JP2006335946A - Composite article and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite article excellent in mechanical properties such as bending strength and to provide a method for producing the article. <P>SOLUTION: The composite article comprises a hydrolyzed condensate of a compound (I) and a silicone-containing polymer, wherein the compound (I) contains a metal atom (M) to which at least one atom group selected from a halogen atom and an alkoxy group is bound and the silicone-containing polymer contains a structural unit derived from a monomer (A) and a monomer (B), the monomer (A) being one shown by the following formula (1) and the monomer (B) being a vinyl compound and/or a carboxylic acid vinyl ester containing a nitrogen-containing hetero ring. H<SB>2</SB>C=CR<SP>1</SP>SiR<SP>2</SP>R<SP>3</SP>R<SP>4</SP>- (1) (wherein R<SP>1</SP>is a hydrogen atom or an alkyl group; R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>are each a halogen atom, or a group selected from an alkyl group, an alkoxy group and a hydroxy group, and at least one of R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>is a halogen atom, an alkoxy group or a hydroxy group). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a composite containing a silicon-containing polymer and a method for producing the same.

  As one of the methods for modifying a polymer substance, there is a compound with an inorganic substance. As one of the techniques, a so-called sol-gel method has been tried. Specifically, attempts have been made to perform hydrolysis and polycondensation of metal alkoxides in the presence of a polymer substance or in a polymerization system of raw material monomers of the polymer substance. According to this method, a composite composed of a polymer substance and a metal oxide (for example, silica) can be obtained. This method has been attempted for various polymer materials such as olefin polymers, acrylic polymers, vinyl alcohol polymers, and siloxane polymers.

  In recent years, application to coating applications has been energetically studied. For example, composites composed of a vinyl alcohol polymer and a metal oxide have been disclosed (see, for example, Patent Documents 1 and 2).

  As another example, a method of forming a coating film by hydrolytic condensation of tetraethoxysilane in the presence of a vinyltrimethoxysilane radical polymer is disclosed (see Non-Patent Document 1).

The properties of the composite of the polymer substance and the metal oxide are greatly influenced by the degree of polymerization of the polymer substance used. As a result of the study by the authors, the polymer had to have a number average molecular weight of 10,000 or more in order for the composite to exhibit sufficient physical properties. The vinyl methoxysilane conventionally used for the introduction of cross-linking by alkoxysilyl groups has low polymerization as a vinyl compound, and it is difficult to obtain a degree of polymerization that expresses the physical properties of the composite by itself. . In addition, the polymer substance obtained by polymerizing a monomer containing an alkoxysilyl group is very easy to gel due to its properties, and when actually used as a composite, the alkoxysilyl group concentration is too high, In addition to the reaction between the metal oxide and the polymer material, a reaction in which the polymer materials are cross-linked and aggregated may occur, which sometimes hinders the expression of physical properties as a composite.
JP-A-8-99390 JP-A-9-278968 Journal of the Ceramic Society of Japan, Vol. 105, p555 (1997)

  Currently, further improvements in properties are desired for conventional composites containing metal oxides and polymeric substances.

  In view of such a situation, an object of the present invention is to provide a composite having excellent mechanical properties such as bending strength and a method for producing the same.

  As a result of studies to achieve the above object, the present inventors have found that a composite having excellent mechanical properties can be obtained by using a specific silicon-containing polymer and a specific metal-containing compound. The present invention is based on this new finding.

  The first complex of the present invention is a complex comprising a hydrolysis condensate of compound (I) and a silicon-containing polymer, wherein the compound (I) is at least one selected from a halogen atom and an alkoxy group. It is at least one compound containing a metal atom (M) to which two atomic groups are bonded, and the silicon-containing polymer is composed of a structural unit (A) derived from the monomer (A) and a monomer (B). The monomer (A) is at least one compound represented by the following formula (1), and the monomer (B) is a nitrogen-containing complex. It is at least one compound selected from the group consisting of a vinyl compound having a ring and a carboxylic acid vinyl ester compound.

［式中、Ｒ¹は水素原子またはアルキル基である。Ｒ²、Ｒ³およびＲ⁴はそれぞれ独立に、ハロゲン原子、アルキル基、アルコキシ基および水酸基から選ばれる１つの原子団であり、Ｒ²、Ｒ³およびＲ⁴から選ばれる少なくとも１つの原子団（Ｇ）はハロゲン原子、アルコキシ基または水酸基である。］

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one atomic group selected from R ² , R ³ and R ⁴ ( G) is a halogen atom, an alkoxy group or a hydroxyl group. ]

  The second composite of the present invention is a composite containing a metal oxide containing a metal atom (M) and a silicon-containing polymer, and the silicon-containing polymer is added to the monomer (A). The structural unit (A) derived from and the structural unit (B) derived from the monomer (B), wherein the monomer (A) is at least one compound represented by the following formula (1) The monomer (B) is at least one compound selected from the group consisting of a vinyl compound having a nitrogen-containing heterocycle and a carboxylic acid vinyl ester compound.

［式中、Ｒ¹は水素原子またはアルキル基である。Ｒ²、Ｒ³およびＲ⁴はそれぞれ独立に、ハロゲン原子、アルキル基、アルコキシ基および水酸基から選ばれる１つの原子団であり、Ｒ²、Ｒ³およびＲ⁴から選ばれる少なくとも１つの原子団（Ｇ）はハロゲン原子、アルコキシ基または水酸基である。］

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one atomic group selected from R ² , R ³ and R ⁴ ( G) is a halogen atom, an alkoxy group or a hydroxyl group. ]

  The production method of the present invention for producing a composite is a first method for obtaining a silicon-containing polymer by polymerizing a plurality of types of monomers including a monomer (A) and a monomer (B). A mixture comprising: a step; at least one selected from the group consisting of a compound (I), a hydrolyzate of compound (I), and a hydrolyzed condensate of compound (I); the silicon-containing polymer; and a solvent. A second step of preparation. The monomer (A) is at least one compound represented by the following formula (1), and the monomer (B) includes a vinyl compound having a nitrogen-containing heterocyclic ring and a carboxylic acid vinyl ester. And at least one compound selected from the group consisting of compounds, wherein the compound (I) includes at least one metal atom (M) to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded. A compound.

［式中、Ｒ¹は水素原子またはアルキル基である。Ｒ²、Ｒ³およびＲ⁴はそれぞれ独立に、ハロゲン原子、アルキル基、アルコキシ基および水酸基から選ばれる１つの原子団であり、Ｒ²、Ｒ³およびＲ⁴から選ばれる少なくとも１つの原子団（Ｇ）はハロゲン原子、アルコキシ基または水酸基である。］

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one atomic group selected from R ² , R ³ and R ⁴ ( G) is a halogen atom, an alkoxy group or a hydroxyl group. ]

  The composite obtained by the production method of the present invention constitutes another aspect of the composite of the present invention. Moreover, the lump of the present invention is composed of the complex of the present invention.

  According to the present invention, a composite that is transparent and excellent in mechanical properties such as bending strength and compressive strength can be obtained. The composite of the present invention can be used as a substitute for a metal material in a specific field.

  Hereinafter, embodiments of the present invention will be described. In the following description, specific compounds are exemplified as compounds that exhibit a specific function, but the present invention is not limited to these. Moreover, as long as there is no description in particular, the illustrated material may be used independently and may be used in combination of 2 or more type.

(Complex)
The composite of the present invention is a composite comprising a hydrolysis condensate of compound (I) and a silicon-containing polymer.

  Compound (I) is at least one compound containing a metal atom (M) to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded. As shown in the so-called sol-gel method, the metal atom (M) of the compound (I) is linked through oxygen by a hydrolysis condensation reaction. When this hydrolysis-condensation reaction proceeds sufficiently, the hydrolysis-condensation product of compound (I) substantially becomes a metal oxide (for example, metal oxide particles having a functional group on the surface). The hydrolyzed condensate of the compound (I) in the present invention includes a product obtained by partially hydrolyzing and condensing the compound (I). Furthermore, the present invention provides a composite in which the hydrolysis condensate of the compound (I) is a metal oxide containing a metal atom (M), that is, a composite containing a metal atom (M) and a silicon-containing polymer. Include. In the latter case, “hydrolysis condensate of compound (I)” can be read as “metal oxide” in the following description of the composite.

  The metal atom (M) is selected from Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La and Nd At least one atom selected from Si, Al, Ti and Zr. Among these, silicon (Si) is preferable because a highly transparent composite can be obtained. Si may be classified as a similar metal element, but in this specification, it will be described as a metal element.

  Examples of the halogen atom contained in the compound (I) include chlorine and bromine. Examples of the alkoxy group contained in the compound (I) include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, and a t-butoxy group. Can be mentioned.

