JP2008201892A - Polymerizable composition, curable material for dentistry or surgery and cured material, and method for producing molded article for dentistry or surgery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition excellent in curing sensitivity, to provide a curable material for dentistry or surgery, to provide a cured material for dentistry or surgery, excellent in abrasion resistance and stability, to provide a cured article, and to provide a method for producing the same. <P>SOLUTION: This polymerizable composition is characterized by comprising a compound represented by formula (I), a polymer having monomer units represented by formula (II) and/or another addition polymerization type polymer, and inorganic particles. In formulas (I) and (II), Q<SP>1</SP>is a cyano group or -COX<SP>2</SP>group; X<SP>1</SP>is H, an organic residue or a polymer chain bound to the α-carbon atom through a heterogeneous atom, or a halogen atom; X<SP>2</SP>is H, an organic residue or a polymer chain bound to a carbonyl group through a heterogeneous atom, or a halogen atom; R<SP>a</SP>and R<SP>b</SP>are each independently a halogen atom, cyano group or organic residue; X<SP>1</SP>and X<SP>2</SP>, R<SP>a</SP>and R<SP>b</SP>, and X<SP>1</SP>and R<SP>a</SP>or R<SP>b</SP>may be each bound to each other to form a cyclic structure. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polymerizable composition, a dental or surgical curable material and a curable material, and a method for producing a dental or surgical molded article.

An artificial bone prosthetic material for dentistry and surgery should preferably have a hardness similar to that of hydroxyapatite Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ constituting the tooth (bone). Particularly in the case of a dental material, if it is too hard, the teeth to be meshed may be damaged, and if it is soft, the artificial material will be scraped off by prolonged engagement. On the other hand, in terms of hardness, it is desired to use the inorganic material including the apatite as an artificial material as it is, but there is a problem that the inorganic material is difficult to process and mold. In order to avoid the problem, composites with an inorganic material as a filler and a photopolymerizable organic compound that is excellent in terms of workability are being actively performed. And considering the point of hardness which is the original purpose, it is important how the content of the inorganic material can be increased. For example, various inorganic-organic composite materials have been prototyped for dental use.

Taking a composite resin, which is a composite material filled with an inorganic substance in a polyfunctional methacrylate as an example, the transition of the technology of the composite resin can be said to be the history of controlling the particle size of the inorganic substance.
At the time of creation, a material using a macro filler with a particle size of several tens of μm was developed, but it could not be used for restoration of the front tooth part because of poor polishing. The second generation uses microfillers with a particle size of several tens of nanometers, but it is based on a filling method that is blended directly into the polyfunctional methacrylate. It was not sufficient in terms of shrinkage, wear resistance and rigidity, and the appearance was opaque due to high-order aggregation. Therefore, for the purpose of improving the filling property of the micro filler, an organic composite filler obtained by polymerizing and curing a mixture of a micro filler and a polyfunctional methacrylate and grinding it to several tens of μm has been developed. It was inferior and could not be sufficiently filled to suppress the shrinkage rate. Moreover, since the micro filler aggregated in the organic composite filler, the appearance was still opaque.
In the filling method in which such a microfiller having a particle size of several tens of nm is directly blended with the polyfunctional methacrylate, a uniform dispersion state cannot be obtained due to high-order aggregation, and thus high filling cannot be achieved. Further, even an organic composite filler using a microfiller could not be sufficiently filled because of its irregular shape by pulverization. Therefore, a high performance dental material excellent in filling property, low shrinkage, wear resistance, abrasiveness, rigidity, transparency and the like has not been obtained as a composite material.

  In particular, in terms of important dispersion stabilization, it has been disclosed to use fine inorganic particles of the order of nm in a polymer by suspension polymerization (polymer beads) (Patent Document 1). This is not only troublesome in the case of coating with a polymer in advance, but it is difficult to increase the filler content, and the hardness derived from the original filler cannot be sufficiently exhibited.

  Also, it continues to be highly necessary in dentistry to prevent secondary caries that often occurs after the use of dental restorative materials such as filled composites. For this reason, filled complexes that can release ions (eg, fluorine, calcium, or hydroxyl ions) in the oral cavity have also been recently studied. These ions are advantageous because they have remineralization, bioactivity, or cariostatic effects.

  The restoration | restoration dental material which produces a caries inhibitory action because it contains a fluorine source (for example, specific chlorohexidine fluoride) is indicated (nonpatent literature 1). Further examples of ion-release filling materials are disclosed that glass ionomer cements, or compomers whose organic matrix is always made from monomers, oligomers or polymers having carboxyl groups (2) 4).

  Although these filler materials exhibit a high degree of ion release, a clear decrease in mechanical properties, especially strength, occurs after prolonged contact with water. Furthermore, a dental composite material used as a reliable material or cement is disclosed (Patent Document 2). In addition to conventional (meth) acrylates, composite materials include certain glasses that release calcium and hydroxyl ions. However, the glass is too milky and as a result gives the composite material an unnatural lifeless appearance and therefore cannot be used in fields that require aesthetic restoration. The low translucency also prevents the light curing of the composite material, so that the high through-curing depth that is precisely required for deep cavity filling materials cannot be achieved. . Finally, the glass also contains only a very small amount of fluorine that can be derived from cryolite, NaF, or KF, which is used as a flux as needed.

Japanese Patent Laid-Open No. 7-17820 European Patent No. 0449339 U.Salz, Phillip Journal, 1997, vol.14, p.296 A.D.Wilson, J.W.McLean, Glass Ionomer Cement, Quintessence Publishers, Chicago, 1988 J.Nicholson, M.Anstice, Trends Polym.Sci., 1994, vol.2, p.272 R. Hickel, L. Kremers, C. Haffner, Quintessenz, 1996, vol. 47, p. 1581

It is an object of the present invention to provide a polymerizable composition that is fully cured by light and / or heat even in deep layers, and also has high transparency that can be used as a dental restorative material that requires an aesthetic appearance. It is providing the polymeric composition which gives the hardening material of this.
As a dental or surgical curable material, a composition in which inorganic particles and a curable compound were stably dispersed was given, and a composition having good curability by photopolymerization and / or thermal polymerization was obtained. The problem is that deterioration can be prevented even when the curable material comes into contact with moisture for a long period of time. Furthermore, from the point of forming a cured material of several mm to several centimeters, highly sensitive curability (curability in the depth direction and shortening the exposure or heating work time) is important. Good adhesion to the substrate is also required.
As described above, the problem to be solved by the present invention is to provide a polymerizable composition excellent in curing sensitivity and a dental or surgical curable material, and in dental that is excellent in wear resistance and stability. Or surgical curable material, molded article and method for producing the same.

The above object has been achieved by the means described below.
<1> A compound represented by the formula (I), a polymer having a monomer unit represented by the formula (II) and / or other addition polymerization type polymer, and inorganic particles. Polymerizable composition,

