can be easily prepared. In addition, a molded product obtained by curing the composition of the present invention is excellent in toughness while having high strength and high elastic modulus, and also has a low water absorption. Therefore, the composition is suitably used for manufacturing a denture base or a mouthpiece, and is also suitably used as a dental adhesive or bone cement. Furthermore, according to the kit of this invention, the said composition can be manufactured simply.

22 is a microscopic image of a thin section of a molded product in Example 21. FIG. In Examples 1 to 6 and Comparative Example 2, the content (mass%) of 1,4-pentadien-3-ol (b3) is plotted on the horizontal axis, and the flexural modulus (GPa) of the obtained test piece is plotted on the vertical axis. Is a graph in which is plotted. In Examples 1 to 6 and Comparative Example 2, the content (mass%) of 1,4-pentadien-3-ol (b3) is plotted on the horizontal axis, and the bending strength (MPa) of the test piece obtained is plotted on the vertical axis. Is a graph in which is plotted. In Examples 1 to 6 and Comparative Example 2, the content (mass%) of 1,4-pentadien-3-ol (b3) is plotted on the horizontal axis, and the maximum deflection amount (mm) of the test piece obtained on the vertical axis. Is a graph in which is plotted. In Examples 1 to 6 and Comparative Example 2, the content (mass%) of 1,4-pentadien-3-ol (b3) is plotted on the horizontal axis, and the breaking energy (KJ / m) of the test piece obtained is plotted on the vertical axis. ² ) is a graph obtained by plotting. In Examples 1 to 7 and Comparative Examples 1 and 2, the horizontal axis represents the content (mass%) of 1,4-pentadien-3-ol (b3), and the vertical axis represents the apparent saturated water absorption rate of the obtained test piece. It is the graph which plotted (mass%). In Examples 11 to 20 and Comparative Example 3, the content (mass%) of 1,4-pentadien-3-ol (b3) is plotted on the horizontal axis, and the flexural modulus (GPa) of the test piece obtained is plotted on the vertical axis. Is a graph in which is plotted. In Examples 11 to 20 and Comparative Example 3, the content (mass%) of 1,4-pentadien-3-ol (b3) is plotted on the horizontal axis, and the bending strength (MPa) of the obtained test piece is plotted on the vertical axis. Is a graph in which is plotted. In Examples 11 to 20 and Comparative Example 3, the horizontal axis represents the content (% by mass) of 1,4-pentadien-3-ol (b3), and the vertical axis represents the maximum deflection amount (mm) of the obtained test piece. Is a graph in which is plotted. In Examples 11 to 20 and Comparative Example 3, the content (mass%) of 1,4-pentadien-3-ol (b3) is plotted on the horizontal axis, and the breaking energy (KJ / m) of the obtained test piece is plotted on the vertical axis. ² ) is a graph obtained by plotting. In Examples 11 to 20 and Comparative Example 3, the horizontal axis represents the content (mass%) of 1,4-pentadien-3-ol (b3), and the vertical axis represents the apparent saturated water absorption (mass). %).

The composition of the present invention is a composition containing a polymer (A), a monomer (B) and a polymerization initiator (C);
Containing 100 to 280 parts by mass of the polymer (A) with respect to 100 parts by mass of the monomer (B),
The polymer (A) contains 70% by mass or more of methyl methacrylate units,
The monomer (B) is represented by the following formula (1)

[Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and at least one of R ₁ and R ₂ is a hydrogen atom. ]
70 to 99.5% by mass of at least one compound selected from the compound (b1) and methyl methacrylate (b2) represented by formula (2):

1,4-pentadien-3-ol (b3) represented by the formula:

Polymer (A) is a polymer containing 70% by mass or more of methyl methacrylate units. By containing 70% by mass or more of methyl methacrylate units, a molded product having high strength and high elastic modulus can be obtained. Therefore, such a molded article is suitably used as a denture base material, a mouthpiece material, or the like that requires a predetermined strength and elastic modulus. Further, the polymer (A) containing 70% by mass or more of methyl methacrylate units has higher biocompatibility than a polymer containing a halogen atom or a polymer containing an aromatic ring. Furthermore, the polymer (A) is an amorphous polymer having a relatively high glass transition temperature, and a powder having a particle size suitable for the practice of the present invention can be easily obtained by suspension polymerization or the like. The polymer (A) may be a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and other monomers. The content of the methyl methacrylate unit in the polymer (A) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. When the methyl methacrylate unit is less than 70% by mass, the strength and elastic modulus of the obtained molded product are lowered.

When the polymer (A) is a copolymer, the monomer to be copolymerized with methyl methacrylate is not particularly limited as long as it is a monomer copolymerizable with methyl methacrylate. For example, alkyls such as methyl acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate or t-butyl (meth) acrylate ( Meth) acrylate; olefins such as ethylene and propylene; vinyl carboxylates such as vinyl acetate; maleic anhydride; acrylonitrile; styrene; vinyl chloride and the like. These monomers can be used alone or in combination of two or more. From the viewpoint of polymerizability, alkyl (meth) acrylate is preferred. From the viewpoint of ease of swelling of the polymer (A) in the case of producing a composition using the powder of the polymer (A) and the liquid agent of the monomer (B), ethyl methacrylate is preferable. is there. The content of these monomers is 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.

The molecular weight of the polymer (A) is not particularly limited, but those having a weight average molecular weight of 5,000 to 2,000,000 are usually used. When the molecular weight is lower than 5,000, the strength of the obtained molded product may be insufficient. The molecular weight is more preferably 200,000 or more, and further preferably 300,000 or more. The molecular weight of the polymer (A) is more preferably 1,500,000 or less, and more preferably 1,000,000 or less. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

The monomer (B) contained in the composition of the present invention contains 70 to 99.5 mass of at least one compound selected from the compound (b1) represented by the above formula (1) and methyl methacrylate (b2). % And 1,4-pentadien-3-ol (b3) represented by the above formula (2) in an amount of 0.5 to 30% by mass. Here, the greatest feature of the present invention is that the monomer (B) contains 1,4-pentadien-3-ol (b3). By including 1,4-pentadien-3-ol (b3), the toughness of the obtained molded product is greatly improved. At this time, since the elastic modulus and strength do not decrease so much, a molded product having high strength and high elastic modulus and excellent toughness can be obtained. Further, by including 1,4-pentadien-3-ol (b3), the water absorption of the obtained molded product is lowered. Furthermore, since none of the compound (b1) represented by the above formula (1), methyl methacrylate (b2) and 1,4-pentadien-3-ol (b3) contains a halogen element or an aromatic ring, the present invention This composition is considered to be highly biocompatible.