  Examples of the atomic group bonded to the metal atom (M) other than the halogen atom and the alkoxy group include an alkyl group. The number of atomic groups bonded to the metal atom (M) is equal to the valence of the metal atom (M). In a typical example, the atomic group bonded to the metal atom (M) consists of only a halogen atom, only an alkoxy group, or only a halogen atom and an alkoxy group. Such compound (I) is represented by the following formula.

M (OR) _mn X _n
[Wherein M represents a metal atom. R represents an alkyl group (carbon number is preferably 6 or less, for example 3 or less). X represents a halogen atom. m is equal to the valence of the metal atom M. n is an integer of 0 or more and m or less. ]

  Specific examples of the compound (I) include silicon alkoxides such as tetramethoxysilane, tetraethoxysilane, chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, and trichloroethoxysilane; tetra Halogenated silanes such as chlorosilane and tetrabromosilane; alkoxytitanium compounds such as tetramethoxytitanium, tetraethoxytitanium and tetraisopropoxytitanium; titanium halides such as tetrachlorotitanium; trimethoxyaluminum, triethoxyaluminum and triisopropoxyaluminum , Alkoxy aluminum compounds such as tributoxy aluminum and diethoxy aluminum chloride; tetraethoxy zirconium, tetraisopropyl Po carboxymethyl zirconium, and the like alkoxy zirconium compound such as methyl triisopropoxy zirconium.

  Hereinafter, the silicon-containing polymer contained in the composite of the present invention will be described. The silicon-containing polymer includes a structural unit (A) derived from the monomer (A) and a structural unit (B) derived from the monomer (B). The silicon-containing polymer may further contain a structural unit (C) derived from the monomer (C). The monomer (A) is at least one compound represented by the following formula (1).

［式中、Ｒ¹は水素原子またはアルキル基である。Ｒ²、Ｒ³およびＲ⁴はそれぞれ独立に、ハロゲン原子、アルキル基、アルコキシ基および水酸基から選ばれる１つの原子団であり、Ｒ²、Ｒ³およびＲ⁴から選ばれる少なくとも１つの原子団（Ｇ）はハロゲン原子、アルコキシ基または水酸基である。］

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one atomic group selected from R ² , R ³ and R ⁴ ( G) is a halogen atom, an alkoxy group or a hydroxyl group. ]

Examples of the alkyl group applicable to R ¹ , R ² , R ³ and R ⁴ include alkyl groups such as a methyl group, an ethyl group and a propyl group. Examples of the halogen atom applicable to R ² , R ³ and R ⁴ include chlorine and bromine. Examples of the alkoxy group applicable to R ² , R ³ and R ⁴ include alkyloxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group; alkoxyalkyleneoxy groups such as 2-methoxyethoxy group; benzyloxy group And aralkyloxy groups such as In a typical example of R ^{2 to} R ⁴ , R ² , R ³ and R ⁴ are each independently a halogen atom or an alkoxy group.

At least one selected from R ² , R ³ and R ⁴ is preferably a halogen atom or an alkoxy group. In monomer (A-1) which is a preferred example of monomer (A), R ¹ is a hydrogen atom, and R ^{2 to} R ⁴ are halogen atoms. In monomer (A-2) which is another preferred example of monomer (A), R ¹ is a hydrogen atom, and R ^{2 to} R ⁴ are alkoxy groups. In monomer (A-3), which is another preferred example of monomer (A), R ¹ is a hydrogen atom, R ^{2 to} R ⁴ are either an alkoxy group or a halogen atom, and at least 1 One is an alkoxy group and at least one is a halogen atom. Specific examples of the monomer (A) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, vinyldiethoxyethylsilane. Vinylethoxydimethylsilane, vinylethoxydiethylsilane, vinyltris (2-methoxyethoxy) silane, and vinyltrichlorosilane.

  The monomer (B) is at least one compound selected from the group consisting of a vinyl compound having a nitrogen-containing heterocycle and a carboxylic acid vinyl ester compound. Examples of the monomer (B) having a nitrogen-containing heterocyclic ring include vinyl pyrrolidone (N-vinyl-2-pyrrolidone), vinyl imidazole, N-vinyl purine, N-vinyl piperazine, and N-vinyl piperidine. Examples of the carboxylic acid vinyl ester include vinyl acetate, vinyl benzoate, vinyl propionate, vinyl butyrate, and vinyl caproate.

  The vinyl imidazole may be any of N-vinyl imidazole, 2-vinyl imidazole, 4-vinyl imidazole, or a mixture thereof, but from the viewpoint of copolymerization with the monomer (A). N-vinylimidazole is preferred. Since these monomers (B) are highly copolymerizable with the monomer (A) and the monomer (C) described later, a silicon-containing polymer having a uniform and high polymerization degree is obtained. By using it, the mechanical properties of the composite are improved. The monomer (B) may be at least one compound selected from vinyl pyrrolidone and vinyl imidazole, and is preferably any one of them.

  The silicon-containing polymer used in the present invention may contain a structural unit (C) derived from the monomer (C). Monomer (C) is at least one compound containing two or more carbon-carbon double bonds. As the monomer (C), for example, triallyl isocyanurate, triallyl trimellitate, diallyl chlorendate, divinyl adipate, divinyl succinate, divinyl ether, divinyl sulfone, divinyl phthalate, diallyl phthalate, divinyl Benzene or the compounds described below can be mentioned.

The monomer (C) is a group represented by (CR ⁵ ═CH ₂ ) (where R ⁵ is a hydrogen atom or an alkyl group) and a group represented by (CR ⁶ ═CH ₂ ) (where R ^{6 is} R ^6). Is preferably a hydrogen atom or an alkyl group) and is preferably at least one compound containing a silicon atom to which is bonded. Since such a compound contains two carbon-carbon double bonds, a polymer having a crosslinked structure introduced into the main chain can be obtained by using the compound. In particular, when using a monomer in which a group represented by (CR═CH ₂ ) (where R is a hydrogen atom or an alkyl group) is directly bonded to a silicon atom, the monomer (C) Polymerizability with the monomer (A) is improved. As a result, a silicon-containing polymer having a higher molecular weight is obtained, and when a crosslinked structure is introduced, a silicon-containing polymer in which the main chain of the polymer is strongly constrained is obtained. As a result, an effect of improving the mechanical properties of the composite containing such a silicon-containing polymer can be obtained.

  Moreover, it is preferable that a monomer (C) is at least 1 type of compound represented by the following formula | equation (2).

［式中、Ｒ⁵およびＲ⁶はそれぞれ独立に水素原子またはアルキル基である。Ｒ⁷およびＲ⁸はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、水酸基および（ＣＲ⁹＝ＣＨ₂）で表される基（ただしＲ⁹は水素原子またはアルキル基である）から選ばれる１つの原子団である。］

[Wherein, R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a group represented by (CR ⁹ ═CH ₂ ) (where R ⁹ is a hydrogen atom or an alkyl group). One selected atomic group. ]

At least one selected from R ⁷ and R ⁸ is preferably a halogen atom, an alkoxy group, a hydroxyl group, or a group represented by (CR ⁹ ═CH ₂ ), and particularly preferably a halogen atom or an alkoxy group. preferable.

Examples of the alkyl group applicable to R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ include a methyl group, an ethyl group and a propyl group. Examples of the halogen atom applicable to R ⁷ and R ⁸ include chlorine and bromine. Examples of the alkoxy group applicable to R ⁷ and R ⁸ include alkyloxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group; alkoxyalkyleneoxy groups such as 2-methoxyethoxy group; aralkyl such as benzyloxy group An oxy group is mentioned.

Examples of the monomer (C) represented by the formula (2) will be described below. In the first monomer (C-1), at least one of R ⁷ and R ⁸ is an alkoxy group, and preferably R ⁷ and R ⁸ are both alkoxy groups. In the second monomer (C-2), at least one of R ⁷ and R ⁸ is a halogen atom, and preferably R ⁷ and R ⁸ are both halogen atoms. In the third monomer (C-3), R ⁷ is a group represented by (CR ⁹ ═CH ₂ ), and R ⁸ is an alkoxy group, a halogen atom, or an alkyl group. In the monomers (C-1) to (C-3), R ⁵ and R ⁶ may be a hydrogen atom or an alkyl group.

  Specific examples of the compound represented by the formula (2) include, for example, diethoxydivinylsilane, dimethoxydivinylsilane, methoxymethyldivinylsilane, dichlorodivinylsilane, methyltrivinylsilane, chlorotrivinylsilane, methoxytrivinylsilane, ethoxytrivinylsilane. Is mentioned.