式（Ｉ）及び式（ＩＩ）中、Ｑ¹はシアノ基又は−ＣＯＸ²基を表し、Ｘ¹は、ヘテロ原子を介してα炭素に結合する水素原子、有機残基若しくはポリマー鎖、又は、ハロゲン原子を表し、Ｘ²は、ヘテロ原子を介してカルボニル基に結合する水素原子、有機残基若しくはポリマー鎖、又は、ハロゲン原子を表し、Ｒ^a、Ｒ^bは各々独立して、水素原子、ハロゲン原子、シアノ基又は有機残基を表し、Ｘ¹とＸ²、Ｒ^aとＲ^b、Ｘ¹とＲ^a又はＲ^bとが互いに結合して環状構造を形成してもよい、
＜２＞前記Ｘ¹の該ヘテロ原子が、酸素原子である＜１＞に記載の重合性組成物、
＜３＞前記Ｘ¹が、ヒドロキシ基、エーテル結合及びエステル結合よりなる群から選ばれた少なくとも１つの基又は結合を有する＜１＞又は＜２＞に記載の重合性組成物、
＜４＞前記Ｘ¹及び／又はＸ²がヒドロキシ基を有する＜１＞〜＜３＞いずれか１つに記載の重合性組成物、
＜５＞前記無機粒子の含有率が、重合性組成物全量に対して２０〜８０重量％である＜１＞〜＜４＞いずれか１つに記載の重合性組成物、
＜６＞前記無機粒子が、シリカゾル、コロイダルシリカ及びハイドロキシアパタイトよりなる群から選ばれた少なくとも１種である＜１＞〜＜５＞いずれか１つに記載の重合性組成物、
＜７＞＜１＞〜＜６＞いずれか１つに記載の重合性組成物を含有する歯科用又は外科用硬化性材料、
＜８＞＜１＞〜＜６＞いずれか１つに記載の重合性組成物を硬化して得られた歯科用又は外科用硬化材料、
＜９＞歯科用又は外科用成形品の製造方法であって、＜１＞〜＜６＞いずれか１つに記載の重合性組成物に光重合開始剤を添加し、光重合性組成物を調製する工程、前記光重合性組成物を供給する工程、及び、前記供給した光重合性組成物に活性放射線を照射して、前記光重合性組成物を硬化させる工程を含むことを特徴とする歯科用又は外科用成形品の製造方法、
＜１０＞歯科用又は外科用成形品の製造方法であって、＜１＞〜＜６＞いずれか１つに記載の重合性組成物に熱重合開始剤を添加し、熱重合性組成物を調製する工程、前記熱重合性組成物を供給する工程、及び、前記供給した熱重合性組成物を加熱して硬化させる工程を含むことを特徴とする歯科用又は外科用成形品の製造方法。

In Formula (I) and Formula (II), Q ¹ represents a cyano group or a —COX ² group, and X ¹ is a hydrogen atom, an organic residue or a polymer chain bonded to the α carbon via a hetero atom, or Represents a halogen atom, X ² represents a hydrogen atom bonded to a carbonyl group via a hetero atom, an organic residue or a polymer chain, or a halogen atom, and R ^a and R ^b each independently represent a hydrogen atom, Represents a halogen atom, a cyano group or an organic residue, and X ¹ and X ² , R ^a and R ^b , X ¹ and R ^a or R ^b may be bonded to each other to form a cyclic structure;
<2> The polymerizable composition according to <1>, wherein the hetero atom of X ¹ is an oxygen atom,
<3> The polymerizable composition according to <1> or <2>, wherein X ¹ has at least one group or bond selected from the group consisting of a hydroxy group, an ether bond and an ester bond.
<4> The polymerizable composition according to any one of <1> to <3>, wherein X ¹ and / or X ² have a hydroxy group,
<5> The polymerizable composition according to any one of <1> to <4>, wherein the content of the inorganic particles is 20 to 80% by weight based on the total amount of the polymerizable composition.
<6> The polymerizable composition according to any one of <1> to <5>, wherein the inorganic particles are at least one selected from the group consisting of silica sol, colloidal silica, and hydroxyapatite,
<7> Dental or surgical curable material containing the polymerizable composition according to any one of <1> to <6>,
<8><1> to <6> A dental or surgical curable material obtained by curing the polymerizable composition according to any one of the above,
<9> A method for producing a dental or surgical molded article, wherein a photopolymerization initiator is added to the polymerizable composition according to any one of <1> to <6>, and the photopolymerizable composition is obtained. A step of preparing, a step of supplying the photopolymerizable composition, and a step of irradiating the supplied photopolymerizable composition with active radiation to cure the photopolymerizable composition. A method for producing a dental or surgical molded article,
<10> A method for producing a dental or surgical molded article, wherein a thermal polymerization initiator is added to the polymerizable composition according to any one of <1> to <6>, and the thermal polymerizable composition is obtained. A method for producing a dental or surgical molded article comprising a step of preparing, a step of supplying the thermopolymerizable composition, and a step of heating and curing the supplied thermopolymerizable composition.

  According to the present invention, a polymerizable composition and a dental or surgical curable material excellent in curing sensitivity are provided, and a dental or surgical curable material and molded article excellent in wear resistance and stability. And a method for manufacturing the same.

<Polymerizable composition>
The polymerizable composition of the present invention contains a compound represented by the formula (I), a polymer having a monomer unit represented by the formula (II) and / or other addition polymerization type polymer, and inorganic particles. It is characterized by doing.

式（Ｉ）及び式（ＩＩ）中、Ｑ¹はシアノ基又は−ＣＯＸ²基を表し、Ｘ¹は、ヘテロ原子を介してα炭素に結合する水素原子、有機残基若しくはポリマー鎖、又は、ハロゲン原子を表し、Ｘ²は、ヘテロ原子を介してカルボニル基に結合する水素原子、有機残基若しくはポリマー鎖、又は、ハロゲン原子を表し、Ｒ^a、Ｒ^bは各々独立して、水素原子、ハロゲン原子、シアノ基又は有機残基を表し、Ｘ¹とＸ²、Ｒ^aとＲ^b、Ｘ¹とＲ^a又はＲ^bとが互いに結合して環状構造を形成してもよい。

In Formula (I) and Formula (II), Q ¹ represents a cyano group or a —COX ² group, and X ¹ is a hydrogen atom, an organic residue or a polymer chain bonded to the α carbon via a hetero atom, or Represents a halogen atom, X ² represents a hydrogen atom bonded to a carbonyl group via a hetero atom, an organic residue or a polymer chain, or a halogen atom, and R ^a and R ^b each independently represent a hydrogen atom, It represents a halogen atom, a cyano group or an organic residue, and X ¹ and X ² , R ^a and R ^b , X ¹ and R ^a or R ^b may be bonded to each other to form a cyclic structure.

  The compound represented by formula (I) will be described below.

In the formula (I), Q ¹ represents a cyano group or a —COX ² group, X ¹ represents a hydrogen atom, an organic residue or a polymer chain bonded to the α carbon via a hetero atom, or a halogen atom, X ² represents a hydrogen atom bonded to a carbonyl group via a hetero atom, an organic residue or a polymer chain, or a halogen atom, and R ^a and R ^b each independently represent a hydrogen atom, a halogen atom, a cyano group Or it represents an organic residue, and X ¹ and X ² , R ^a and R ^b , X ¹ and R ^a or R ^b may be bonded to each other to form a cyclic structure.

In the present invention, the compound represented by the formula (I) has at least one ethylenically unsaturated group in which two substituents are bonded to one carbon atom forming an ethylenically unsaturated double bond.
X ¹ and X ² may be monovalent organic residues, and X ¹ or X ² may be linked to each other by a divalent or n-valent (n ≧ 3; n represents an integer of 3 or more) organic linking group. It may be a bifunctional type or an n functional type, or may be a polymer type by forming a residue of a monomer unit in an oligomer or polymer.