Both the compound (b1) represented by the above formula (1), which is the main component in the monomer (B), and methyl methacrylate (b2) are composed by rapidly swelling the particles of the polymer (A). Since a product can be obtained, productivity is good. And all the moldings obtained by hardening the said composition are high intensity | strength and high elasticity modulus.

The structure of the compound (b1) used as the main component in the monomer (B) is as represented by the following formula (1).

The compound (b1) represented by the above formula (1) is a crosslinkable monomer having two polymerizable groups having an ethylenic double bond. Two polymerizable groups in the compound (b1) are linked by an ester bond, and the distance between the polymerizable groups is short. In addition, the compound (b1) includes a methacryloyl group (when R ₁ is a methyl group and R ₂ is a hydrogen atom in the formula (1)), an acryloyl group (in the formula (1), R ₁ and R ₂ are A hydrogen atom) or a crotonoyl group (in the formula (1), when R ₁ is a hydrogen atom and R ₂ is a methyl group) and a carboxylic acid vinyl ester group. Since these substituents all have a function of swelling the polymer (A), the compound (b1) can swell the powder of the polymer (A) in a short time. Here, in the compound (b1), the carbonyl group in the methacryloyl group, acryloyl group or crotonoyl group and the carbonyl group in the carboxylic acid vinyl ester group are the same.

As the compound (b1), R ₁ in the above formula (1) is a methyl group and R ₂ is a hydrogen atom, or R ₁ and R ₂ in the formula (1) are hydrogen atoms Is preferred. From the viewpoint of excellent biocompatibility and the strength and breaking energy of the obtained molded product, the compound (b1) is one in which R ₁ in the formula (1) is a methyl group and R ₂ is a hydrogen atom. More preferred.

In the composition of the present invention, the structure of 1,4-pentadien-3-ol (b3) contained in the monomer (B) is as represented by the following formula (2).

1,4-pentadien-3-ol (b3) represented by the above formula (2) is a crosslinkable monomer having two polymerizable groups having an ethylenic double bond. Since the two polymerizable groups in 1,4-pentadien-3-ol (b3) are linked via one carbon atom, the distance between the polymerizable groups is very close. In addition, since the hydroxyl group is bonded to the carbon atom and the boiling point is increased, the volatilization during the production of the composition is small, which is preferable from the viewpoint of the working environment. Furthermore, since it has a hydroxyl group at the allylic position from the ethylenic double bond, the reactivity of the two ethylenic double bonds is high.

The monomer (B) comprises 70 to 99.5% by mass of at least one compound selected from the compound (b1) represented by the above formula (1) and methyl methacrylate (b2), 1,4-pentadiene -3-ol (b3) is contained in an amount of 0.5 to 30% by mass. When the content of at least one compound selected from the compound (b1) and methyl methacrylate (b2) is less than 70% by mass, the elastic modulus and strength are insufficient. The content of the compound is preferably 85% by mass or more, and more preferably 92% by mass or more. On the other hand, when the content of at least one compound selected from the compound (b1) and methyl methacrylate (b2) exceeds 99.5% by mass, the effect of improving toughness and the effect of decreasing the water content are insufficient. Become. The content of the compound is preferably 99% by mass or less, and more preferably 98% by mass or less. On the other hand, when the content of 1,4-pentadien-3-ol (b3) is less than 0.5% by mass, the effect of improving toughness and the effect of reducing water content are insufficient. The content of 1,4-pentadien-3-ol (b3) is preferably 1% by mass or more, and more preferably 2% by mass or more. On the other hand, when the content of 1,4-pentadien-3-ol (b3) exceeds 30% by mass, the elastic modulus and strength are insufficient. The content of 1,4-pentadien-3-ol (b3) is preferably 15% by mass or less, and more preferably 8% by mass or less.

By using the monomer (B) of the present invention, a molded article having high strength, high elastic modulus and excellent toughness can be obtained. The details of the mechanism at this time are not clear, but the following is presumed.

In the resin composition of the present invention, the monomer (B) is polymerized after the monomer (B) enters between the molecular chains of the polymer (A), whereby the molecule of the polymer (A) is polymerized. It is presumed that a chain and a polymer composed of a plurality of types of monomers in the monomer (B) form a so-called “semi-interpenetrating network structure” that is intertwined with each other. At this time, it is considered that excellent toughness can be imparted to the obtained molded article by using 1,4-pentadien-3-ol (b3) having a very short distance between the crosslinking points after polymerization.

In the resin composition of the present invention, the entire composition is preferably not uniform and has a non-uniform structure derived from the particles of the polymer (A). In a preferred method for producing the resin composition of the present invention, the powder of the polymer (A) and the liquid of the monomer (B) are mixed and thickened in the presence of the polymerization initiator (C). At this time, the particles of the polymer (A) remain without being completely dissolved, the content of the monomer (B) is small at the center of the particle, and the content of the monomer (B) is large between the particles. The heterogeneous structure is formed. It is considered that a molded body having high strength and high elastic modulus and excellent toughness can be obtained by curing a composition having such a heterogeneous structure.

In the composition of the present invention, by using the monomer (B) containing 1,4-pentadien-3-ol (b3), the water absorption of the obtained molded article is lowered. Although this mechanism is not clear, the following is presumed.

When a molded product is produced by polymerizing the composition of the present invention, the obtained molded product contains the compound (b1) or methyl methacrylate (b2) and 1,4-pentadien-3-ol (b3). It is considered that a network-like crosslinked structure is formed. The crosslinked structure is considered to be entangled with the molecular chain of the polymer (A), and the crosslinked structure and the polymer (A) form a “semi-interpenetrating network structure”. It is estimated to be. Here, as described above, since 1,4-pentadien-3-ol (b3) has a very short distance between the polymerizable groups, the crosslinked structure is considered to have a short distance between the crosslinking points. . For this reason, it is considered that the vicinity of the surface of the polymer (A) particles in the molded product becomes partially extremely rigid, water absorption swelling is suppressed, and the water absorption rate of the molded product decreases. Thus, the fact that the water absorption rate can be lowered by blending a monomer having a hydroxyl group has been revealed for the first time by the present inventors, and is surprising. The merit of reducing the water absorption rate without introducing an aromatic group or a fluorine atom having a low biocompatibility is very large. On the other hand, as described above, by forming a “semi-interpenetrating network structure”, it is considered that a molded product having excellent strength and elastic modulus and excellent toughness can be obtained.