  The monomer (A) described above and the monomer (B) and monomer (C) described above can be polymerized in any combination. For example, the monomer (A-1), vinylpyrrolidone, and any of the monomers (C-1), (C-2), and (C-3) may be combined. Further, the monomer (A-2), vinylpyrrolidone, and any of the monomers (C-1), (C-2), and (C-3) may be combined. Further, the monomer (A-3), vinylpyrrolidone, and any of the monomers (C-1), (C-2), and (C-3) may be combined. In the above combination, vinylpyrrolidone may be replaced with vinylimidazole. An example of such a combination is shown in the examples. The combination of structural units constituting the silicon-containing polymer is determined according to the combination of monomers at the time of polymerization.

  The monomer (A), monomer (B), monomer (C) and compound (I) may be commercially available or synthesized by a known method. Good.

  A preferred ratio of the structural unit (A) and the structural unit (B) in the total structural unit of the silicon-containing polymer composed of the monomer (A) and the monomer (B) is the monomer (A) as a material. Depending on the type of monomer (B) and the intended use of the composite containing the resulting silicon-containing polymer. Considering that the molecular weight of the resulting polymer and the proportion of alkoxysilyl groups relative to the entire side chain affect the physical properties of the composite, the following proportions are preferred. The proportion of the structural unit (A) in the total structural unit of the silicon-containing polymer is in the range of 5 to 60 mol%, and the proportion of the structural unit (B) in the total structural unit of the silicon-containing polymer is 20 to 95 mol. % Is preferable. The molar ratio of structural unit (A) / structural unit (B) is preferably 60/40 to 5/95, more preferably 55/45 to 10/90, and even more preferably 50 / 50-20 / 80.

  In the case of the silicon-containing polymer comprising the monomer (A), the monomer (B) and the monomer (C), the structural unit (A), the structural unit (B), the structural unit ( The preferred proportion of C) depends on the type of monomer (A), monomer (B) and monomer (C) as materials, and the intended use of the composite containing the resulting silicon-containing polymer. Change. Considering the influence of the molecular weight and the ratio of the alkoxysilyl group to the entire side chain, the following ratio is preferable. In a typical example, the sum of the proportion of the structural unit (A) and the proportion of the structural unit (C) in the total structural units of the silicon-containing polymer is in the range of 5 to 60 mol%, It is preferable that the ratio of the structural unit (B) to the total structural unit of the coalescence is in the range of 20 to 95 mol%. The molar ratio of (structural unit (A) + structural unit (C)) / structural unit (B) is preferably a ratio of 60/40 to 5/95, more preferably 55/45 to 10/90. More preferably, it is 50 / 50-20 / 80. The molar ratio of structural unit (A) / structural unit (C) is preferably a ratio of 70/30 to 99.5 / 0.5, more preferably 80/20 to 97/3, Preferably it is 85 / 15-95 / 5. By making the molar ratio of (structural unit (A) + structural unit (C)) / structural unit (B) and the molar ratio of structural unit (A) / structural unit (C) within this range, gelation during polymerization And a high molecular weight polymer can be obtained.

  In the complex of the present invention, the ratio of the hydrolysis condensate of compound (I) contained in the complex is preferably in the range of 1 to 40% by weight. By setting it as this range, the composite_body | complex excellent in mechanical physical properties, such as bending strength, can be obtained. The ratio is more preferably in the range of 2 to 35% by weight, and still more preferably in the range of 3 to 30% by weight.

  The ratio of the silicon-containing polymer contained in the composite is preferably in the range of 30 to 99% by weight. By setting it as this range, the composite_body | complex excellent in mechanical physical properties, such as bending strength, can be obtained. The ratio is more preferably in the range of 40 to 98% by weight, and still more preferably in the range of 60 to 97% by weight.

  Since the silicon-containing polymer contained in the composite of the present invention has a plurality of structural units (A) derived from the monomer (A), it has at least one atomic group (G). It has a plurality of silyl groups. In the composite of the present invention, the silyl group having the atomic group (G) is condensed and / or hydrolyzed with another functional group in at least a part of the plurality of structural units (A) contained in the silicon-containing polymer. Condensation is preferred. At least a part of the silyl group having these atomic groups (G) may be condensed directly with other functional groups, or may be condensed after hydrolysis. When the silyl group having the atomic group (G) is condensed and / or hydrolytically condensed, mechanical properties such as bending strength are improved. The other functional group on which the silyl group having the atomic group (G) is condensed and / or hydrolyzed is a functional group (or a functional group present on the surface of the metal oxide) contained in the hydrolytic condensate of the compound (I). But may be other functional groups in the silicon-containing polymer (for example, a silyl group having one atomic group (G) and a silyl group having another atomic group (G)). Condensation and / or hydrolytic condensation). The condensation of the silyl group having the atomic group (G) of the structural unit (A) can be confirmed by measuring the spectrum of silicon by solid-state NMR.

  When the structural unit (C) in the silicon-containing polymer has a silyl group directly bonded to a functional group that can contribute to condensation and / or hydrolysis condensation of a halogen atom, an alkoxy group, a hydroxyl group, etc., At least a part of these silyl groups may be condensed and / or hydrolytically condensed with other functional groups as in the case of the silyl group having the atomic group (G) in the structural unit (A). .

  The silicon-containing polymer preferably has a number average molecular weight (Mn) of 10,000 or more, more preferably 12,000 or more, and further preferably 15,000 or more. When the number average molecular weight (Mn) is 10,000 or more, the mechanical properties (for example, tensile strength, tensile elongation, flexibility) of the composite containing the silicon-containing polymer are particularly good. The upper limit of the number average molecular weight (Mn) is not particularly limited, but is preferably within a range that dissolves in the polar organic solvent described above. The number average molecular weight (Mn) and the weight average molecular weight (Mw) referred to in the present specification are values in terms of polystyrene measured by GPC (Gel Permeation Chromatography), as described in Examples.

  Further, the molecular weight distribution of the silicon-containing polymer, that is, the value represented by the ratio “Mw / Mn” between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 1 to 15, more preferably. Is in the range of 1-10, more preferably in the range of 1-3. When the molecular weight distribution is in a preferred range, the mechanical properties of the resulting composite are good.

  The complex of the present invention is typically composed of only the hydrolysis condensate of compound (I) and the silicon-containing polymer, or substantially only of these, but other substances may be used as long as the effects of the present invention can be obtained. May be included. For example, the composite of the present invention may be made of other materials such as polyamide, polyurethane, polyester, polycarbonate, polyoxymethylene resin, acrylic resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyolefin, polystyrene, styrenic block copolymer, etc. A polymer may be included. The composite of the present invention further comprises a stabilizer, a lubricant, a pigment, an impact resistance improver, a processing aid, a crystal nucleating agent, a reinforcing agent, a colorant, a flame retardant, a weather resistance improver, an ultraviolet absorber, and an antioxidant. Agents, hydrolysis resistance improvers, fungicides, antibacterial agents, light stabilizers, antistatic agents, silicone oil, antiblocking agents, mold release agents, foaming agents, fragrances, etc .; glass fibers, polyester fibers Ingredients such as various fibers such as talc, silica, wood powder, and various coupling agents may be included.

  The composite of the present invention contains a hydrolyzed condensate of compound (I) and a silicon-containing polymer, and is characterized by high mechanical properties such as hardness and bending strength and high translucency. In particular, when the hydrolysis condensate of compound (I) and the silicon-containing polymer are condensed (bonded), particularly excellent mechanical properties are exhibited. According to the present invention, it is possible to obtain a composite having a three-point bending strength of 100 MPa or more.

  The composite of the present invention can be used in the form of a mass or a thin film. As a lump, the thing of the magnitude | size of 0.5 mm square or more, More preferably, the thing of the magnitude | size of 1 mm square or more, More preferably, the thing of a magnitude | size of 4 mm square or more can be illustrated.

  Since the composite of the present invention is hard and excellent in mechanical properties such as bending strength, it can be preferably used for applications such as dental materials, optics, and electrical / electronic component materials. Specific examples of dental materials include crown materials such as crowns, inlays, onlays and bridges, metal frames used for hard resin front crowns and metal bond porcelains, artificial teeth, dentures, denture bases and denture base linings. Materials, implant superstructure, various implant members (screw fixture, abutment, etc.), dental posts, clasps, fillers for dental composite resins, and the like.

  As a manufacturing method of these denture materials, in the manufacturing method of the present invention to be described later, a fluid mixture containing a solvent or the like is poured into a mold having voids of a desired shape and molded, Moreover, the method etc. which cut the lump which consists of a composite_body | complex of this invention and make it the target shape are mentioned.

  The dental composite resin is a composite material composed of a polymerizable monomer and an inorganic filler (inorganic powder). This composite resin is used as a crown material for filling a hole formed by cutting a part of a tooth, building an abutment, or crown.

  In these dental composite resins, conventionally, silica or silica-based glass has been used as the inorganic filler material. When the powder obtained from the composite of the present invention is used as an inorganic filler in place of these conventional inorganic fillers, the dental is excellent in mechanical strength and polishing lubricity, and further in lubrication durability in the oral cavity. Composite resin is obtained.