Hereinafter, representative compound groups i) to iv) represented by the formula (I) will be described.
In the following description, since X ² is directly bonded to the carbonyl group at the α-position of the ethylenically unsaturated bond, as with X ¹ , “a hydrogen atom bonded to an α carbon via a heteroatom, a monovalent organic Also referred to as “residue or halogen atom”.
In the case where Q ¹ represents —COX ² , the compound represented by formula (I) is a hydrogen atom, a monovalent organic residue, or a halogen atom in which X ¹ and X ² are bonded to the α-carbon via a hetero atom. I) monofunctional ethylenically unsaturated compounds (Exemplary Compounds A-1 to A-42), X ¹ and X ² , R ^a and R ^b , X ¹ and R ^a or When R ^b is bonded to each other to form a cyclic structure, it becomes a monofunctional ethylenically unsaturated compound having a cyclic structure (Exemplary Compounds B-1 to B-9).
In the case where Q ¹ represents —COX ² , the compound represented by formula (I) is a hydrogen atom, a monovalent organic residue, or a halogen atom in which X ¹ is bonded to the α-carbon via a hetero atom. , X ² is a divalent group bonded to two carbonyl groups via a hetero atom, ii) becomes a bifunctional ethylenically unsaturated compound (Exemplary Compounds C-1 to C-14), X ^A bifunctional ethylenic group in which 1 is a divalent organic residue bonded to two α-carbons via a heteroatom and X ² is a hydrogen atom, a monovalent organic residue or a halogen atom. It becomes an unsaturated compound (Exemplary Compounds D-1 to D-30).
In the compound represented by the formula (I), when X ¹ is a monovalent group and X ² is an n-valent organic residue (n ≧ 3), iii) the number of functional groups of three or more functional types (Exemplary compounds E-1 to E-22), X ¹ is an n-valent organic residue (n ≧ 3), and X ² is a hydrogen atom, a monovalent organic Also in the case of a residue or a halogen atom, it becomes an n-functional ethylenically unsaturated compound (Exemplary Compounds F-1 to F-30).
In the compound represented by the formula (I), when either X ¹ or X ² is preferred, X ² is a residue of an oligomer or polymer monomer unit produced by addition polymerization or addition copolymerization. Iv) a polymer type ethylenically unsaturated compound (Exemplary Compounds G-1 to G-15).
Compounds of formula (I), in a case where Q ¹ is a cyano group, as in the case Q ¹ is a COX ^2, i as given later) monofunctional type, ii) 2 tetrafunctional Iii) a polyfunctional compound and iv) a polymer compound (H-1 to H-8).
In the case where Q ¹ represents —COX ² or —CN, it goes without saying that a person skilled in the art can produce many variations of compounds other than the above four compound groups.

In the above-described polymer type ethylenically unsaturated compound, at least one of X ¹ and X ² is bonded to the main chain of the polymer. That is, a form in which a structure derived from the formula (I) is present in the side chain of the polymer chain is employed. Here, examples of the polymer include the following linear organic polymer.
That is, examples thereof include vinyl polymers such as polyurethane, novolac, polyvinyl alcohol, polyhydroxystyrene, polystyrene, poly (meth) acrylic acid ester, poly (meth) acrylic acid amide, and polyacetal. These polymers may be homopolymers or copolymers (copolymers).

In formula (I), Q ¹ is a cyano group or a —COX ² group, and in X ¹ or X ² , a heteroatom bonded to the α-carbon, an organic residue or the like means an atom other than carbon, preferably non-carbon. A metal atom, specifically, an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. An oxygen atom, a sulfur atom, and a nitrogen atom are preferable, and an oxygen atom and a nitrogen atom are more preferable.
The hetero atom bonded to the α carbon and the organic residue in X ¹ is preferably an oxygen atom.
When X ¹ or X ² is a halogen atom, a chlorine atom, a bromine atom, an iodine atom, and fluorine atom and the like, preferably a chlorine atom or a bromine atom.

X ¹ is preferably a hydroxy group, a substituted oxy group, a mercapto group, a substituted thio group, an amino group, a substituted amino group, a sulfo group, a sulfonate group, a substituted sulfinyl group, a substituted sulfonyl group, a phosphono group, a substituted phosphono group, or a phosphonate. Selected from the group consisting of a group, a substituted phosphonato group, a nitro group and a heterocyclic group (linked by a heteroatom), a hydrogen atom bonded to the α-carbon via a heteroatom, an organic residue or a polymer chain More preferably an organic residue or polymer chain having at least one group or bond selected from the group consisting of a hydroxy group, an ether bond and a carboxylic acid ester bond, particularly preferably at least one hydroxy group It is an organic residue or polymer chain having

X ² is preferably a hydrogen atom bonded to a carbonyl group via a hetero atom, an organic residue or a polymer chain, and is a hydroxy group, a substituted oxy group, a mercapto group, a substituted thio group, an amino group, a substituted amino group Examples thereof include a group and a heterocyclic group (which are linked by a hetero atom). X ¹ and / or X ² preferably have a hydroxy group. When it has a hydroxy group, it is excellent in the dispersibility of inorganic particles, and is excellent in biocompatibility when used as a dental or surgical curable material.

R ^a and R ^b each independently represent more preferably a hydrogen atom, a halogen atom, a cyano group, or an organic residue, and the organic residue may have a substituent and have an unsaturated bond. Which may contain a hydrocarbon group, a substituted oxy group, a substituted thio group, a substituted amino group, a substituted carbonyl group, or a carboxylate group, and R ^a and R ^b may be bonded to each other to form a cyclic structure. Good.

Next, examples of substituents allowed for X ¹ , X ² , R ^a and R ^b in formula (I) are shown. This substituent includes a hydrocarbon group, an acyl group, and a heterocyclic group that may further have a substituent and may contain an unsaturated bond.

  Examples of the hydrocarbon group which may have the above-mentioned substituent and may contain an unsaturated bond include an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, and an alkynyl group. And substituted alkynyl groups.

  The acyl group includes an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group.

  The heterocyclic group includes a 5-membered or 6-membered heterocyclic group containing a nitrogen, oxygen, or sulfur atom as a heteroatom, and a group condensed with an aromatic group.

  Examples of the alkyl group include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and pentyl. Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group , Isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

  A substituted alkyl group is a group composed of a bond between a substituent and an alkylene group, and examples of the substituent include monovalent nonmetallic atoms (groups) excluding hydrogen, and a compound represented by the formula (I) Any atom or group is permissible as long as the polymerization reaction is not inhibited. A substituted alkenyl group, a substituted alkynyl group, and a substituted aryl group can be defined similarly. In these groups, examples of preferred substituents include a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, an aryloxy group, an acyloxy group, and a cyano group. Other acceptable substituents are described in paragraphs 0017 to 0041 of JP 2001-92127 A.

  Examples of the aryl group include those having 6 to 20 carbon atoms in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

  The alkenyl group is preferably a group having 2 to 20 carbon atoms. The substituted alkenyl group is a group in which the substituent is replaced with a hydrogen atom of the alkenyl group, and the substituent in the above-described substituted alkyl group is used as this substituent.

  The alkynyl group preferably has 2 to 20 carbon atoms. The substituted alkynyl group is a group in which the substituent is replaced with a hydrogen atom of the alkynyl group, and the substituent in the above-described substituted alkyl group is used as this substituent.

Next, examples of the cyclic structure formed by combining X ¹ and X ² , R ^a and R ^b , or X ¹ and R ^a or R ^b are shown. Aliphatic rings formed by combining X ¹ and X ² , R ^a and R ^b , or X ¹ and R ^a or R ^b with each other include 5-membered rings, 6-membered rings, 7-membered rings, and 8-membered rings. And, more preferably, a 5-membered or 6-membered aliphatic ring. These may further have a substituent on the carbon atoms constituting them (examples of the substituent include those allowed for the above-mentioned substituted alkyl group), and ring Part of the constituent carbon atoms may be substituted with a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.). Furthermore, a part of the aliphatic ring may form a part of the aromatic ring.

  Examples of the compound represented by the formula (I) are shown below in the order of i) monofunctional type, ii) bifunctional type, iii) polyfunctional type, and iv) polymer type.

  In addition to the specific examples illustrated below, other specific examples are illustrated in paragraphs 0043 to 0066 of JP-A-2001-92127 and paragraphs 0043 to 0051 of JP-A-2002-105128.

  Among the above exemplified compounds, A-1, A-12, A-17, A-22, A-27, A-38, B-5, C-1, D-7, E-4, F- For 3, G-5 and G-13, the synthesis method is described in paragraphs 0322 to 0335 of Patent Document 3. Other exemplary compounds can also be synthesized according to these synthesis methods. In addition, Exemplified Compounds H-1, H-2, H-3, H-4, and H-5 are also described in Japanese Patent Application Laid-Open No. 2002-105128, paragraphs 0178-0182, and other exemplified compounds. Can also be synthesized according to these synthesis methods.