When a molded product having a high water absorption rate is used for a long time in a wet state, the molded product may be colored or a bad odor may be generated. Furthermore, mechanical properties may be deteriorated due to water absorption of the molded product. In particular, denture bases and mouthpieces may be colored with coffee or tea or used for a long period of time, which may cause bad odors and have a high water absorption rate. Therefore, the use of 1,4-pentadien-3-ol (b3) in the resin composition of the present invention is significant in that the water absorption rate can be greatly reduced.

In a preferred embodiment of the resin composition of the present invention, the monomer (B) contains 70 to 99.5% by mass of the compound (b1) represented by the above formula (1) and 1,4-pentadiene-3- All (b3) 0.5 to 30% by mass is contained. At this time, the content rate of a compound (b1) becomes like this. Preferably it is 85 mass% or more, More preferably, it is 92 mass% or more. On the other hand, the content rate of a compound (b1) is 99 mass% or less suitably, More preferably, it is 98 mass% or less. The content of 1,4-pentadien-3-ol (b3) is preferably 1% by mass or more, and more preferably 2% by mass or more. On the other hand, the content of 1,4-pentadien-3-ol (b3) is preferably 15% by mass or less, and more preferably 8% by mass or less.

At this time, if the focus is on reducing the water absorption rate, it may be preferable to increase the content of 1,4-pentadien-3-ol (b3). Specifically, the content of 1,4-pentadien-3-ol (b3) is preferably 3% by mass or more. At this time, it is preferable that the content rate of a compound (b1) shall be 97 mass% or less.

Here, when the compound (b1) represented by the above formula (1) is used as the main component in the monomer (B), the obtained molded product is obtained as compared with the case where the methyl methacrylate (b2) is used. The water absorption can be reduced. Compound (b1) is a crosslinkable monomer having a short distance between polymerizable groups, and as shown in the examples below, even when only compound (b1) is used as monomer (B), methyl The apparent saturated water absorption rate could be reduced by 10% or more compared to a commercial product of a denture base composition containing “methacrylate” as a main component of the liquid (“ACRON” manufactured by GC Corporation).

The compound (b1) is a relatively hydrophilic compound, but it is surprising that the water absorption of the obtained molded product is lower than when the more hydrophobic methyl methacrylate (b2) is used. Moreover, by using 1,4-pentadien-3-ol (b3) having a hydroxyl group in the molecule in addition to the compound (b1), the water absorption rate can be further reduced.

In another preferred embodiment of the resin composition of the present invention, the monomer (B) contains 70 to 99.5% by mass of methyl methacrylate (b2) and 1,4-pentadien-3-ol (b3) 0. 5 to 30% by mass. At this time, the content of methyl methacrylate (b2) is preferably 85% by mass or more, and more preferably 92% by mass or more. On the other hand, the content of methyl methacrylate (b2) is preferably 99% by mass or less, and more preferably 98% by mass or less. The content of 1,4-pentadien-3-ol (b3) is preferably 1% by mass or more, and more preferably 2% by mass or more. On the other hand, the content of 1,4-pentadien-3-ol (b3) is preferably 15% by mass or less, and more preferably 8% by mass or less.

At this time, if the main focus is on high elastic modulus and high strength, it may be preferable to reduce the content of 1,4-pentadien-3-ol (b3). Specifically, the content of 1,4-pentadien-3-ol (b3) is preferably 5% by mass or less. At this time, the content of methyl methacrylate (b2) is preferably 95% by mass or more.

The composition containing the polymer (A) and methyl methacrylate (b2) is the composition most widely used at present as a denture base composition, dental adhesive, bone cement or the like. Methyl methacrylate (b2) can swell the powder of the polymer (A) in a short time and has good operability. In addition, a molded product obtained by curing the composition has high strength and high elastic modulus. However, the toughness may be insufficient depending on the application. In such a case, it is significant that the toughness can be greatly improved by adding a relatively small amount of 1,4-pentadien-3-ol (b3). Further, the water absorption can be greatly reduced by adding a relatively small amount of 1,4-pentadien-3-ol (b3), which is extremely useful in practice.

The monomer (B) is a compound (b1) represented by the formula (1), methyl methacrylate (b2) and 1,4-pentadien-3-ol (b3) as long as the effects of the present invention are not impaired. A monomer other than) may be contained. The monomer at this time is not particularly limited as long as it is copolymerizable with (b1), (b2) and (b3). For example, methyl acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methoxydiethylene glycol ( (Meth) acrylate, ethoxydiethylene glycol (meth) acrylate, 4-methacryloxyethyl trimellitic anhydride (4-META), 4-acryloxyethyl trimetic acid (4-AET), 4-methacryloxyethyl trimellitic acid ( 4-MET), monofunctional (meth) acrylates such as 2-methacryloyloxyethylphenyl hydrogen phosphate (Phenyl-P); ethylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, 2- [10- (methacryloyloxy) decyl] malonic acid (MAC-10), polyfunctional (meth) acrylates such as 10-methacryloyloxydecyl dihydrogen phosphate (MDP); vinyl carboxylates such as vinyl acetate; maleic anhydride Acid; acrylonitrile; and olefins. The monomer content other than (b1), (b2) and (b3) in the monomer (B) is usually 20% by mass or less, preferably 10% by mass or less, and 5% by mass. The following is more preferable, and 2% by mass or less is more preferable.

The polymerization initiator (C) is not particularly limited as long as it can polymerize the monomer (B), and a radical polymerization initiator, a photopolymerization initiator, or the like is used. As the radical polymerization initiator, an organic peroxide or an organic azo compound is preferably used. These radical polymerization initiators may generate radicals by heating, or may generate radicals at room temperature by mixing with a reducing agent such as an amine. Moreover, when using a photoinitiator, the combination of a sensitizer and a reducing agent etc. are employ | adopted.

Polymerization initiators that generate radicals upon heating include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-tolyl peroxide, t-butylperoxybenzoate, di-t-butylperoxyisophthalate 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di [(o-benzoyl) benzoylperoxy] hexane, t-butylperoxy-2- Examples thereof include ethyl hexanoate and t-butyl peroxyisopropyl carbonate.