  When the composite of the present invention is used as a filler for a dental composite resin, the composite of the present invention is pulverized by a method such as a ball mill to obtain a powder having an appropriate particle size. The particle size of the powder is usually in the range of 0.05 to 50 μm in average particle size and 0.01 to 200 μm in particle size range.

  Moreover, a well-known thing is used without a restriction | limiting as a polymerizable monomer. In a dental composite resin containing the composite of the present invention as a filler, the blending ratio of the filler of the present invention relative to 100 parts by weight of the polymerizable monomer is usually in the range of 10 to 1,000 parts by weight.

  The composite of the present invention can also be used for various applications such as paints, inks, adhesives, pressure-sensitive adhesives, compatibilizing agents, and sealing materials.

(Production method of composite)
Hereinafter, the manufacturing method of a composite_body | complex is demonstrated. According to the production method of the present invention, the above-described composite can be produced. The composite manufactured by the manufacturing method of the present invention constitutes another aspect of the composite of the present invention.

  The production method of the present invention includes a first step of obtaining a silicon-containing polymer by polymerizing a plurality of types of monomers including the monomer (A) and the monomer (B). This first step is a step of obtaining a silicon-containing polymer by polymerizing a plurality of types of monomers including the monomer (A), the monomer (B), and the monomer (C). Good. Further, this production method comprises at least one selected from compound (I), a hydrolyzate of compound (I), and a hydrolyzed condensate of compound (I), and the silicon-containing polymer obtained in the first step. A second step of preparing a mixture comprising a solvent. The monomer (A) is at least one compound represented by the above formula (1). The monomer (B) is at least one compound selected from the group consisting of a vinyl compound having a nitrogen-containing heterocycle and a carboxylic acid vinyl ester compound. Monomer (C) is at least one compound containing two or more carbon-carbon double bonds. Compound (I) is at least one compound containing a metal atom (M) to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded.

  Since the compound applicable to the monomer (A), the monomer (B) and the monomer (C), and the combination thereof have been described above, redundant description will be omitted. Moreover, since the compound applicable to compound (I) was also mentioned above, the overlapping description is abbreviate | omitted.

  First, the first step (polymerization step) for obtaining a silicon-containing polymer will be described. The first step can be performed according to a known polymerization method such as anionic polymerization, cationic polymerization, radical polymerization, etc., but is preferably performed by radical polymerization.

  In the case where a plurality of types of monomers including the monomer (C) are polymerized by radical polymerization, it is preferably carried out at a temperature of 80 ° C. or higher in the presence of a polymerization initiator. The polymerization initiator to be used is not particularly limited, but it is preferable that the activation energy for decomposition of the polymerization initiator is 126 kJ / mol (30 kcal / mol) or more. The activation energy is more preferably 147 kJ / mol (35 kcal / mol) or more. Specific examples of the polymerization initiator having an activation energy of 126 kJ / mol or more include cumene hydroperoxide, t-butyl hydroperoxide, sec-butyl peroxide, dicumyl peroxide, di-t-butyl peroxide. , T-amyl peroxide, t-butyl-α-cumyl peroxide, dimethyl peroxide, t-butyl perbenzoate, 2,2′-azobis (2-methylpropane), 1,1′-azobis (cyclohexane-1 -Carbonitrile) and the like. In particular, the polymerization step is performed at a temperature of 80 ° C. or higher in the presence of a polymerization initiator, and the polymerization initiator is cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide. It is preferably at least one selected from oxide, t-butyl perbenzoate, and 1,1′-azobis (cyclohexane-1-carbonitrile). These polymerization initiators have a decomposition activation energy of 147 kJ / mol or more.

  When the monomer used as the material for the silicon-containing polymer does not contain the monomer (C), the polymerization step is preferably performed at a temperature of 40 ° C. or higher in the presence of a polymerization initiator. The polymerization initiator to be used is not particularly limited. In addition to the above polymerization initiator, a polymerization initiator having an activation energy for decomposition of less than 126 kJ / mol (30 kal / mol) may be used. For example, various organic peroxides and azo polymerization initiators may be used as the polymerization initiator. Specific examples include 2,2'-azobisisobutyronitrile, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, and the like.

  The amount of the polymerization initiator used is not particularly limited, but when the monomer used as the material of the silicon-containing polymer includes the monomer (C), all monomers (plural types of monomers) 1 Preferably it is the range of 0.01-0.5 mol per mole, More preferably, it is the range of 0.02-0.2 mol, More preferably, it is the range of 0.03-0.1 mol. Moreover, when the monomer used as the material of the silicon-containing polymer does not contain the monomer (C), it is preferably 0.001 to 10 per mole of all the monomers (plural types of monomers). It is the range of mol, More preferably, it is the range of 0.005-5 mol. When the usage-amount of a polymerization initiator exists in a preferable range, a higher molecular silicon-containing polymer is easy to be obtained.

  When the silicon-containing polymer is produced from the monomer (A) and the monomer (B), the monomer (A) and the monomer (B The preferred ratio of () varies depending on the types of the monomer (A) and the monomer (B) and the purpose of use of the resulting composite, and therefore cannot be specified unconditionally. In a typical example, the proportion of the monomer (A) in the total monomer (a plurality of monomers) is in the range of 5 to 60 mol%, and the monomer (B) in the total monomer Is in the range of 20 to 95 mol%. The molar ratio of monomer (A) / monomer (B) is preferably 60/40 to 5/95, more preferably 55/45 to 10/90, and still more preferably. 50/50 to 20/80.

  When the silicon-containing polymer is produced from the monomer (A), the monomer (B), and the monomer (C), the monomer (A) occupying the whole monomer (a plurality of monomers) The preferred ratio of the monomer (B) and the monomer (C) depends on the type of the monomer (A), the monomer (B) and the monomer (C) and the intended use of the resulting composite. Since it changes depending on the situation, it cannot be specified in general. In a typical example, the ratio of the monomer (A) to the total monomer (a plurality of monomers) and the ratio of the monomer (C) are in the range of 5 to 60 mol%, The ratio of the monomer (B) in the monomer is in the range of 20 to 95 mol%. The molar ratio of (monomer (A) + monomer (C)) / monomer (B) is preferably a ratio of 60/40 to 5/95, more preferably 55/45 to 10/90, more preferably 50/50 to 20/80. The molar ratio of monomer (A) / monomer (C) is preferably a ratio of 70/30 to 99.5 / 0.5, more preferably 80/20 to 97/3. More preferably, it is 85/15 to 95/5.

  In the first step of the present invention, the polymerization step may be performed by bulk polymerization without using a solvent, or the polymerization step may be performed in the presence of a solvent. When carrying out the polymerization step in the presence of a solvent, it is preferable to use an organic solvent as the solvent. As the organic solvent, for example, dioxane, chlorobenzene, methyl benzoate, toluene, xylene, mesitylene, decalin, ethylene glycol dimethyl ether, and acetonitrile can be used.

  When carrying out the polymerization step in the presence of a solvent, prepare a polymerizable mixture containing monomer (A), monomer (B), organic solvent, and, if necessary, monomer (C). To do. During the polymerization step, the mixture is preferably bubbled with an inert gas. Moreover, it is preferable to perform a superposition | polymerization process in inert gas atmosphere. For example, nitrogen gas or argon gas can be used as the inert gas. When it does not contain a monomer (C), it is preferable to adjust the temperature of this mixture in a superposition | polymerization process to 40 degreeC or more, and it is more preferable to adjust to 60 degreeC or more. When the monomer (C) is contained, the temperature of the mixture in the polymerization step is preferably adjusted to 80 ° C or higher, and more preferably adjusted to 100 ° C or higher (for example, 120 ° C or higher). The temperature of the mixture is preferably adjusted to 50 ° C. or less of the boiling point of the monomer (A), and more preferably adjusted to 40 ° C. or less (eg, 30 ° C. or less) of the boiling point of the monomer (A). .

  The polymerization initiator may be mixed in advance with the monomer (A), the monomer (B), or the monomer (C), or may be added to the polymerizable mixture described above. The total amount of the polymerization initiator may be added at once, or may be added in several divided portions. Although there is no particular limitation on the timing of adding the polymerization initiator, it is preferable to add the polymerization initiator after starting bubbling with an inert gas. The polymerization initiator may be added after adjusting the mixture to the polymerization temperature, or may be added before adjusting the mixture to the polymerization temperature. In particular, when a polymerization initiator having an activation energy of 126 kJ / mol (30 kcal / mol) or less is used, it is preferable to add the polymerization initiator after adjusting the mixture to the polymerization temperature.