<Polymerizable compound other than the compound represented by formula (I)>
In the polymerizable composition of the present invention, a polymerizable compound other than the compound represented by the formula (I) can be used in combination. Polymeric compounds other than the compound represented by formula (I) include acrylic esters, ordinary methacrylic esters having no hetero atom at the α-position, acrylamides, and usually having no hetero atom at the α-position. Includes known polymerizable compounds such as methacrylamides, vinyl esters, ethylenically unsaturated compounds having aromatic groups such as styrene, acrylonitriles, (meth) acrylamides, maleic anhydride, maleic imides, etc. Of these, (meth) acrylic acid esters and ordinary methacrylic acid esters having no hetero atom at the α-position are preferred.

  Suitable polymerizable compounds are the polymerizable compound itself, the polymerizable prepolymer produced therefrom, as well as mixtures thereof. Particularly suitable as polymerizable compounds are monofunctional or polyfunctional (meth) acrylic esters, which can be used alone or in a mixture.

  Specific examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methoxydiethylene glycol Examples thereof include (meth) acrylate, methacryloyloxyethyl trimerotic acid ester and acid anhydrides thereof.

Specific examples of polyfunctional (meth) acrylic acid esters include triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, decanediol di (meth) acrylate, dodecanediol di (meth) acrylate, bisphenol-A-di (meth) acrylate, trimethylol And propanetri (meth) acrylate and ethoxylated bisphenol-A-di (meth) acrylate, and bis-GMA (2,2-bis-4- (3-methacryloxy-2-hydroxy). Propyl) - phenyl propane) and an isocyanate, di especially - and / or reaction products from triisocyanates, and OH group-containing (meth) acrylate.
Examples of reaction products of isocyanates are conversion products of 1 mole of hexamethylene diisocyanate and 2 moles of 2-hydroxyethyl methacrylate, 1 mole of (tri (6-isocyanato-hexyl) biuret and 3 moles of hydroxyethyl methacrylate. Conversion products, and conversion products of 1 mole of trimethylhexamethylene diisocyanate and 2 moles of hydroxyethyl methacrylate, also referred to as urethane dimethacrylate.

In the present invention,
(A) at least one non-acidic, non-ionic hydrophilic crosslinking monomer, and
(B) at least one non-acidic, non-ionic hydrophilic diluent monomer having a viscosity of less than 1 Pa · s;
Is particularly preferably used as a polymerizable compound other than the compound represented by the formula (I).

It is preferred that the crosslinking monomer and dilution monomer are hydrophilic. That is, they are preferably capable of hydrophilic interaction with inorganic particles. Monomers containing one or more, preferably 1 to 2 urethane bonds and / or OH groups, preferably OH groups are preferred.
Non-acidic monomer has no strong acid group such as carboxy group, phosphoric acid group, phosphonic acid group, phosphinic acid group, or sulfonic acid group, preferably phenolic OH group, SH group, or CH acidic group It refers to a monomer having no weakly acidic group such as (for example, β diketone group or β diketo ester group).
The nonionic monomer means a monomer that does not contain an ionic group such as a cationic ammonium group, a sulfonium group, or an anionic acid residue of the strong acid group.

<Non-acidic, nonionic hydrophilic cross-linking monomer>
Cross-linking monomer represents a monomer containing at least 2, preferably 2 to 4 polymerizable groups per monomer molecule.
The preferred crosslinking monomer is 2,2-bis-4- (3-methacryloxy-2-hydroxypropyl) -phenylpropane) (bis-GMA), ie the reaction product of glycidyl methacrylate and bisphenol A (containing OH groups). And 7,7,9, -trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyl-dimethacrylate (UDMA), ie 2 moles of 2-hydroxy It is a urethane dimethacrylate obtained from ethyl methacrylate (HEMA) and 1 mol of 2,2,4-trimethylhexamethylene diisocyanate (containing a urethane group).
As the crosslinking monomer, glycidyl methacrylate and other bisphenols (for example, bisphenol-B (2,2′-bis- (4-hydroxyphenyl) -butane), bisphenol-F (2,2′-methylenediphenol) are preferable. ) Or 4,4′-dihydroxydiphenyl), as well as 2 moles of HEMA or 2-hydroxypropyl- (meth) acrylate and in particular 1 mole of a known diisocyanate (eg hexamethylene diisocyanate, m-xyl Diisocyanate or toluylene diisocyanate).

<Non-acidic, nonionic hydrophilic diluent monomer>
Diluting monomers are understood to mean monomers having a viscosity of less than 1 Pa · s, preferably less than 100 mPa · s, which are usually suitable for diluting high viscosity crosslinking monomers. In this way, it is possible to produce a polymerizable composition having a high inorganic particle content. The viscosity is measured at 23 ° C. with a plate according to DIN 53018 or with a rotational viscometer.
The diluting monomer also contains at least 2, preferably 2 to 3 polymerizable groups, and at least 1, preferably 1 to 2 OH groups and / or urethane linkages, preferably OH groups.
A particularly preferred diluent monomer is glycerol dimethacrylate (GDMA). Other preferred dilution monomers can be produced by reaction of low viscosity di- or triepoxides (eg, ethylene glycol diglycidyl ether, glycerol triglycidyl ether or trimethylolpropane triglycidyl ether) with (meth) acrylic acid. Further preferred is also the reaction product of 2 or 3 moles of methacrylic acid and glycerol triglycidyl ether or trimethylolpropane triglycidyl ether.

  Specific examples of the other monomers include polymerizable compounds described in paragraphs 0051 to 0056 of JP-A No. 2002-107927.

  The content of the compound represented by the formula (I) is preferably 30% by weight or more, more preferably 50% by weight or more, and more preferably 70% by weight or more based on the total amount of the polymerizable compound. Particularly preferred.

The polymerizable composition of the present invention includes a polymer having a monomer unit represented by the formula (II) or other addition polymerizable polymer.
The polymer having a monomer unit represented by the formula (II) will be described.

Wherein ^{(II), Q 1, X} 1, X 2, R a and R ^b are the same as ^{Q 1, X 1, X 2} , R a and R ^b in Formula (I), preferable ranges are also the same It is. In the case where the compound represented by the formula (I) and the polymer having the monomer unit represented by the formula (II) are used in combination, Q ¹ , X ¹ , X ² , R ^a and R ^b may be the same. May be different.

  Although it may be a homopolymer consisting only of the monomer unit represented by the above formula (II), it may be a copolymer including other structural units. Other structural units that can be suitably used include, for example, acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic The monomer unit introduce | transduced from well-known monomers, such as an acid imide, is mentioned.

  The polymer obtained by polymerizing the monomer unit having the structure represented by the formula (II) may be a random polymer, a block polymer, a graft polymer or the like, but is preferably a random polymer. Next, specific examples of the polymer obtained by polymerizing the monomer unit having the structure represented by the formula (II) are shown.