A combination of a peroxide and a reducing agent that generates radicals at room temperature includes peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-tolyl peroxide, and t-butyl peroxide. Oxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di [(o-benzoyl) benzoylper Oxy] hexane, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate, etc. are exemplified, and as the reducing agent, N, N-dimethylaniline, N, N-dimethyl-p-toluidine N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl- , 5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-i-propylaniline, N, N-dimethyl-4 -T-propylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2- Hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-i-propylaniline, N, N- Bis (2-hydroxyethyl) -4-t-propylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-i-propylaniline, N, N-bis (2-hydroxyethyl)- 3,5- Fragrances such as di-t-propylaniline, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, n-butoxyethyl 4-dimethylaminobenzoate or ethyl (2-methacryloyloxy) 4-dimethylaminobenzoate Tertiary amine, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, p-tolyldiethanolamine, (2-dimethylamino) ethyl methacrylate, N-methyldiethanolamine Dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate Aliphatic tertiary amines such as benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, lithium benzenesulfinate, toluenesulfinate, sodium toluenesulfinate, potassium toluenesulfinate, toluenesulfinate Calcium, lithium toluenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzene Calcium sulfinate, lithium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate 2,4,6-triethylbenzenesulfinic acid calcium, 2,4,6-i-propylbenzenesulfinic acid, potassium 2,4,6-triisopropylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid Examples thereof include sulfinic acid such as calcium or a salt thereof.

In the case of a photopolymerization initiator, sensitizers and reducing agents include camphorquinone, benzyl, diacetyl, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl di (2-methoxyethyl) ketal, 4,4′-dimethylbenzyl- Dimethyl ketal, anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-bromoanthraquinone, thioxanthone, 2-isopropylthioxanthone, 2 -Nitrothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chloro-7-trifluoromethyl Thioxanthone, thioxanthone-10,10-dioxide, thioxanthone-10-oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, bis (4-dimethylaminophenyl) ketone, 4,4'-bis Diethylaminobenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoylphenylphosphine oxide, Benzoyl di- (2,6-dimethylphenyl) phosphonate, 2,4,6-trimethylbenzoylethoxyphenyl phosphite Oxide, 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris ( Sensitizers such as tribromomethyl) -s-triazine or 2-methyl-4,6-bis (trichloromethyl) -s-triazine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 2- Tertiary amines such as dimethylaminoethyl methacrylate, N, N-bis {(meth) acryloyloxyethyl} -N-methylamine, N-methyldiethanolamine, 4-dimethylaminobenzophenone, and aldehydes such as dimethylaminobenzaldehyde and terephthalaldehyde And 2-mercaptobenzoxazole, decane Compounds having a thiol group such as all, 3-mercaptopropyltrimethoxysilane, thiobenzoic acid, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, lithium benzenesulfinate, toluenesulfinate, toluene Sodium sulfinate, potassium toluenesulfinate, calcium toluenesulfinate, lithium toluenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzene Potassium sulfinate, calcium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzene Nzensulfinic acid, potassium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-i-propylbenzenesulfinic acid, 2,4,6-triisopropylbenzene Examples of the reducing agent include sulfinic acid such as potassium sulfinate and calcium 2,4,6-triisopropylbenzenesulfinate or a salt thereof.

The composition of the present invention contains 100 to 280 parts by mass of the polymer (A) with respect to 100 parts by mass of the monomer (B). When the content of the polymer (A) exceeds 280 parts by mass, the composition of the present invention is prepared using the powder of the polymer (A) and the liquid of the monomer (B). There exists a possibility that the powder of a polymer (A) may not fully swell. If the powder does not swell sufficiently, the mechanical properties of the resulting molded product may be reduced. The content of the polymer (A) is more preferably 270 parts by mass or less. On the other hand, when the content rate of a polymer (A) is less than 100 mass parts, there exists a possibility that the mechanical property of the molded article obtained may fall or a polymerization shrinkage rate may become high. The content of the polymer (A) is more preferably 180 parts by mass or more, and further preferably 200 parts by mass or more. From the viewpoint of the mechanical properties of the obtained molded product in the case of producing a molded product using the polymer (A) powder and the monomer (B) solution, the content of the polymer (A) is In the range where the polymer (A) is sufficiently swollen, it is preferable that the amount is larger.

The content of the polymerization initiator (C) is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the monomer (B). If the content of the polymerization initiator (C) is less than 0.01 parts by mass with respect to 100 parts by mass of the monomer (B), the effect of promoting the polymerization reaction may not be sufficient. Preferably it is 0.1 mass part or more. On the other hand, when the content of the polymerization initiator (C) exceeds 10 parts by mass with respect to 100 parts by mass of the monomer (B), the effect of accelerating the polymerization reaction reaches its peak, and the polymerization initiator ( There is also a possibility that the eluted components derived from C) may increase. The amount is preferably 5 parts by mass or less.

The composition of the present invention may contain components other than the polymer (A), the monomer (B) and the polymerization initiator (C) as long as the effects of the present invention are not impaired. For example, fillers, colorants, antibacterial agents, fragrances, and the like can be blended depending on the application. 40 mass% or less is suitable for the content rate of the said filler in the composition of this invention, and 20 mass% or less is more suitable. By containing a filler, the strength and elastic modulus of the obtained molded product are further improved. From the viewpoint of lowering the water absorption of the obtained molded product, an inorganic filler is more preferable. On the other hand, the content of components other than the polymer (A), the monomer (B), the polymerization initiator (C) and the filler is preferably less than 20% by mass, and more preferably 10% by mass or less. It is.

A preferred method for producing the composition of the present invention is a method in which the powder of the polymer (A) and the liquid of the monomer (B) are mixed and thickened in the presence of the polymerization initiator (C). is there. After mixing the powder agent and the liquid agent, the mixture physically changes from a paste shape to a candy shape to a rubber shape, that is, from a viscous material to an elastic material. Here, the bowl shape is a state having both viscosity and fluidity. Since the cocoon-shaped composition has good operability, it is possible to easily perform a shaping operation and the like. When the powder of the polymer (A) and the liquid of the monomer (B) are mixed, it becomes a cocoon in about 2 to 5 minutes. By forming the cocoon in such a short time, the preparation and shaping of the composition can be performed in a short time, so that the merit is great. When mixing powder and liquid, if you want to prevent air bubbles from entering the composition, stir after spraying the liquid or soaking the liquid in the liquid. It is preferable to stand still without increasing the viscosity. However, in order to improve the speed of thickening or to make the whole homogeneous, stirring is preferable.

When the powder of the polymer (A) and the liquid of the monomer (B) are mixed, the monomer (B) is gradually impregnated into the particles of the polymer (A) constituting the powder, so that the particles Swells. When the composition becomes cocoon-like, the particles impregnated with the monomer (B) are soft enough to be easily deformed by the stress during molding. At this time, it is considered that the particles are swollen by impregnating a large amount of the monomer (B) in the vicinity of the surface. Thus, it is considered that the particles of the polymer (A) are swollen by the monomer (B).