  In the first step in the present invention, the monomer (A), the monomer (B), and the monomer (C) as necessary are copolymerized. Due to the presence of (C), the molecular weight of the resulting silicon-containing polymer can be dramatically increased. In the first step in the present invention, a silicon-containing polymer having a number average molecular weight of 10,000 or more, more preferably 12,000 or more, and further preferably 15,000 or more can be obtained. In addition, by using a monomer containing a silicon atom as the monomer (C), characteristics (for example, bending strength and compressive strength) expected for a composite containing a silicon-containing polymer to be obtained are high. A polymer is obtained.

  The production method of the present invention may further include a step of removing a component dissolved in the hydrocarbon solvent from the silicon-containing polymer obtained by the polymerization step. According to this step, since the low molecular weight component dissolved in the hydrocarbon solvent can be removed, a silicon-containing polymer having a higher number average molecular weight, for example, a silicon-containing polymer having a number average molecular weight of 15,000 or more can be obtained. The low molecular weight component can be removed, for example, by immersing the silicon-containing polymer in a hydrocarbon solvent and then performing filtration. A high molecular weight silicon-containing polymer is usually not soluble in a hydrocarbon solvent and can be easily separated by filtration. The silicon-containing polymer having a larger number average molecular weight thus obtained is usually a polar organic solvent (for example, tetrahydrofuran; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; methanol, ethanol, propanol, ethylene glycol, etc.) A polymer that dissolves in alcohol, chloroform, dimethyl sulfoxide, acetone, sulfolane, etc.) and is not produced by gelation (hydrolytic condensation reaction between polymers).

  The hydrocarbon solvent is a solvent composed of hydrocarbon, and for example, at least one selected from n-hexane, cyclohexane, n-heptane, toluene, benzene and xylene can be used. Among these, n-hexane is preferable. The amount of the hydrocarbon solvent to be used is not particularly limited, but it is preferably 5 to 100 times the weight of the silicon-containing polymer, more preferably 10 to 50 times the weight. The temperature of the hydrocarbon solvent to be used is not particularly limited, but when the boiling point of the hydrocarbon solvent is T ° C., the temperature is preferably in the range of 20 ° C. to T ° C., and 20 ° C. to (T-20) ° C. A range is more preferable. The time for immersing the silicon-containing polymer in the hydrocarbon-based solvent is not particularly limited, but it is preferably immersed for 30 minutes or more, and more preferably for 60 minutes or more. The immersion of the silicon-containing polymer in the hydrocarbon solvent is preferably performed with stirring or shaking.

  Hereinafter, the second step will be described. In the following description, the compound (I), the hydrolyzate of the compound (I), and the hydrolysis condensate of the compound (I) may be collectively referred to as the compound (I) component. The hydrolyzate of compound (I) includes a product obtained by partially hydrolyzing compound (I) and a product obtained by completely hydrolyzing compound (I). The hydrolyzed condensate of compound (I) includes those obtained by partially hydrolyzing and condensing compound (I) and those obtained by completely hydrolyzing and condensing compound (I).

  Hydrolysis and hydrolysis condensation of compound (I) may occur with some functional groups or with all functional groups. The hydrolyzate and hydrolysis condensate of compound (I) can be prepared by a known method, for example, a method used in a sol-gel method. An example of a method for producing the hydrolyzate and hydrolyzed condensate of compound (I) will be described below.

  First, a reaction solution containing an organic solvent, water, compound (I), and, if necessary, a catalyst is prepared. The reaction solution can be prepared, for example, by dissolving compound (I) in an organic solvent and then adding water and a catalyst. In the prepared reaction solution, the compound (I) undergoes hydrolytic condensation to obtain a solution composed of the component (I) and a solvent (hereinafter sometimes referred to as “solution (Sa)”). The degree of condensation of the hydrolyzed condensate of compound (I) can be controlled by the amount of organic solvent and water used, the temperature of the reaction solution, and the like.

  The organic solvent is not particularly limited as long as it is a solvent in which compound (I) is dissolved. For example, alcohols such as methanol, ethanol, isopropanol, and normal propanol are preferably used. When a compound containing a metal atom (M) to which an alkoxy group is bonded is used as the compound (I), the compound (I) is contained. Alcohol having the same molecular structure (alkoxy component) as the alkoxy group is more preferably used. For example, methanol is preferred for tetramethoxysilane and ethanol is preferred for tetraethoxysilane. The amount of the organic solvent used is not particularly limited, but the concentration of compound (I) in the reaction solution is preferably in the range of 1 to 90% by weight, more preferably 10 to 80% by weight, More preferably, it is in the range of 60% by weight.

  The preferred amount of water used for the hydrolysis of compound (I) varies depending on the type of compound (I) and the desired hydrolysis condensate, but usually the alkoxy group or halogen of compound (I) used. The amount is preferably in the range of 0.05 to 10 mol, more preferably in the range of 0.1 to 4 mol, and more preferably in the range of 0.2 to More preferably, it is in the range of 3 moles. When the amount of water used is in this range, the resulting composite is excellent in mechanical properties such as bending strength and compressive strength. In addition, when adding a component containing water, for example, when adding hydrochloric acid as a catalyst as described later, the amount of water added may be determined in consideration of the amount of water introduced by the component. preferable.

As the catalyst used for the hydrolysis of compound (I), an acid catalyst or a basic catalyst can be used, but an acid catalyst is preferred. As the acid catalyst, a known acid catalyst can be used. For example, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, and maleic acid can be used. . Among these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid, and butyric acid are preferable. The preferred amount of the catalyst used varies depending on the type of catalyst used and the like, but is usually preferably in the range of 1 × 10 ⁻⁵ to 10 moles, more preferably relative to 1 mole of the metal atom of the compound (I) used. The range is 1 × 10 ^{−4 to} 5 mol, and more preferably 5 × 10 ⁻⁴ to 1 mol. When the amount of the catalyst used is within this range, a composite having excellent mechanical properties such as bending strength and compressive strength can be obtained.

  Although there is no limitation in particular in the temperature of the reaction solution at the time of producing a hydrolysis condensation reaction, it is the range of 2-100 degreeC normally, Preferably it is the range of 4-60 degreeC, More preferably, it is the range of 6-50 degreeC It is. The reaction time varies depending on the reaction conditions such as the amount and type of the catalyst, but is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, more preferably 0.1. It is in the range of ~ 6 hours. The atmosphere of the reaction system is not particularly limited, and an atmosphere such as an air atmosphere, a carbon dioxide atmosphere, a nitrogen stream, or an argon atmosphere can be employed.

  In the second step, a mixture containing the compound (I) component, the silicon-containing polymer, and the solvent (hereinafter sometimes referred to as the mixture (S)) is prepared. The method for preparing the mixture (S) is not particularly limited, and for example, the mixture (S) can be prepared by adding a silicon-containing polymer to the solution (Sa). The silicon-containing polymer may be added as it is, or may be added in the form of a solution in which it is dissolved (hereinafter sometimes referred to as “solution (Sb)”). The method for mixing the solution (Sa) and the solution (Sb) is not particularly limited. However, in order to obtain a uniform mixture, it is preferable to mix and stir them. When producing the mixture (S) by this method, the solvent contained in the mixture (S) is an organic solvent contained in the solution (Sa), a solvent in the solution (Sb), or a mixed solvent of both.

  The solvent of the solution (Sb) is not particularly limited as long as it is a solvent in which the silicon-containing polymer is dissolved. For example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and propylene glycol; methyl cellosolve, ethyl cellosolve, n-butyl cellosolve, etc. Glycerol; glycerin; acetonitrile; dimethylformamide; dimethyl sulfoxide; sulfolane and the like can be used alone or in combination. Among these, alcohols such as methanol and ethanol are preferable. Although there is no limitation in particular in the usage-amount of a solvent, it is preferable that it is the quantity from which the density | concentration of a silicon-containing polymer will be 1-50 weight% (more preferably 5-30 weight%, for example 5-20 weight%).

  In the second step of the present invention, compound (I) that has not undergone hydrolysis or hydrolysis condensation can be used as the component (I). Even when such a compound (I) is used, the method for preparing the mixture (S) is not particularly limited. For example, a silicon-containing polymer and water and optionally a catalyst are added to a solution in which the compound (I) is dissolved. Can be prepared. The silicon-containing polymer may be added as it is, or may be added in the form of a solution (solution (Sb)) as described above. There is no particular limitation on the method of mixing the solution in which the compound (I) is dissolved, the solution (Sb), water, and optionally the catalyst to be added, but in order to obtain a uniform mixture, these are mixed and stirred. Is preferred. When preparing the mixture (S) by this method, the solvent contained in the mixture (S) is an organic solvent contained in the solution in which the compound (I) is dissolved, a solvent of the solution (Sb), or a mixed solvent of both. . As the organic solvent used in the solution in which the compound (I) is dissolved, the organic solvent used in the solution (Sa) can be used. Further, the preferred amount of water used varies depending on the type of compound (I), etc., but is usually 1 mol of the alkoxy group or halogen atom of compound (I) used (the total when both are present). On the other hand, the range is preferably 0.05 to 10 mol, more preferably 0.1 to 4 mol, and still more preferably 0.2 to 3 mol. When the amount of water used is in this range, the resulting composite is excellent in mechanical properties such as bending strength and compressive strength.