<Synthesis of Polymer Having Monomer Unit Represented by General Formula (II)>
<Synthesis Example 1: Compound P-1>
In the flask, A-1 (0.8 mol), methyl methacrylate (0.2 mol), V-65 (manufactured by Wako Pure Chemical Industries, Ltd., azo-based thermal polymerization initiator) (0.03 mol), N, N-dimethylacetamide (1 L) was mixed and stirred at 70 ° C. for 5 hours. After the reaction, white powder was precipitated when the reaction solution was gradually added to 5 L of water while stirring. This powder was filtered and dried to obtain P-1 in a yield of 90%. The structure of this material was confirmed by NMR, IR and GPC.
<Synthesis Example 2: Compound P-5>
In the flask, α-benzyloxymethacrylate (0.7 mol), methyl methacrylate (0.3 mol), V-65 (manufactured by Wako Pure Chemical Industries, Ltd., azo-based thermal polymerization initiator) (0.03 mol), N, N— Dimethylacetamide (1 L) was mixed and stirred at 70 ° C. for 5 hours. After the reaction, white powder was precipitated when the reaction solution was gradually added to 5 L of water while stirring. The powder was filtered and dried to obtain P-5 in a yield of 95%. The structure of this material was confirmed by NMR, IR and GPC.
<Synthesis Example 3: Compound P-14>
In the flask, α-acetamidomethacrylic acid (0.7 mol), methyl methacrylate (0.3 mol), V-65 (manufactured by Wako Pure Chemical Industries, Ltd., azo-based thermal polymerization initiator) (0.03 mol), N, N— Dimethylacetamide (1 L) was mixed and stirred at 70 ° C. for 5 hours. After the reaction, white powder was precipitated when the reaction solution was gradually added to 5 L of water while stirring. This powder was filtered and dried to obtain P-14 in a yield of 94%. The structure of this material was confirmed by NMR, IR and GPC.
All polymers shown in the specific examples can be synthesized according to the above synthesis examples.

The polymerizable composition of the present invention can be used in place of the polymer having the monomer unit represented by the formula (II) or in addition to the polymer having the monomer unit represented by the formula (II). It may contain molecules.
Other polymers include polymethyl methacrylate, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer Etc. are included. When another polymer is used in combination with the polymer having the monomer unit represented by the formula (II), it is preferable that both have compatibility. Specific examples of other polymers include the polymers described in paragraph 0063 of JP-A-2002-107927.

  The content of the polymer having the monomer unit represented by the formula (II) is preferably 30% by weight or more, more preferably 50% by weight or more, based on the weight of all the components of the polymer. It is particularly preferably 70% by weight or more.

<Inorganic particles>
The polymerizable composition of the present invention contains inorganic particles. By containing inorganic particles, shrinkage at the time of curing can be reduced, and the wear resistance of the molded product after curing can be improved. The inorganic particles preferably have an average particle diameter of 1 nm to 100 μm. Here, the average means a weight average.

  Examples of the inorganic particles include silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, aluminum oxide particles, and calcium compounds. Among these, silicon dioxide particles, zirconium oxide particles, and calcium compound particles are preferable.

  In addition, the inorganic particles include amorphous spherical materials based on the above mixed oxide derived from inorganic particles, fine inorganic particles (for example, pyrogenic silica or precipitated silica), macro or mini inorganic particles (for example, quartz), glass ceramic Alternatively, glass powder having an average particle size of 0.01 to 5 μm, radiopaque inorganic particles (for example, ytterbium trifluoride) and the like are included.

  The use of other glasses that release ions and are known, for example, for the production of glass ionomer cements is also possible. There are conventional fluoroaluminum silicate glass powders having an average particle size of about 0.05 to 15 μm, which contain silicon oxide, aluminum oxide and calcium oxide as the main components (AD Wilson, J (See W. McLean, Glasinomerzment, Quintessenz Verlags-GmbH, 1988, Berlin, page 21).

  The inorganic particles used in the present invention are preferably (non) metal oxide sols. (Non) metal oxide sol means that (non) metal oxide particles are uniformly and stably dispersed in a liquid. Specific examples include silica sol, colloidal silica and zirconia sol, and silica sol and colloidal silica are preferred. Colloidal silica is a preferred example as the inorganic particles used in the present invention, and the preferred average particle size is 10 to 500 nm.

  When the metal oxide sol is used, the dispersion medium is not particularly limited, and examples thereof include alcohols such as isopropyl alcohol, cellosolves, water, dimethylacetamide, and xylene, and alcohols, cellosolves, and water are preferable.

The polymerizable compound and polymer having an α-hetero-substituted methylacrylic group of the present invention is a solvent consisting of a hetero atom substituted at the α-position, resulting in a number of weak interaction sites that are close to each other by polymerization. Makes inorganic particles stably dispersed as if they were to be summed.
Therefore, although the surface treatment of the inorganic particles is not particularly required, the surface of the inorganic particles may be treated with a surface modifier containing an organic segment in order to further increase the affinity. The surface modifier preferably has a functional group capable of forming a bond with the inorganic particle or adsorbing to the inorganic particle and a functional group having high affinity with the organic component in the same molecule.

Examples of the surface modifier having a functional group capable of binding or adsorbing to inorganic particles include metal alkoxide surface modifiers such as silane compounds, aluminum compounds, titanium compounds, and zirconium compounds, phosphate groups, sulfate groups, sulfonate groups, and carboxyl groups. Examples include surface modifiers having an anionic group such as an acid group, metal alkoxide surface modifiers are preferred, and silane compounds are more preferred.
Furthermore, the functional group having a high affinity with the organic component may be simply a combination of the organic component and the hydrophilicity / hydrophobicity, but a functional group that can be chemically bonded to the organic component is preferable, particularly an ethylenically unsaturated group or Ring-opening polymerizable groups are preferred.
Representative examples of these surface modifiers include unsaturated double bond-containing coupling agents, phosphate group-containing organic curable resins, sulfate group-containing organic curable resins, carboxylic acid group-containing organic curable resins, and the like.

  In the present invention, the inorganic particles are preferably treated beforehand with a silane compound represented by the formula (III) as a surface modifier.

[Chemical formula 24]
SiL ¹ _a L ² _b (OL ³ ) _c (III)
In the formula, L ¹ and L ² each independently represent an ether bond, an ester bond, a carbon-carbon double bond, or a C 1-10 hydrocarbon residue that may contain an amino group.
L ³ is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, a and b are each independently an integer of 0 to 3, c is 4-ab, and represents an integer of 1 to 4.

Examples of the silane compound of the formula (III) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, β-acryloyloxyethyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane , P-vinylphenyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidylo And cyclopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and partial condensates thereof, and the like, and γ-methacryloyloxypropyltri Methoxysilane is preferred.
These silane compounds can be used alone or in combination of two or more.

The surface modification of the inorganic particles is preferably performed in a solution.
When the inorganic particles are mechanically finely dispersed, the surface modifier is present together, or after the inorganic particles are finely dispersed, the surface modifier is added and stirred, or the surface before the inorganic particles are finely dispersed. Modification may be performed (if necessary, heating or drying may be performed after heating or pH adjustment), and then fine dispersion may be performed. As the solution for dissolving the surface modifier, an organic solvent having a large polarity is preferable. Specific examples include known solvents such as alcohols, ketones and esters.

  The amount of the silane compound used to obtain the inorganic particles is not particularly limited, but the silane compound represented by the formula (III) is preferably 5 to 100 parts by weight of the inorganic particles (solid content of the metal oxide sol). 200 parts by weight, more preferably 25 to 100 parts by weight are used.

  When colloidal silica or zirconia sol is used as the inorganic particles, the silane compound represented by the formula (III) is mixed in the colloidal dispersion and hydrolyzed with water in the system or newly added water. Inorganic particles whose surface is modified with a decomposition product are obtained. An inorganic acid or an organic acid can be used as a catalyst for the hydrolysis reaction of the silane compound. As the inorganic acid, for example, hydrohalic acid such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfur, nitric acid, phosphoric acid and the like are used. Examples of the organic acid include formic acid, acetic acid, oxalic acid, acrylic acid, methacrylic acid and the like.

A solvent can be used in the silane compound hydrolysis reaction system in order to perform the reaction gently and uniformly. As the solvent, a solvent capable of compatibilizing the reactant silane alkoxide with water and a catalyst is desirable. Specific examples include water, alcohols such as isopropyl alcohol, ketones such as acetone, and ethers such as dioxane.
As these solvents, the colloidal dispersion medium described above may be used as it is, or a necessary amount may be newly added. The amount of the solvent used is not particularly limited as long as it can dissolve the reactants uniformly, but if the concentration of the reactants becomes too dilute, the reaction rate may be remarkably slowed. The hydrolysis and condensation reaction of the silane compound is performed at a temperature of about room temperature to 120 ° C. for about 30 minutes to 24 hours, preferably at a temperature of room temperature to about the boiling point of the solvent for about 1 to 10 hours. Is called.