On the other hand, when the polymer (A) powder and the monomer (B) solution are mixed, the gap between the polymer (A) powder and the monomer (B) solution is filled. When the composition becomes bowl-shaped, it is considered that a part of the polymer (A) is dissolved in the monomer (B).

As described above, the soot-like composition obtained by mixing the powder of the polymer (A) and the liquid of the monomer (B) is a polymer (swelled by impregnation with the monomer (B)). It consists of a solution of the monomer (B) in which the polymer (A) is dissolved and present in a form to fill the gaps between the particles.

When such a cocoon-shaped composition is polymerized, the polymer (A) particles impregnated in the monomer (B) impregnated in the vicinity of the surface of the polymer (A) particles. , (B1) or (b2) and (b3) are presumed to form the above-described semi-interpenetrating network structure. Thus, it is considered that a molded product having excellent strength and elastic modulus, excellent toughness, and low water absorption can be obtained. From the viewpoint of the mechanical properties of the resulting molded article, it is preferable that the amount of the monomer (B) solution is small so long as the powder of the polymer (A) can be sufficiently swollen. By increasing the ratio of the portion derived from the polymer (A) particles in the obtained molded article, the mechanical properties are further improved.

When the monomer (B) contains the compound (b1) or methyl methacrylate (b2) represented by the above formula (1) and 1,4-pentadien-3-ol (b3), When the polymer composition is polymerized, the compound (b1) in the monomer (B) impregnated in the particles of the polymer (A) in the portion derived from the vicinity of the surface of the particles of the polymer (A) Alternatively, it is presumed that methyl methacrylate (b2) and 1,4-pentadien-3-ol (b3) are crosslinked to form a semi-interpenetrating network structure having a very high crosslinking density. Thereby, it is considered that the molded product becomes rigid, the water absorption swelling is suppressed, and the water absorption rate of the molded product decreases. Further, an extremely high density crosslinked structure composed of the compound (b1) or methyl methacrylate (b2) and 1,4-pentadien-3-ol (b3) is derived from the vicinity of the surface of the particles of the polymer (A). By forming in the part, it is thought that the penetration | invasion of the water to the part originating from the center vicinity of the particle | grains of a polymer (A) is suppressed, and this also thinks that it has contributed to the fall of water absorption. It is done.

The average particle size of the powder of the polymer (A) is not particularly limited, but is preferably 2 to 200 μm. When the average particle size is smaller than 2 μm, the powder may not be uniformly dispersed when the polymer (A) powder and the monomer (B) liquid are mixed. The average particle size is more preferably 10 μm or more, and further preferably 20 μm or more. Moreover, when the average particle diameter of a polymer (A) is larger than 200 micrometers, there exists a possibility that the swelling rate of a powder may become too slow. The average particle size is more preferably 150 μm or less, and even more preferably 100 μm or less.

The method for mixing the polymerization initiator (C) is not particularly limited. The polymerization initiator (C) may be previously contained in at least one of the powder of the polymer (A) or the liquid of the monomer (B), or may be mixed during preparation of the composition. It is preferable that the polymerization initiator (C) is previously contained in at least one of the powder of the polymer (A) or the liquid of the monomer (B) because the operation can be simplified.

It is preferable that the polymer (A) contains a polymerization initiator (C) in advance. That is, it is preferable that the polymer (A) particles constituting the powder contain a polymerization initiator (C). In such a case, the polymerization initiator added when producing the polymer (A) by suspension polymerization or the like can be used as it is. Moreover, when a polymerization initiator (C) is what mixes multiple types of compounds and generate | occur | produces a radical, the one is previously contained in a polymer (A) and the other in a monomer (B) You can also let them.

By mixing the powder of the polymer (A) and the liquid of the monomer (B), the monomer (B) penetrates into the polymer (A), and the polymer (A) swells. The viscosity gradually rises to a bowl shape. It is preferable to form the molded product by shaping after thickening in this way. It is preferable that the composition at the time of shaping has a bowl-like shape that maintains fluidity while the viscosity is sufficiently increased. The shaping is performed by filling the mold, pressing it, or adjusting the shape by hand.

The time during which the composition maintains a bowl shape after mixing the powder of the polymer (A) and the liquid of the monomer (B) in the presence of the polymerization initiator (C) is not particularly limited, It is preferable that the time required for the operation of shaping the composition is maintained. When the monomer (B) of the present invention is used as the liquid agent, the composition maintains a bowl-like shape for a sufficient time to work.

A cured molded product is obtained by shaping the composition of the present invention and then performing a polymerization reaction. When using a polymerization initiator (C) that causes a polymerization reaction to proceed at room temperature, the polymerization reaction proceeds at the same time as increasing the viscosity even if only mixed, but when the polymerization reaction proceeds using heat or light. In many cases, the polymerization reaction does not substantially proceed until it is treated with heat or light. Although the polymerization reaction can proceed after shaping by heating or light irradiation, a heating method is preferred in consideration of workability. For example, the polymerization reaction can be easily advanced only by immersing in warm water. Since the hardness of the composition can be increased by changing the polymerization degree by adjusting the polymerization conditions such as temperature and the polymerization time during polymerization, a molded product having a desired hardness can be obtained depending on the application. Can be easily obtained.

The composition in the form of a bowl obtained by mixing the powder of the polymer (A) and the liquid of the monomer (B) in the presence of the polymerization initiator (C) is the monomer (B ) And the polymer (A) particles impregnated and swollen, and a solution of the monomer (B) in which the polymer (A) is dissolved and fills the gaps between the particles. When such a cocoon-shaped composition is polymerized, the particles constituting the polymer (A) powder generally maintain its shape after polymerization. The gap between the particle-shaped portions derived from the particles of the polymer (A) is filled with the monomer (B) cured by polymerization. Thus, it is preferable that the molded product obtained by polymerization is composed of a particle-shaped portion derived from the polymer (A) particles and a portion derived from the monomer (B) filling the gap. Thereby, strength, elastic modulus, and toughness are further improved. The particle shape of the part derived from the polymer (A) particles in the molded product may be a shape close to a sphere or a distorted shape. The shape of the part derived from the particles of the polymer (A) may be distorted by the pressure during molding.