Moreover, as a catalyst which can be added by the case, the catalyst quoted in one example of the manufacturing method of the hydrolyzate or hydrolysis-condensation product of compound (I) as mentioned above can be used. The preferred amount of the catalyst used varies depending on the type of catalyst used and the like, but is usually preferably in the range of 1 × 10 ⁻⁵ to 10 moles, more preferably relative to 1 mole of the metal atom of the compound (I) used. The range is 1 × 10 ^{−4 to} 5 mol, and more preferably 5 × 10 ⁻⁴ to 1 mol. When the amount of the catalyst used is within this range, a composite having excellent mechanical properties such as bending strength and compressive strength can be obtained.

  Especially in the concentration of solids contained in the mixture (S) obtained in the second step of the present invention (the total concentration of the compound (I) component, the silicon-containing polymer, and other components that can be added in the following cases) Although there is no limitation, Preferably it is the range of 1-50 weight%, More preferably, it is the range of 2-30 weight% (for example, the range of 3-15 weight%). By setting the solid content concentration contained in the mixture within this range, a composite having better mechanical properties such as bending strength and compressive strength can be obtained.

  The solid content concentration of the mixture (S) can be controlled at any stage of preparing the mixture (S). For example, the solid content concentration of the solution (Sa) and / or the solution (Sb) may be adjusted in advance so that the solid content concentration of the mixture (S) falls within a preferable range. Moreover, you may adjust solid content concentration of a mixture (S) by adding a solvent after mixing a solution (Sa) and a solution (Sb).

  Further, the ratio of the compound (I) component to the solid content contained in the mixture (S) is not particularly limited, but the weight ratio of the metal atom (M) in the compound (I) component to the weight of the silicon-containing polymer is The range is preferably from 0.01 to 1.1, more preferably from 0.02 to 0.7, and even more preferably from 0.05 to 0.5.

  The mixture (S) may contain other components in addition to the compound (I) component and the silicon-containing polymer. Specifically, the above-described substances may be included as other substances that the complex of the present invention may include.

  After obtaining the mixture (S) in the second step, the complex can be obtained by removing the solvent from the mixture (S). The method for removing the solvent is not limited. For example, the mixture (S) may be poured into a molding die and dried, or may be dried after coating the mixture (S) on a substrate. . By pouring the mixture (S) into a molding die and drying it, lumps having various shapes are obtained. Moreover, a thin film is obtained by coating and drying a mixture (S).

  Drying conditions vary depending on the state of the molded or coated mixture (S). Usually, drying temperature becomes like this. Preferably it is the range of 10-180 degreeC, More preferably, it is the range of 20-160 degreeC (for example, the range of 20-140 degreeC). As the molded product becomes thicker, it is preferable to dry at a lower temperature. The drying temperature in the case of producing a thick molded product by pouring the mixture (S) into a mold is preferably in the range of 10 to 80 ° C, more preferably in the range of 20 to 60 ° C. During drying, it is preferable to control the volatilization rate of the solvent during drying, if necessary. The volatilization rate can be controlled, for example, by adjusting the sealing degree of the dry atmosphere.

  The material of the mold into which the mixture (S) is poured is not particularly limited as long as it functions as a mold, and various plastics such as polymethacrylate, polyacrylate, and polystyrene, metal, glass, gypsum, and the like can be applied. Various shapes of lumps can be obtained by changing the shape of the mold to be molded. For example, lumps of shapes such as prisms, cylinders, sheets, and tubes can be obtained. In the composite of the present invention, a lump of at least 0.4 cm square or more can be obtained. Moreover, when forming into a film on a base material, there is no limitation in particular in the material of a base material, For example, resin, such as a polyethylene terephthalate, metal, glass, a sintered compact, etc. are applicable.

  In the production method of the present invention, in the mixture (S), hydrolysis condensation of the compound (I) component and condensation reaction of the compound (I) component and the silicon-containing polymer (for example, hydrolysis condensation reaction) proceed. In particular, the condensation reaction proceeds in the step of removing the solvent from the mixture (S). By this condensation reaction, a composite having particularly excellent mechanical properties can be obtained.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the Shin-Etsu Chemical Co., Ltd. thing was used for the silane compound used in the following Examples. Measurements in the following examples were carried out by the following methods.

(1) Measurement of number average molecular weight and weight average molecular weight A silicon-containing polymer was dissolved in dimethylformamide so as to have a concentration of 0.5% by weight, and used as a sample for GPC (Gel Permeation Chromatography) measurement. The measurement of GPC was performed using GPC-150C manufactured by WATERS. As the column, KD-806 and 802.5 (Shodex) were used. Dimethylformamide was used as the eluent, and the eluent was allowed to flow at a flow rate of 1.0 mL / min. The column oven was set to 40 ° C. A calibration curve for determining the molecular weight was prepared using a polyethylene oxide / polyethylene glycol standard (manufactured standard sample). That is, polyethylene oxide and polyethylene glycol having a known molecular weight were dissolved in dimethylformamide so that the concentration was 0.5% by weight, GPC measurement was performed, and a calibration curve showing the relationship between elution time and molecular weight was created. . The number average molecular weight and weight average molecular weight of the silicon-containing polymer were determined from the GPC elution curve (elution time-elution amount) of the silicon-containing polymer and the calibration curve. Further, the molecular weight distribution, that is, the value of “weight average molecular weight / number average molecular weight” was calculated.

(2) Measurement of flexural strength of composites A prism having a size of approximately 4 mm (vertical) x 4 mm (horizontal) x 20 mm (height) made of the composites of Examples and Comparative Examples was produced, and Shimadzu Corporation The three-point bending strength was measured using a manufactured autograph. The measurement was performed by setting the distance between fulcrums to 8 mm and applying a static load at a crosshead speed of 1 mm / min. The bending strength was calculated from the resistance value against the static load when the fracture or crack occurred and the cross-sectional area of the prism used, and the average value of the six specimens was taken as the bending strength value. The cross-sectional area of the prism was determined by measuring the vertical and horizontal dimensions of the prism with calipers.

(3) Measurement of solid-state NMR The complex of the Example and the comparative example was crushed, and a solid-state NMR spectrum of silicon was obtained by CP-MAS method using JNM-DX270 manufactured by JEOL. By observing the absorption spectrum of silicon contained in the polymer in the range of −150 to 30 ppm, at least a part of the structural unit (A) constituting the silicon-containing polymer is condensed and / or hydrolyzed. It was confirmed.

<Example 1>
A silicon-containing polymer was prepared by the following method. First, 2000 mmol of trimethoxyvinylsilane (monomer (A)) and 2000 mmol of vinylpyrrolidone (monomer (B)) were dissolved in 56 ml of toluene, and a reflux tube was attached under a nitrogen atmosphere. Added to the flask. The mixture of monomer (A) and monomer (B) was bubbled with nitrogen gas. This bubbling was continued until the polymerization reaction was stopped. 30 minutes after the start of bubbling, the flask was immersed in an oil bath adjusted to 70 ° C., and 40 mmol of azobisisobutyronitrile (polymerization initiator) was immediately added to the mixture to initiate polymerization. did. Five minutes after immersing the flask in an oil bath, the temperature of the mixture reached 70 ° C. Six hours after adding the polymerization initiator, the polymerization reaction was continued while stirring the mixture and in an oil bath. Thereafter, the flask was taken out from the oil bath, and the temperature in the flask was lowered to room temperature. It was confirmed by gas chromatography that neither the monomer (A) nor the monomer (B) remained in the reaction product in the flask. A part of the obtained polymer was dissolved in dimethylformamide, and the molecular weight was measured by GPC. As a result, the obtained polymer had a number average molecular weight (Mn) of 11,000, a weight average molecular weight (Mw) of 15,200, and a molecular weight distribution of 1.4.

A part of the obtained polymer was dissolved in deuterated chloroform containing tetramethylsilane as an internal standard, and the structure was analyzed by ¹ H-NMR. As a result, a peak corresponding to the methine proton bonded to the silicon atom was confirmed at 0.7 ppm, a peak corresponding to the methylene proton in the main chain was observed at 1.2 ppm, and a peak corresponding to the methine proton bonded to nitrogen was observed. It was observed at 3.9 ppm, methyl protons encapsulated in the heterocyclic ring were observed at 2.1 ppm, 2.4 ppm, 3.3 ppm, and methyl protons in the methoxysilyl group were observed at 3.5 ppm. From the integrated value of each peak, the molar ratio between the structural unit (A) derived from the monomer (A) and the structural unit (B) derived from the monomer (B), [structural unit (A) / structure The unit (B)] value was calculated to be approximately 5/5.