  The method for uniformly dispersing the surface-modified inorganic particles in the polymerizable compound is not particularly limited. For example, a silane compound represented by the formula (III) and water if necessary in a dispersion of colloidal silica. And a catalyst are mixed, reacted under the above-described reaction conditions, a polymerizable compound is mixed in the liquid after the reaction, and then a volatile component generated by a hydrolysis reaction of a dispersion medium of colloidal silica and a silane compound is removed. Is particularly preferable because it can prevent aggregation of inorganic particles.

In the present invention, calcium compounds can be preferably used as the inorganic particles.
As the calcium compound, calcium phosphate, calcium carbonate and the like are preferably used, and calcium phosphate can be more preferably used. These may be used alone or in combination of two.

  Examples of calcium phosphate include hydroxyapatite, α-tricalcium phosphate, β-tricalcium phosphate, γ-tricalcium phosphate, tetracalcium phosphate, octacalcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, and non- Examples thereof include crystalline calcium phosphate, and hydroxyapatite is preferable. These may be used alone or in combination of two or more.

  The method for producing hydroxyapatite is not particularly limited, and may be produced by any method. Examples of the method for producing hydroxyapatite include a dry method, a semi-dry method, and a wet method.

The average particle size of the inorganic particles used in the present invention is preferably 1 nm to 100 μm, more preferably 5 nm to 30 μm, still more preferably 10 nm to 10 μm, and particularly preferably 10 nm or more and less than 2 μm. preferable.
When the weight average particle diameter of the inorganic particles is in the above range, the appearance and the wear resistance of the cured product are excellent.

  Further, when silica is used as the inorganic particles, the average particle diameter is preferably 1 nm to 500 nm, more preferably 10 nm to 100 nm, and still more preferably 10 nm to 50 nm as described above. Within the above numerical range, since the silica having a particle size smaller than the wavelength of visible light (380 nm to 780 nm) is uniformly dispersed, the polymerizable composition is excellent in transparency and polymerized using visible light. When it is made to be hardened, it can be hardened to the deep part.

Further, when hydroxyapatite is used as the inorganic particles, the weight average particle diameter is preferably 0.5 to 100 μm, more preferably 0.5 to 30 μm, and further preferably 0.5 to 10 μm. 0.5 to 3 μm is particularly preferable. It is preferable in the range of the above numerical values to provide a curing strength suitable for a surgically cured product.
As the inorganic particles used in the present invention, hydroxyapatite can be preferably used along with colloidal silica. A polymerizable composition containing colloidal silica as inorganic particles can be preferably used as a dental curable material, and a polymerizable composition containing hydroxyapatite as inorganic particles can be used as a surgical curable material. .

  The content of the inorganic particles is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and still more preferably 40 to 60% by weight of the total amount of the polymerizable composition in terms of hardness and sensitivity. Within the above numerical range, the sensitivity of the polymerizable composition and the hardness of the molded product are excellent.

<Combination ratio>
The polymerizable composition of the present invention includes (1) a combination of a compound represented by formula (I) and a polymer having a monomer unit represented by formula (II), and (2) a compound represented by formula (I). And a polymer of an ethylenically unsaturated compound having no hetero atom at the α-position such as PMMA, and (3) an ethylenically unsaturated monomer having no hetero atom at the α-position such as MMA and the formula (II) Although there are three modes of using a polymer having a monomer unit represented, both modes (1) and (2) are preferable, and the mode (1) is more preferable.

In the polymerizable composition, an ethylenically unsaturated monomer (a compound represented by the formula (I) and / or a polymerizable compound that can be used in combination), and a polymer (having a monomer unit represented by the formula (II)) The content of the polymer and / or other addition-polymerizable polymer) is preferably 10 to 80% by weight, more preferably 30 to 70% by weight, and still more preferably 50 to 60% by weight.
Within the above numerical range, the sensitivity of the polymerizable composition and the hardness and stability of the molded product after curing are excellent.

  The content of the ethylenically unsaturated monomer (the compound represented by the formula (I) and / or the polymerizable compound that can be used in combination) is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and 40 to 40%. More preferably 60% by weight.

  In the present invention, when the polymer represented by the formula (II) is used, the use ratio thereof is preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight based on the total amount of the polymerizable composition. 0.1 to 10% is more preferable. It is excellent in the point of the sensitivity of polymeric composition and the hardness of a molded article as it is in the range of said numerical value.

In the present invention, although the clear mechanism is unknown, it is considered that the direct interaction of the polymerizable compound having the α-hetero-substituted methylacryl group as the main component with the inorganic particles is important.
That is, the polymerizable compound having an α-hetero-substituted methylacryl group and the polymer have a number of weak interaction sites that are close to each other as a result of polymerization of a substituent composed of a hetero atom substituted at the α-position. The inorganic particles are considered to be stably dispersed as if they were to be summed.

Further, in a polymerizable compound having an α-hetero-substituted methylacryl group, unlike a low-polymerizable itaconic acid group having a substituent at the α-position or an α-alkylacryl group, the hetero atom substituted at the α-position. The polymer has improved polymerizability due to electronic effects and steric effects, and has a polymerizability comparable to acrylic. In particular, the combination of a compound having an α-hetero-substituted methylacryl group and a photoinitiator can significantly reduce the influence of oxygen polymerization inhibition, and can provide a photopolymerizable composition having high sensitivity and good storage stability. JP-A-2001-92127 discloses that the chain growth terminal by matching with the polymerization growth rate constant, the termination rate constant, and the initiator is less likely to react with oxygen. The photocurability when contained is not fully understood.
That is, when the inorganic particles are contained, the content of the polymerizable component is lowered, so that the curability (polymerizability) is generally decreased with respect to the additive-free addition, but in the present invention, It was confirmed that there was no decrease.
In this respect, the interaction with the filler described above has a pseudo-crosslinked structure, and rather has an effect of assisting the curability, and offsets the inherent decrease in curability when inorganic particles are added. I believe that.

<Other additives>
If necessary, the polymerizable composition of the present invention can be blended with an inorganic filler (silica powder, quartz powder, glass powder and the like having an average particle size of more than 100 μm).
If necessary, rubber, pigment (eg, titanium oxide, iron oxide, etc.), solvent (eg, ethanol, ethyl acetate, etc.), polymerization inhibitor (eg, hydroquinone, phenols, etc.), oxidation stabilizer, ultraviolet absorber, etc. It can also be added.

  The content of other additives is preferably 0.1 to 15% by weight of the total amount of the polymerizable composition, more preferably 0.1 to 10% by weight, and still more preferably 0.1 to 5% by weight. Within the above numerical range, the sensitivity of the curable composition and the hardness of the obtained molded product are excellent.

<Method for producing molded product>
Another aspect of the present invention relates to a method for producing a molded article. (1) A photopolymerization initiator is added to the polymerizable composition described in any one of the above items <1> to <6>, and photopolymerization is performed. And (2) supplying the photopolymerizable composition, and (3) irradiating the supplied photopolymerizable composition with active radiation to prepare the photopolymerizable composition. It includes a step of curing.
Here, the photopolymerizable composition refers to a composition obtained by adding a photopolymerization initiator to the polymerizable composition of the present invention, and as a thermopolymerizable composition using a thermal polymerization initiator instead of the photopolymerization initiator. Also good. A thermopolymerizable composition refers to a composition obtained by adding a thermal polymerization initiator to a polymerizable composition.
The method for producing the molded product of the present invention will be described below.