At this time, it is preferable that the ratio of the part derived from the particles of the polymer (A) in the molded product is as large as possible. By doing so, the structure which the part derived from the particle | grains of the polymer (A) presumed that the “semi-interpenetrating network structure” is formed can be taken. Thereby, the strength, elastic modulus and toughness of the molded product are further improved. The structure of the molded product composed of the part derived from the polymer (A) particles and the part derived from the monomer (B) solution is to observe a thin slice obtained by thinly slicing the molded product with an optical microscope. Etc. can be confirmed.

As described above, the polymer (A) and the monomer (B) are considered to be highly safe. Moreover, according to the manufacturing method of the composition of this invention using the powder of a polymer (A) and the liquid agent of a monomer (B) mentioned above, in addition to being able to produce a composition easily, the obtained composition It is also easy to produce a molded product using Therefore, the composition of the present invention is suitably used as a medical composition. A preferred embodiment of the medical composition is bone cement.

The medical composition is preferably used as a dental composition. Specifically, it can be suitably used as a dental adhesive. The dental adhesive is used to bond dental materials such as enamel and dentin to dental metal, dental resin, dental porcelain, and the like. It is desirable to have excellent toughness for bonding materials with significantly different linear expansion coefficients and elastic moduli, and to be subjected to repeated loads after bonding. As desired, the composition of the present invention is preferably used. Further, a denture base or a mouthpiece obtained by curing the dental composition is a preferred embodiment. In general, dentures are produced by taking a patient's oral impression and preparing a plaster model, then forming a denture base using wax on the plaster model, and arranging artificial teeth on the wax. The denture is buried in a flask using an investment material and a wax denture mold is formed, and then wax is poured in hot water or the like to form a cavity in the denture base in the investment material. After filling the cavity with a soot-like composition and polymerizing and curing it, it is taken out from the investment material, and is subjected to final stage shape correction and polishing to complete. Moreover, the manufacturing method of a mouthpiece is substantially the same as the manufacturing method of a denture except the point which arranges artificial teeth. The denture base and mouthpiece produced using the composition of the present invention have a high strength and a high elastic modulus, and also have an excellent toughness. Damage due to occlusal pressure or impact can be suppressed. Since the water absorption of the obtained molded product is low, coloring of the denture base and mouthpiece due to coffee or the like and generation of bad odor are unlikely to occur, and mechanical properties are not easily lowered.

A powder of a polymer (A) containing 70% by mass or more of a methyl methacrylate unit;
Following formula (1)

[Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and at least one of R ₁ and R ₂ is a hydrogen atom. ]
70 to 99.5% by mass of at least one compound selected from the compound (b1) and methyl methacrylate (b2) represented by formula (2):

And a solution of monomer (B) containing 0.5 to 30% by mass of 1,4-pentadien-3-ol (b3) represented by the formula: wherein at least one of the powder or the solution is polymerized A kit containing the initiator (C) is also a preferred embodiment of the present invention.

In such a kit, a composition can be prepared by an easy operation by simply mixing the two components of the powder and the liquid. The use of the kit is not particularly limited, but a medical kit is preferable, and a bone cement kit is a preferred embodiment. A dental kit is also suitable, and among them, a dental adhesive kit, a denture base kit, or a mouthpiece kit is a preferred embodiment. As a method of using such a kit to contain the polymerization initiator (C) in a powder or liquid, the method described in the method for producing the composition can be employed.

Hereinafter, the present invention will be described using examples. Preparation and measurement of the test pieces in the examples were carried out in a laboratory at 23 ° C. and a humidity of 50%. The monomers used in this example are as follows.

[Monomer]
(B1) Vinyl methacrylate (VMA)
[A monomer represented by the above formula (1), R ₁ is a methyl group, and R ₂ is a hydrogen atom. ]
Specific gravity at 25 ° C .: 0.933 g / ml
(B2) Methyl methacrylate (MMA)
Specific gravity at 25 ° C .: 0.936 g / ml
(B3) 1,4-pentadien-3-ol (14PD3OH)
[A monomer represented by the above formula (2). ]
Specific gravity at 25 ° C .: 0.865 g / ml

Example 1
Polymethylmethacrylate powder produced by suspension polymerization (“Hyperl D-100M” manufactured by Negami Kogyo Co., Ltd .: weight average molecular weight 500,000, average particle size of about 50-80 μm, benzoyl peroxide 0.5-1. 4 g of 0% by weight), 1.98 ml (1.85 g) of vinyl methacrylate (hereinafter sometimes abbreviated as VMA) and 1,4-pentadien-3-ol (hereinafter abbreviated as 14PD3OH). ) 0.02 ml (0.02 g) was mixed with the liquid mixture and allowed to stand. The powder / liquid ratio was 2.0 g / ml. The content of 1,4-pentadien-3-ol in the monomer (B) was 0.92% by mass. Moreover, 215 mass parts of polymers (A) were mix | blended with respect to 100 mass parts of monomers (B). After about 3 minutes, the mixture in the cocoon state was inserted into a Teflon (registered trademark) mold that can form a 2 mm × 2 mm × 25 mm test piece and clamped, and a constant temperature chamber (“ST-101B1” manufactured by ESPEC CORP.) ) Was heated at 65 ° C. for 60 minutes and then at 100 ° C. for 90 minutes to proceed the polymerization. After natural cooling, the test piece taken out of the Teflon (registered trademark) mold was left in the air for one day, and then subjected to a three-point bending test and a water absorption test.

A universal testing machine (Instron 5544) was used for the three-point bending test. The distance between fulcrums was set to 20 mm, the crosshead speed was set to 0.5 mm / min, and the bending elastic modulus, bending strength, maximum deflection amount and breaking energy were measured. Five samples were measured for each measurement. When it did not break, the test was stopped when it was bent about 10 mm. The results of the four types of bending characteristics measurements are shown in Table 1 and FIGS.

The water absorption test was performed by immersing the test piece in water at 37 ° C. for 180 days and measuring the apparent saturated water absorption rate of the test piece when no increase in water absorption was observed. Here, the apparent saturated water absorption (mass%) is obtained by multiplying the number obtained by dividing the increase in the mass of the test piece after immersion in water by the mass of the test piece before immersion by 100. The result at this time is shown in FIG.