  The silicon-containing polymer thus obtained was dissolved in ethanol to obtain a solution (Sb1) having a solid content concentration of 10% by weight.

  On the other hand, 100 parts by weight of tetraethoxysilane was dissolved in 100 parts by weight of ethanol, 17 parts by weight of water and 1.2 parts by weight of 12N hydrochloric acid were added, and stirred at room temperature for 30 minutes to obtain a solution (Sa1). Immediately after the solution (Sa1) was obtained, 540 parts by weight of the solution (Sb1) was added while stirring the solution (Sa1), and then stirred at room temperature for 30 minutes to obtain a mixture (S1).

  Next, the mixture (S1) was cast into a polystyrene mold having a size of 10 mm × 10 mm × 45 mm, and then the mold was sealed with a polyethylene film. This mold was placed in an atmosphere having a temperature of 60 ° C. and a humidity of 2%, and the volatilization rate of the solvent was controlled. After 72 hours, the mixture (S1) gelled. The mold was placed under the above atmosphere until the weight change of the gel gradually decreased and reached a substantially constant value. Thereafter, the mold sealed with the polyethylene film was left as it was in a hot air dryer at 60 ° C. for 2 weeks. Thereafter, the molded composite was taken out of the mold and placed in a hot air dryer at 150 ° C. for 12 hours to obtain a transparent mass (size 4 mm × 4 mm × 25 mm) made of the composite.

  The three-point bending strength of the lump was 200 MPa, and very good results were obtained. Further, as a result of measuring solid NMR of the mass, it was confirmed that the reactant of the structural unit (A) constituting the silicon-containing polymer was condensed and / or hydrolyzed.

<Example 2>
870 mmol of trimethoxyvinylsilane (monomer (A)), 1000 mmol of vinylpyrrolidone (monomer (B)) and 130 mmol of diethoxydivinylsilane (monomer (C)) Under an atmosphere, it was added to a flask equipped with a reflux tube. The mixture of monomer (A), monomer (B) and monomer (C) was bubbled with nitrogen gas. This bubbling was continued until the polymerization reaction was stopped. 30 minutes after the start of bubbling, the flask was immersed in an oil bath adjusted to 100 ° C., and 100 mmol of dicumyl peroxide (polymerization initiator) was immediately added to the mixture to initiate polymerization. Five minutes after immersing the flask in the oil bath, the temperature of the mixture reached 100 ° C. The polymerization reaction was continued in the oil bath while stirring the mixture for 1 hour after the addition of the polymerization initiator. Thereafter, the flask was taken out from the oil bath, and the temperature in the flask was lowered to room temperature. The reaction product in the flask was analyzed by gas chromatography, and it was confirmed that the monomer (A), monomer (B) and monomer (C) were consumed.

  Next, the entire amount of the obtained polymer was put into 1000 ml of n-hexane and stirred for 60 minutes. After 60 minutes, the polymer that did not dissolve in n-hexane was collected by filtration. The recovered polymer was dried at room temperature under reduced pressure. The weight of the recovered polymer after drying was 15% of the total weight of the monomer (A), the monomer (B) and the monomer (C). A part of the polymer thus obtained was dissolved in dimethylformamide, and the molecular weight was measured by GPC. As a result, the obtained polymer had a number average molecular weight (Mn) of 20,000, a weight average molecular weight (Mw) of 38,000, and a molecular weight distribution of 1.9. The silicon-containing polymer thus obtained was dissolved in ethanol to obtain a solution (Sb2) having a solid content concentration of 10% by weight.

  A mixture (S2) was prepared in the same manner as in Example 1 except that 540 parts by weight of the solution (Sb2) was used instead of 540 parts by weight of the solution (Sb1). Next, the mixture (S2) was cast into a polystyrene mold having a size of 10 mm × 10 mm × 45 mm, and then the mold was sealed with a polyethylene film. This mold was placed in an atmosphere having a temperature of 60 ° C. and a humidity of 2%, and the volatilization rate of the solvent was controlled. After 48 hours, the mixture (S2) gelled. The mold was placed under the above atmosphere until the weight change of the gel gradually decreased and reached a substantially constant value. Thereafter, the mold sealed with a polyethylene film was left as it was in a hot air dryer at 60 ° C. for 3 weeks. Thereafter, the molded composite was taken out from the mold and placed in a hot air dryer at 150 ° C. for 12 hours to obtain a transparent mass (size 4.5 mm × 4.5 mm × 30 mm) made of the composite.

  The three-point bending strength of the lump was 150 MPa, and good results were obtained. Further, as a result of measuring solid NMR of the mass, it was confirmed that the reactant of the structural unit (A) constituting the silicon-containing polymer was condensed and / or hydrolyzed.

<Example 3>
First, 1200 mmol of trimethoxyvinylsilane (monomer (A)) and 800 mmol of vinylpyrrolidone (monomer (B)) were dissolved in 56 ml of toluene, and a reflux tube was attached under a nitrogen atmosphere. Added to the flask. The mixture of monomer (A) and monomer (B) was bubbled with nitrogen gas. This bubbling was continued until the polymerization reaction was stopped. 30 minutes after starting bubbling, immerse the flask in an oil bath adjusted to 70 ° C., and immediately add 40 mmol of azobisisobutyronitrile (polymerization initiator) to the mixture to initiate polymerization. did. Five minutes after immersing the flask in an oil bath, the temperature of the mixture reached 70 ° C. Six hours after adding the polymerization initiator, the polymerization reaction was continued while stirring the mixture and in an oil bath. Thereafter, the flask was taken out from the oil bath, and the temperature in the flask was lowered to room temperature. It was confirmed by gas chromatography that neither the monomer (A) nor the monomer (B) remained in the reaction product in the flask. A part of the obtained polymer was dissolved in dimethylformamide, and the molecular weight was measured by GPC. As a result, the polymer obtained had a number average molecular weight (Mn) of 2100, a weight average molecular weight (Mw) of 3300, and a molecular weight distribution of 1.6.

  The silicon-containing polymer thus obtained was dissolved in ethanol to obtain a solution (Sb3) having a solid content concentration of 10% by weight.

  A mixture (S3) was prepared in the same manner as in Example 1 except that 821 parts by weight of the solution (Sb3) was used instead of 540 parts by weight of the solution (Sb1). Next, the mixture (S3) was cast into a polystyrene mold having a size of 10 mm × 10 mm × 45 mm, and then the mold was sealed with a polyethylene film. This mold was placed in an atmosphere having a temperature of 60 ° C. and a humidity of 2%, and the volatilization rate of the solvent was controlled. After 96 hours, the mixture (S3) gelled. The mold was placed under the above atmosphere until the weight change of the gel gradually decreased and reached a substantially constant value. Thereafter, the mold sealed with a polyethylene film was left as it was in a hot air dryer at 60 ° C. for 3 weeks. Thereafter, the molded composite was taken out from the mold and placed in a hot air dryer at 150 ° C. for 12 hours to obtain a transparent mass (size 4 mm × 4 mm × 20 mm) made of the composite.

  The three-point bending strength of the lump was 80 MPa, and good results were obtained. Further, as a result of measuring solid NMR of the mass, it was confirmed that the reactant of the structural unit (A) constituting the silicon-containing polymer was condensed and / or hydrolyzed.

<Example 4>
700 mmol of trimethoxyvinylsilane (monomer (A)), 1000 mmol of vinylpyrrolidone (monomer (B)), and 300 mmol of diethoxydivinylsilane (monomer (C)) Under an atmosphere, it was added to a flask equipped with a reflux tube. The mixture of monomer (A), monomer (B) and monomer (C) was bubbled with nitrogen gas. This bubbling was continued until the polymerization reaction was stopped. 30 minutes after the start of bubbling, the flask was immersed in an oil bath adjusted to 100 ° C., and 100 mmol of dicumyl peroxide (polymerization initiator) was immediately added to the mixture to initiate polymerization. Five minutes after immersing the flask in the oil bath, the temperature of the mixture reached 100 ° C. The polymerization reaction was continued in the oil bath while stirring the mixture for 0.5 hour after the addition of the polymerization initiator. Thereafter, the flask was taken out from the oil bath, and the temperature in the flask was lowered to room temperature. The reaction product in the flask was analyzed by gas chromatography, and it was confirmed that the monomer (A), monomer (B) and monomer (C) were consumed.