The above molded product can be used for dentistry or surgery.
Moreover, if the process of supplying a polymerizable composition is exemplified, it may be supplied to a concave part which is a dental treatment part, may be supplied to a curable mold for manufacturing a denture or an implant, or a prosthetic material for artificial bone In this case, it may be supplied into a curing frame having a desired shape.

<Polymerization initiator>
In the present invention, a known radical polymerization initiator can be used as the polymerization initiator.
The radical polymerization initiator that can be used in the polymerizable compound of the present invention is a compound that absorbs external energy and generates a radical polymerization initiating species. External energy used for initiating polymerization is roughly divided into heat and actinic radiation, and a thermal polymerization initiator and a photopolymerization initiator are used, respectively. Examples of the active radiation include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays.
A radical polymerization initiator may be used independently and may use 2 or more types together. It is arbitrarily selected and used depending on the polymerization mode suitable for each dental or surgical curable material.

<Thermal polymerization initiator>
The thermal polymerization initiator that can be used in the present invention refers to a compound that generates radicals by thermal energy and initiates and accelerates polymerization of a compound having a polymerizable ethylenically unsaturated group.
In the present invention, as the thermal radical generator, a known thermal polymerization initiator or a compound having a bond having a small bond dissociation energy can be selected and used. For example, an onium salt compound, a triazine compound having a trihalomethyl group, an organic peroxide. Compounds, azo polymerization initiators, azide compounds, quinonediazide compounds, metallocene compounds and the like can be mentioned, among which organic peroxide compounds can be preferably used.
Examples of the organic peroxide compound include diacyl peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, etc. Among them, diacyl peroxide is preferable.

  Specifically, the diacyl peroxide includes octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic acid peroxide, dibenzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-toluyl. Peroxydicarbonates include di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, and di- (2-ethoxyethyl) peroxydicarbonate. Peroxyesters include tert-butylperoxyisobutyrate, tert-butylperoxypivalate, tert-butylperoxyoctanoate, octyl Peroxyoctanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxyneododecanoate, octylperoxyneododecanoate, tert-butylperoxylaurate, tert-butylperoxybenzoate Dialkyl peroxides include di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- (tert-butylperoxy) hexane; 2,2-bis (tert-butylperoxy) butane, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylsilane Rhohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate; ketone peroxide includes methyl ethyl ketone peroxide; hydroperoxide includes p-menthane hydroperoxide, cumene hydroperoxide, Dibenzoyl peroxide is preferred.

  In the present invention, a thermal polymerization initiator having a 10-hour half-life temperature of preferably 60 ° C. or higher, desirably 70 ° C. or higher can be used alone or in combination of two or more.

  The addition amount of the thermal polymerization initiator is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 1% by weight, and more preferably 0.01 to 0.1% by weight with respect to 100 parts by weight of the polymerizable composition. Is more preferable.

<Photopolymerization initiator>
Examples of the photopolymerization initiator include ketal compounds such as benzophenones and benzoin dimethyl ether, benzoin alkyl ethers, anthraquinones, thioxanthones, acylphosphine oxides, and α-diketones, among which α-diketones are preferable.
Examples of the α-diketone include 9,10-phenanthrenequinone, diacetyl, furyl, anisyl, 4,4′-dichlorobenzyl, 4,4′-dialkoxybenzyl, and camphorquinone, among which camphorquinone is preferable.
In the case of photopolymerization, a reducing agent such as a tertiary amine may be used in combination. Further, an oxidizing agent such as a peroxide and a reducing agent may be blended separately and mixed at the time of use to perform redox polymerization.
Tertiary amines include cyanoethyl methylaniline, dimethylaminoethyl methacrylate, triethylamine, triethanolamine, N, N-dimethylaniline, N-methyldiphenylamine, and N, N-dimethyl-sym. -Xylidine, N, N-dimethyl-p-toluidine, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, and the like, and p-dimethylaminobenzoic acid is more preferable.

  The addition amount of the photopolymerization initiator is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 7% by weight, and still more preferably 0.01 to 5% by weight with respect to 100 parts by weight of the polymerizable composition. preferable.

  The step of irradiating the photopolymerizable composition with actinic radiation to cure the photopolymerizable composition will be described.

<Actinic radiation>
The photopolymerizable composition of the present invention is cured by irradiation with actinic radiation.
This is because the photopolymerization initiator contained in the photopolymerizable composition of the present invention is decomposed by irradiation with actinic radiation to generate radicals, acids, bases and other starting species, and the function of the starting species is radically polymerizable. This is because the polymerization reaction of the compound occurs and is accelerated. Examples of the active radiation include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays, and ultraviolet rays and visible rays are preferable, and visible rays are more preferable.

The thermopolymerizable composition of the present invention is cured by heating.
When curing the thermopolymerizable composition, suitable curing conditions can be selected as appropriate.
It is preferable to heat the molded article for 1 hour to 3 hours using a heat medium of preferably 40 to 80 ° C, more preferably 50 to 70 ° C.
Further, after this heating, it is preferably polymerized by post-heating in a temperature range of preferably 60 to 100 ° C., more preferably 70 to 90 ° C. for 1 hour to 3 hours.

<Application>
The polymerizable composition of the present invention can be used as a dental material. When used as a dental material, the polymerizable composition is applied to a natural or artificial tooth defect to be treated or injected into a denture or implant form as necessary, and then polymerized and cured. . The polymerizable composition of the present invention can be particularly preferably used as a repair material such as a cavity filling material.
In addition, the polymerizable composition of the present invention can be used as a surgical artificial bone filling material or the like, and can be used as a bone filling material for a bone defect in the fields of surgery, orthopedics and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are given concretely and this invention is demonstrated in detail, this invention is not limited to a following example. Unless otherwise specified, “%” represents “% by weight” and “part” represents “part by weight”.

<Photopolymerizable composition>
(Example 1)
Polymerizable compound (X) A-6 in Table 1 50 parts Polymer (Y) P-1 in Table 1 7 parts Inorganic particles: Surface-treated colloidal silica (manufactured by Catalyst Chemical Industry Co., Ltd.) 40 parts Photopolymerization initiator: Camphor-quinone / p-dimethylaminobenzoic acid = 1/4 weight ratio
3 parts were dissolved to obtain a photopolymerizable composition.
The inorganic particles are isopropyl alcohol-dispersed colloidal silica (silica content 30%, average particle size 15 nm, manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name OSCAL-1432), γ-methacryloyloxypropyltrimethoxysilane 11 .2 parts and 3 parts of 0.01 N hydrochloric acid aqueous solution were added and the mixture stirred at 40 ° C. for 1 hour was used.

<Evaluation of wear resistance>
The photopolymerizable composition is filled in a stainless steel mold having an inner diameter of 10 mm and a thickness of 1 mm with a cover glass having a thickness of 0.1 mm on the lower surface, and the same cover glass is brought into close contact with the upper surface. Light irradiation was performed with an irradiator “G-Light” (manufactured by GC Corporation) for 60 seconds to obtain a cured product. The output peak wavelength region of visible light was 465 nm to 475 nm.
Furthermore, a toothbrush wear test (condition: toothbrush “Prospec” (manufactured by GC Corporation), load 100 g, 50,000 strokes in water) is performed on the cured product, which is commonly used in evaluation of dental materials, and a wear resistance test. And evaluated. The allowable level of wear depth is 3 μm or less. The results are shown in Table 1.

<Evaluation of sensitivity>
The photopolymerizable composition is filled in a stainless steel mold having an inner diameter of 10 mm and a thickness of 1 mm with a cover glass having a thickness of 0.1 mm on the lower surface, and the same cover glass is brought into close contact with the upper surface. Light irradiation was performed with an irradiator “G-light” (manufactured by GC Corporation) for 45 seconds to obtain a cured product.
Furthermore, the said toothbrush abrasion test was implemented about this hardened | cured material. The allowable level of wear depth is 5 μm or less. When the wear depth did not change with respect to the irradiation time of 60 seconds and the number was small, it was judged that the sensitivity was good. The results are shown in Table 1.