Examples 2-7, Comparative Example 1
A test piece was prepared and evaluated (three-point bending test and water absorption test) in the same manner as in Example 1 except that the amounts of VMA and 14PD3OH used were changed as follows. The results are shown in Table 1 and FIGS. For Example 7 and Comparative Example 1, only the water absorption test was performed.
Example 2
VMA: 1.96 ml (1.83 g), 14PD3OH: 0.04 ml (0.04 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 1.86% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 215 parts by mass / Example 3
VMA: 1.94 ml (1.81 g), 14PD3OH: 0.06 ml (0.05 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 2.79% by mass
Amount of polymer (A) to 100 parts by mass of monomer (B): 215 parts by mass / Example 4
VMA: 1.92 ml (1.79 g), 14PD3OH: 0.08 ml (0.07 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 3.72% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 215 parts by mass / Example 5
VMA: 1.90 ml (1.77 g), 14PD3OH: 0.10 ml (0.09 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 4.66% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 215 parts by mass / Example 6
VMA: 1.80 ml (1.68 g), 14PD3OH: 0.20 ml (0.17 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 9.34% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 216 parts by mass / Example 7
VMA: 1.60 ml (1.49 g), 14PD3OH: 0.40 ml (0.35 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 18.80% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 218 parts by mass / Comparative Example 1
VMA: 1.00 ml (0.93 g), 14PD3OH: 1.00 ml (0.87 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 48.11% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 223 parts by mass

Comparative Example 2
A test piece was prepared and evaluated (three-point bending test and water absorption test) in the same manner as in Example 1 except that only 2.00 ml (1.87 g) of VMA was used as the monomer (B). . The results are shown in Table 1 and FIGS.

Example 8
4 g of the same polymethyl methacrylate powder as in Example 1, 1.98 ml (1.85 g) of methyl methacrylate (hereinafter sometimes abbreviated as MMA) and 0.02 ml of 1,4-pentadien-3-ol (0 0.02 g) was mixed and left standing. About 5 minutes later, the mixture in a wrinkled state was molded in the same manner as in Example 1 to obtain a test piece, which was subjected to a three-point bending test. The results are shown in Table 1.

Examples 9 and 10
A test piece was prepared and evaluated (three-point bending test) in the same manner as in Example 8 except that the amounts of MMA and 14PD3OH used were changed as follows. The results are shown in Table 1.
Example 9
MMA: 1.96 ml (1.84 g), 14PD3OH: 0.04 ml (0.04 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 1.85% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 214 parts by mass / Example 10
MMA: 1.90 ml (1.78 g), 14PD3OH: 0.10 ml (0.09 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 4.64% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 215 parts by mass

Example 11
4 g of the same polymethyl methacrylate powder as in Example 1 was mixed with a solution obtained by mixing 1.98 ml (1.85 g) of methyl methacrylate and 0.02 ml (0.02 g) of 1,4-pentadien-3-ol. Left to stand. The content of 1,4-pentadien-3-ol in the liquid agent in the monomer (B) was 0.92% by mass. At this time, 214 parts by mass of the polymer (A) was blended with 100 parts by mass of the monomer (B). About 5 minutes later, the mixture in a wrinkled state was molded in the same manner as in Example 1 to obtain a test piece, which was subjected to a three-point bending test and a water absorption test. In the water absorption test, the test period was 90 days. The results are shown in Table 2.

Examples 12-20
A test piece was prepared and evaluated (three-point bending test and water absorption test) in the same manner as in Example 11 except that the amounts of MMA and 14PD3OH were changed as follows. The results are shown in Table 2.
Example 12
MMA: 1.96 ml (1.83 g), 14PD3OH: 0.04 ml (0.03 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 1.85% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 214 parts by mass / Example 13
MMA: 1.94 ml (1.82 g), 14PD3OH: 0.06 ml (0.05 g)
Content of 14PD3OH in the liquid agent in the monomer (B): 2.78% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 214 parts by mass / Example 14
MMA: 1.92 ml (1.80 g), 14PD3OH: 0.08 ml (0.07 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 3.71% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 214 parts by mass / Example 15
MMA: 1.90 ml (1.78 g), 14PD3OH: 0.10 ml (0.09 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 4.64% by mass
Amount of polymer (A) to 100 parts by mass of monomer (B): 214 parts by mass / Example 16
MMA: 1.88 ml (1.76 g), 14PD3OH: 0.12 ml (0.10 g)
Content of 14PD3OH in the liquid agent in the monomer (B): 5.57% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 215 parts by mass / Example 17
MMA: 1.86 ml (1.74 g), 14PD3OH: 0.14 ml (0.12 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 6.50% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 215 parts by mass / Example 18
MMA: 1.84 ml (1.72 g), 14PD3OH: 0.16 ml (0.14 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 7.44% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 215 parts by mass / Example 19
MMA: 1.82 ml (1.70 g), 14PD3OH: 0.18 ml (0.16 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 8.37% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 215 parts by mass / Example 20
MMA: 1.80 ml (1.68 g), 14PD3OH: 0.20 ml (0.17 g)
Content ratio of 14PD3OH in the liquid agent in the monomer (B): 9.31% by mass
Amount of polymer (A) with respect to 100 parts by mass of monomer (B): 215 parts by mass

Comparative Example 3
A test piece was prepared and evaluated (three-point bending test and water absorption test) in the same manner as in Example 11 except that only 2.00 ml (1.87 g) of MMA was used as the monomer (B). . The results are shown in Table 2.

Comparative Example 4
Using a commercially available acrylic denture base resin “Acron” (manufactured by GC Corporation), a test piece having a size of 2 mm × 2 mm × 25 mm was prepared by the method instructed by the instruction manual. A point bending test and a water absorption test were performed. The results are shown in Tables 1 and 2 and FIGS.

2 to 5 show the content of 14PD3OH on the horizontal axis and the vertical axis on the test pieces prepared in Examples 1 to 6 and Comparative Example 2 when the main component in the monomer (B) is VMA. 6 is a graph in which the bending elastic modulus (FIG. 2), bending strength (FIG. 3), maximum deflection (FIG. 4), and breaking energy (FIG. 5) are respectively plotted. As can be seen from these graphs, as the content of 14PD3OH increases, the bending elastic modulus and bending strength decrease, but the decrease is not so great. On the other hand, as the content of 14PD3OH increases, the maximum deflection amount and the breaking energy increase significantly. It can be seen that the addition of only 1% by mass shows a value more than twice that of the commercial product.

FIG. 6 shows the content of 14PD3OH on the horizontal axis and the vertical axis for the test pieces prepared in Examples 1 to 7 and Comparative Examples 1 and 2 when the main component in the monomer (B) is VMA. It is the graph which plotted apparent saturation water absorption (mass%). Even in Comparative Example 2 in which the total amount in the monomer (B) is VMA, the apparent saturated water absorption is lower by 10% by mass or more than the commercial denture base resin “Acron” whose main component is MMA. I understand that. And when 14PD3OH is mix | blended with VMA, it turns out that a saturated water absorption rate falls large. It becomes the minimum when it contains about 14% by mass of 14PD3OH, and the apparent saturated water absorption increases at a content higher than that.