  Next, the entire amount of the obtained polymer was put into 1000 ml of n-hexane and stirred for 60 minutes. After 60 minutes, the polymer that did not dissolve in n-hexane was collected by filtration. The recovered polymer was dried at room temperature under reduced pressure. The weight of the recovered polymer after drying was 15% of the total weight of the monomer (A), the monomer (B) and the monomer (C). A part of the polymer thus obtained was dissolved in dimethylformamide, and the molecular weight was measured by GPC. As a result, the obtained polymer had a number average molecular weight (Mn) of 19,000, a weight average molecular weight (Mw) of 45,000, and a molecular weight distribution of 2.4. The silicon-containing polymer thus obtained was dissolved in ethanol to obtain a solution (Sb4) having a solid content concentration of 10% by weight.

  A mixture (S4) was prepared in the same manner as in Example 1 except that 540 parts by weight of the solution (Sb4) was used instead of 540 parts by weight of the solution (Sb1). Next, the mixture (S4) was cast into a polystyrene mold having a size of 10 mm × 10 mm × 45 mm, and then the mold was sealed with a polyethylene film. This mold was placed in an atmosphere having a temperature of 60 ° C. and a humidity of 2%, and the volatilization rate of the solvent was controlled. After 48 hours, the mixture (S4) gelled. The mold was placed under the above atmosphere until the weight change of the gel gradually decreased and reached a substantially constant value. Thereafter, the mold sealed with a polyethylene film was left as it was in a hot air dryer at 60 ° C. for 3 weeks. Thereafter, the molded composite was taken out from the mold and placed in a hot air dryer at 150 ° C. for 12 hours to obtain a transparent mass (size 4.5 mm × 4.5 mm × 30 mm) made of the composite.

  The three-point bending strength of the lump was 100 MPa, and good results were obtained. Moreover, as a result of measuring solid NMR of the mass, it was confirmed that the reactant of the structural unit (A) constituting the silicon-containing polymer was condensed and / or hydrolyzed.

<Comparative Example 1>
2000 mmol of trimethoxyvinylsilane (monomer (A)) was added to a flask equipped with a reflux tube under a nitrogen atmosphere. The monomer (A) was bubbled with nitrogen gas. This bubbling was continued until the polymerization reaction was stopped. 30 minutes after the start of bubbling, the flask was immersed in an oil bath adjusted to 130 ° C., and 100 mmol of dicumyl peroxide (polymerization initiator) was immediately added to initiate polymerization. Five minutes after immersing the flask in the oil bath, the temperature of the mixture reached 130 ° C. The polymerization reaction was continued in the oil bath while stirring the mixture for 5 hours after the addition of the polymerization initiator. Thereafter, the flask was taken out from the oil bath, and the temperature in the flask was lowered to room temperature. It was confirmed by gas chromatography that no monomer (A) remained in the reaction product in the flask. A part of the polymer thus obtained was dissolved in tetrahydrofuran, and the molecular weight was measured by GPC. As a result, the obtained polymer had a number average molecular weight (Mn) of 3200, a weight average molecular weight (Mw) of 6100, and a molecular weight distribution of 1.9. The silicon-containing polymer thus obtained was dissolved in ethanol to obtain a solution (SbC1) having a solid content concentration of 10% by weight.

  A mixture (SC1) was prepared in the same manner as in Example 1 except that 540 parts by weight of the solution (SbC1) was used instead of 540 parts by weight of the solution (Sb1). Next, the mixture (SC1) was cast into a polystyrene mold having a size of 10 mm × 10 mm × 45 mm, and then the mold was sealed with a polyethylene film. This mold was placed in an atmosphere having a temperature of 60 ° C. and a humidity of 2%, and the volatilization rate of the solvent was controlled. The mixture (SC1) gelled after 72 hours. The mold was placed under the above atmosphere until the weight change of the gel gradually decreased and reached a substantially constant value. Thereafter, the mold sealed with a polyethylene film was left as it was in a hot air dryer at 60 ° C. for 3 weeks. Thereafter, the molded composite was taken out from the mold and placed in a hot air dryer at 150 ° C. for 12 hours to obtain a transparent mass (size 4 mm × 4 mm × 20 mm) made of the composite.

  The three-point bending strength of the lump was 43 MPa, which was lower than that of the example. Moreover, as a result of measuring solid NMR of the mass, it was confirmed that the reactant of the structural unit (A) constituting the silicon-containing polymer was condensed and / or hydrolyzed.

  The composite and the lump of the present invention can be applied to various fields, and can be used as materials for molding materials, insulator materials, coating films, and various compositions, for example. Specifically, it can be used as materials for dental, optical, electrical / electronic parts, paints, inks, adhesives, adhesives, compatibilizers, sealing materials, and the like.

Claims (16)

A composite comprising a hydrolysis condensate of compound (I) and a silicon-containing polymer,
The compound (I) is at least one compound containing a metal atom (M) to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded,
The silicon-containing polymer includes a structural unit (A) derived from the monomer (A) and a structural unit (B) derived from the monomer (B), and the monomer (A) is: And the monomer (B) is at least one selected from the group consisting of a vinyl compound having a nitrogen-containing heterocyclic ring and a carboxylic acid vinyl ester compound. Complex that is a kind of compound.

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one atomic group selected from R ² , R ³ and R ⁴ ( G) is a halogen atom, an alkoxy group or a hydroxyl group. ] A composite comprising a metal oxide containing a metal atom (M) and a silicon-containing polymer,
The silicon-containing polymer includes a structural unit (A) derived from the monomer (A) and a structural unit (B) derived from the monomer (B), and the monomer (A) is: The monomer (B) is at least one selected from the group consisting of a vinyl compound having a nitrogen-containing heterocyclic ring and a carboxylic acid vinyl ester compound. Complex that is a kind of compound.

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one atomic group selected from R ² , R ³ and R ⁴ ( G) is a halogen atom, an alkoxy group or a hydroxyl group. ] The silicon-containing polymer further comprises a structural unit (C) derived from the monomer (C),
The complex according to claim 1 or 2, wherein the monomer (C) is at least one compound containing two or more carbon-carbon double bonds. The complex according to claim 3, wherein the monomer (C) is at least one compound represented by the following formula (2).

[Wherein, R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a group represented by (CR ⁹ ═CH ₂ ) (where R ⁹ is a hydrogen atom or an alkyl group). One selected atomic group. ]   The number of moles of the structural unit (A) / number of moles of the structural unit (C) in the silicon-containing polymer is in the range of 70/30 to 99.5 / 0.5. The complex described.   The complex according to any one of claims 1 to 5, wherein the monomer (B) is at least one compound selected from vinylpyrrolidone and vinylimidazole.   The silyl group having the atomic group (G) is condensed and / or hydrolyzed and condensed in at least a part of the plurality of structural units (A) contained in the silicon-containing polymer. The composite according to claim 1.   The composite according to any one of claims 1 to 7, wherein the silicon-containing polymer has a number average molecular weight (Mn) of 10,000 or more.   The composite according to claim 1 or 2, wherein [number of moles of the structural unit (A) / number of moles of the structural unit (B)] in the silicon-containing polymer is in the range of 60/40 to 5/95. . A first step of polymerizing a plurality of types of monomers including the monomer (A) and the monomer (B) to obtain a silicon-containing polymer;
First, a mixture comprising at least one selected from the group consisting of compound (I), a hydrolyzate of compound (I) and a hydrolysis condensate of compound (I), the silicon-containing polymer, and a solvent is prepared. A method for producing a composite comprising two steps,
The monomer (A) is at least one compound represented by the following formula (1):
The monomer (B) is at least one compound selected from the group consisting of a vinyl compound having a nitrogen-containing heterocycle and a carboxylic acid vinyl ester compound.
The method for producing a complex, wherein the compound (I) is at least one compound containing a metal atom (M) to which at least one atomic group selected from a halogen atom and an alkoxy group is bonded.

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one atomic group selected from R ² , R ³ and R ⁴ ( G) is a halogen atom, an alkoxy group or a hydroxyl group. ] The first step is a step of obtaining a silicon-containing polymer by polymerizing a plurality of types of monomers including the monomer (A), the monomer (B), and the monomer (C). Yes,
The production method according to claim 10, wherein the monomer (C) is at least one compound containing two or more carbon-carbon double bonds. The production method according to claim 11, wherein the monomer (C) is at least one compound represented by the following formula (2).

[Wherein, R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a group represented by (CR ⁹ ═CH ₂ ) (where R ⁹ is a hydrogen atom or an alkyl group). One selected atomic group. ]   The number average molecular weight of the said silicon containing polymer is 10,000 or more, The manufacturing method of any one of Claims 10-12. The polymerization in the first step is performed at a temperature of 80 ° C. or higher in the presence of a polymerization initiator,
The production method according to claim 11 or 12, wherein an activation energy of decomposition of the polymerization initiator is 126 kJ / mol or more.   The composite_body | complex obtained by the manufacturing method of any one of Claims 10-14.   The lump which consists of a composite_body | complex of any one of Claims 1-9 and Claim 15.