<Evaluation of stability>
The photopolymerizable composition is filled in a stainless steel mold having an inner diameter of 10 mm and a thickness of 1 mm with a cover glass having a thickness of 0.1 mm on the lower surface, and the same cover glass is brought into close contact with the upper surface. Light irradiation was performed with an irradiator “G-Light” (manufactured by GC Corporation) for 60 seconds to obtain a cured product.
Further, the cured product was kept in water at 60 ° C. for one week. Thereafter, the toothbrush wear test was conducted. The allowable level of wear depth is 5 μm or less. The results are shown in Table 1.

(Examples 2 to 8)
Abrasion resistance, sensitivity, and stability were evaluated in the same manner as in Example 1 except that the polymerizable compounds and polymers described in Table 1 were used. The results are shown in Table 1.

(Examples 9 and 10)
Abrasion resistance, sensitivity and stability were evaluated in the same manner as in Example 1 except that the polymerizable compounds shown in Table 1 were used and polymethyl methacrylate was used as the polymer. The results are shown in Table 1.

(Comparative Examples 1-4)
Abrasion resistance, sensitivity, and stability were evaluated in the same manner as in Example 1 except that the polymerizable compounds and polymers described in Table 1 were used. The results are shown in Table 1.

The symbols in the table are as shown below.
X1: Triethylene glycol dimethacrylate / A-15 = 50/50 (%)
X2: Triethylene glycol dimethacrylate / D-11 = 70/30 (%)
T1: 2,2-bis-4- (3-methacryloxy-2-hydroxypropyl) phenylpropane T2: hexanediol dimethacrylate T3: triethylene glycol dimethacrylate T4: pentaerythritol tetramethacrylate PMMA: polymethyl methacrylate Mw5. 0,000

<Thermopolymerizable composition>
(Example 13)
Polymeric compound (X) A-1 in Table 2 50 parts Polymer (Y) P-5 in Table 2 10 parts Inorganic particles: Hydroxyapatite powder (average particle size 1 μm, manufactured by PENTAX Corporation)
40 parts Thermal polymerization initiator: 0.05 part of benzoyl peroxide was dissolved to obtain a thermally polymerizable composition.

<Evaluation of wear resistance>
The thermopolymerizable composition was filled in a stainless steel mold having an inner diameter of 10 mm and a thickness of 1 mm with a cover glass having a thickness of 0.1 mm on the lower surface, and the same cover glass was brought into close contact with the upper surface. Heated for an hour and then post-heated at 80 ° C. for 2 hours to obtain a cured product.
Furthermore, a toothbrush wear test (condition: toothbrush “Prospec” (manufactured by GC Corporation), load 100 g, 50,000 strokes in water) is performed on the cured product, which is commonly used in evaluation of dental materials, and a wear resistance test. And evaluated. The allowable level of wear depth is 3 μm or less. The results are shown in Table 2.

<Evaluation of sensitivity>
The thermopolymerizable composition was filled in a stainless steel mold having an inner diameter of 10 mm and a thickness of 1 mm with a cover glass having a thickness of 0.1 mm on the lower surface, and the same cover glass was brought into close contact with the upper surface. Heated for an hour and then post-heated at 80 ° C. for 1 hour to obtain a cured product.
Furthermore, the said toothbrush abrasion test was implemented about this hardened | cured material. The allowable level of wear depth is 5 μm or less. The wear depth did not change with respect to the post-heating time of 2 hours, and a small number was judged to have good sensitivity. The results are shown in Table 2.

<Evaluation of stability>
The thermopolymerizable composition is filled in a stainless steel mold having an inner diameter of 10 mm and a thickness of 1 mm with a cover glass having a thickness of 0.1 mm on the lower surface, and the same cover glass is brought into close contact with the upper surface. Light irradiation was performed with an irradiator “G-Light” (manufactured by GC Corporation) for 60 seconds to obtain a cured product.
Further, the cured product was kept in water at 60 ° C. for one week. Thereafter, the toothbrush wear test was performed. The allowable level of wear depth is 5 μm or less. The results are shown in Table 2.

(Examples 14 to 22)
Abrasion resistance, sensitivity, and stability were evaluated in the same manner as in Example 13 except that the polymerizable compounds and polymers described in Table 2 were used. The results are shown in Table 2.

(Examples 23 and 24)
Abrasion resistance, sensitivity and stability were evaluated in the same manner as in Example 13 except that the polymerizable compounds shown in Table 2 were used and polymethyl methacrylate was used as the polymer. The results are shown in Table 2.

(Comparative Examples 5 to 8)
Abrasion resistance, sensitivity, and stability were evaluated in the same manner as in Example 13 except that the polymerizable compounds and polymers described in Table 2 were used. The results are shown in Table 2.

The symbols in the table are as shown below.
X1: Methyl methacrylate / A-5 = 50/50 (%)
X2: Methyl methacrylate / D-21 = 70/30 (%)
T4: n-butyl methacrylate T5: Methyl methacrylate / hexanediol dimethacrylate = 70/30 (%)
T6: Methyl methacrylate / pentaerythritol tetramethacrylate = 70/30 (%)
MMA: Methyl methacrylate

  From the results shown in Tables 1 and 2, the polymerizable composition of the present invention has good dispersion stability of inorganic particles, particularly high sensitivity, high wear resistance, and high stability, particularly in a dental polymerizable composition. .

Claims (10)

A compound represented by formula (I),
A polymer having a monomer unit represented by the formula (II) and / or other addition polymerization type polymer, and
A polymerizable composition comprising inorganic particles.

In Formula (I) and Formula (II), Q ¹ represents a cyano group or a —COX ² group, and X ¹ is a hydrogen atom, an organic residue or a polymer chain bonded to the α carbon via a hetero atom, or Represents a halogen atom, X ² represents a hydrogen atom bonded to a carbonyl group via a hetero atom, an organic residue or a polymer chain, or a halogen atom, and R ^a and R ^b each independently represent a hydrogen atom, It represents a halogen atom, a cyano group or an organic residue, and X ¹ and X ² , R ^a and R ^b , X ¹ and R ^a or R ^b may be bonded to each other to form a cyclic structure. The polymerizable composition according to claim ¹ , wherein the hetero atom of X ¹ is an oxygen atom. The polymerizable composition according to claim 1, wherein X ¹ has at least one group or bond selected from the group consisting of a hydroxy group, an ether bond and an ester bond. The polymerizable composition according to claim ^1, wherein X ¹ and / or X ² have a hydroxy group.   The content rate of the said inorganic particle is 20 to 80 weight% with respect to the polymerizable composition whole quantity, The polymerizable composition as described in any one of Claims 1-4.   The polymerizable composition according to claim 1, wherein the inorganic particles are at least one selected from the group consisting of silica sol, colloidal silica, and hydroxyapatite.   A dental or surgical curable material containing the polymerizable composition according to any one of claims 1 to 6.   A dental or surgical curable material obtained by curing the polymerizable composition according to any one of claims 1 to 6. A method of manufacturing a dental or surgical molded article,
Adding a photopolymerization initiator to the polymerizable composition according to any one of claims 1 to 6 to prepare a photopolymerizable composition;
Supplying the photopolymerizable composition; and
A method for producing a dental or surgical molded article, comprising the step of irradiating the supplied photopolymerizable composition with actinic radiation to cure the photopolymerizable composition. A method of manufacturing a dental or surgical molded article,
Adding a thermal polymerization initiator to the polymerizable composition according to any one of claims 1 to 6 to prepare a thermally polymerizable composition;
Supplying the thermopolymerizable composition; and
A method for producing a dental or surgical molded article, comprising a step of heating and curing the supplied thermopolymerizable composition.