7 to 10 show the content of 14PD3OH on the horizontal axis and the vertical axis on the test pieces prepared in Examples 11 to 20 and Comparative Example 3 when the main component in the monomer (B) is MMA. 9 is a graph in which the bending elastic modulus (FIG. 7), bending strength (FIG. 8), maximum deflection (FIG. 9), and breaking energy (FIG. 10) are respectively plotted. As can be seen from these graphs, when the content of 14PD3OH is up to 3% by mass, the flexural modulus is equal to or higher than that of MMA alone, and significantly increased in Example 12 (MMA 2.78% by mass). When the content of 14PD3OH is up to 3% by mass, the bending strength is almost the same as when MMA alone is used. If it exceeds 3% by mass, the flexural modulus and bending strength gradually decrease, but a relatively high value can be maintained up to about 5% by mass. On the other hand, as the content of 14PD3OH increases, the maximum deflection amount and the breaking energy increase significantly. The sample increases significantly by adding only 1% by mass, and when it exceeds 2% by mass, a sample that does not break is included, and when it exceeds 4% by mass, it no longer breaks.

FIG. 11 shows the content of 14PD3OH on the horizontal axis and the vertical axis on the test pieces prepared in Examples 11 to 20 and Comparative Example 3 when the main component in the monomer (B) is MMA. It is the graph which plotted the saturated water absorption (mass%). Comparative Example 3 in which the total amount in the monomer (B) is MMA has an apparent saturated water absorption rate comparable to that of a commercial denture base resin “Acron” whose main component is MMA. And just adding about 1% by mass of 14PD3OH with respect to MMA, the apparent saturated water absorption is greatly reduced, and it is reduced by 24% from “Akron”. In Examples 11 to 20, the time required to reach the apparent saturated water absorption when immersed in water is shorter than that of Comparative Example 3 in which the total amount of the monomer (B) is MMA, and is almost constant over two weeks. Became value. That is, an interesting phenomenon was observed that the molded product of the present invention had a low saturated water absorption rate despite a high water absorption rate. In Example 20 (MMA 9.31 mass%), the weight decreased as the immersion time in water increased, suggesting that unreacted monomers were eluted. This phenomenon was also observed to some extent in Examples 17 to 19 (MMA 6.50 to 8.37% by mass). Therefore, it is considered necessary to consider the elution of the monomer depending on the application.

Example 21
The structure of the molded product obtained by polymerizing the composition of the present invention was observed. As a powder, a powder containing a pigment (dark pink) in polymethylmethacrylate particles [“ACRON” powder manufactured by GC Corporation (corresponding standard: JIS T6501 “acrylic resin for denture base (first type)”)] was used. A test piece was prepared in the same manner as in Example 6 except that. The test piece was cut into 2 mm × 2 mm × 10 mm, placed in a silicon embedding plate for microtome, embedded with an epoxy resin (Epofix cold embedding resin, manufactured by Struers), and cured for 24 hours. The test piece embedded in the epoxy resin was cut with a glass knife (45 °) using a microtome (ULTRACUT E, manufactured by Leica) to obtain a thin slice having a thickness of about 5 μm. A thin slice sample was observed with an optical microscope (Olympus Co., Ltd., “BX51”) under transmitted light conditions of 200 times (objective lens 20 times, eyepiece 10 times), and a digital camera attached to the eyepiece Thin sections were photographed with (Canon PowerShot S95). A microscopic image of the thin section is shown in FIG.

In FIG. 1, a plurality of black circles can be seen. The black circle is due to the pigment contained in the polymethyl methacrylate, and it can be seen that the circle is a portion derived from the polymethyl methacrylate particles. On the other hand, the gap portion of the circle is white and light is transmitted therethrough. Therefore, it turns out that the said part originates in the liquid agent (mixture of VMA and 14PD3OH) which does not contain a pigment.

In FIG. 1, the portions derived from the black polymethyl methacrylate particles are almost in contact with each other, and the area of the portion through which the light derived from the liquid (mixture of VMA and 14PD3OH) is transmitted is very small.

Claims (13)

1. A composition comprising a polymer (A), a monomer (B) and a polymerization initiator (C);
   Containing 100 to 280 parts by mass of the polymer (A) with respect to 100 parts by mass of the monomer (B),
   The polymer (A) contains 70% by mass or more of methyl methacrylate units,
   The monomer (B) is represented by the following formula (1)
   

   

   [Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and at least one of R ₁ and R ₂ is a hydrogen atom. ]
   70 to 99.5% by mass of at least one compound selected from the compound (b1) and methyl methacrylate (b2) represented by formula (2):
   

   

   1,4-pentadien-3-ol (b3) represented by the formula: 0.5-30% by mass.
2. The composition according to claim 1, which has a heterogeneous structure derived from particles of the polymer (A).
3. The monomer (B) contains 70 to 99.5% by mass of the compound (b1) and 0.5 to 30% by mass of 1,4-pentadien-3-ol (b3). Composition.
4. The monomer (B) contains 70 to 99.5% by mass of methyl methacrylate (b2) and 0.5 to 30% by mass of 1,4-pentadien-3-ol (b3) according to claim 1 or 2. The composition as described.
5. A medical composition comprising the composition according to any one of claims 1 to 4.
6. A dental composition comprising the medical composition according to claim 5.
7. A dental adhesive comprising the dental composition according to claim 6.
8. A bone cement comprising the medical composition according to claim 5.
9. A molded product obtained by curing the composition according to any one of claims 1 to 4.
10. A denture base or mouthpiece obtained by curing the dental composition according to claim 6.
11. The powder of the polymer (A) and the liquid agent of the monomer (B) are mixed and thickened in the presence of the polymerization initiator (C). A method for producing the composition described.
12. The method for producing a composition according to claim 11, wherein the polymer (A) contains a polymerization initiator (C) in advance.
13. A powder of a polymer (A) containing 70% by mass or more of a methyl methacrylate unit;
    Following formula (1)
    

    

    [Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and at least one of R ₁ and R ₂ is a hydrogen atom. ]
    70 to 99.5% by mass of at least one compound selected from the compound (b1) and methyl methacrylate (b2) represented by formula (2):
    

    

    And a solution of monomer (B) containing 0.5 to 30% by mass of 1,4-pentadien-3-ol (b3) represented by the formula: wherein at least one of the powder or the solution is polymerized A kit containing an initiator (C).

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