JP2006233095A - Layered crystal compound containing fluoropolymer and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a layered crystal compound which is excellent in dispersibility into a resin and can elevate effectively the physical properties of a resin composition; a manufacturing method thereof; and a resin composition and a molded body containing a homogeneously dispersed layered crystal compound and having good physical properties. <P>SOLUTION: The layered crystal compound is formed by treating a layered inorganic compound with a fluorine-containing polymer of the formula (I): Rf<SP>1</SP>-(CH<SB>2</SB>CR<SP>3</SP>Z<SP>1</SP>)<SB>m</SB>-(CH<SB>2</SB>CR<SP>4</SP>Z<SP>2</SP>)<SB>n</SB>-Rf<SP>2</SP>(wherein, Rf<SP>1</SP>and Rf<SP>2</SP>are each a polyfluoroalkyl or polyfluorooxalkyl group containg ≥3 carbons; R<SP>3</SP>and R<SP>4</SP>are each H, methyl or the like; Z<SP>1</SP>is a univalent organic group or the like; Z<SP>2</SP>is -CONR<SP>5</SP>R<SP>6</SP>, and R<SP>5</SP>and R<SP>6</SP>are each an alkyl group or the like, or R<SP>5</SP>and R<SP>6</SP>bond together to form a 2-8C divalent alkylene group or ether group or form a ring together with an adjacent nitrogen atom; and m/n is 0/100-99/1). The resin composition and the molded body each containing the above compound are disclosed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a layered crystal compound obtained by treating a layered inorganic compound with a fluoropolymer, a method for producing the layered crystal compound, a resin composition comprising the layered crystal compound and a resin, and molding the resin composition. It relates to a molded article.

  In resin materials, for the purpose of improving physical properties such as dimensional stability, it is known to add a layered inorganic compound such as saponite or montmorillonite as a filler to a resin to form a resin composition (Patent Document 2). When a layered inorganic compound is used as a filler, since the layered inorganic compound is highly polar, it is subjected to an organic treatment using a guest molecule such as an organic compound, and the layered crystal compound having a low polarity and high dispersibility in a resin (hereinafter referred to as this compound) Generally, a compound subjected to such treatment is sometimes referred to simply as a “layered crystal compound”) and then added to the resin (Patent Document 1).

  However, since organic compounds used for organic treatment are generally low-molecular compounds, resin compositions using layered crystal compounds that have undergone organic treatment have improved physical properties due to the addition of fillers and physical properties due to the inclusion of low-molecular compounds. The reduction effect may be offset and physical properties may not be improved. For example, in general, when a layered inorganic compound is added to a resin composition, the linear expansion coefficient decreases and the dimensional stability increases according to the amount added, but when a layered crystal compound subjected to organic treatment is added, it is attributed to guest molecules. However, plasticity will increase. As a result, even if the addition amount of the layered crystal compound is increased, the decrease in the linear expansion coefficient reaches its peak, and the linear expansion coefficient cannot be effectively reduced.

JP-A-8-333114 JP-A-9-1224836

Accordingly, an object of the present invention is to provide a layered crystal compound that is excellent in dispersibility in a resin and can effectively improve the physical properties of a resin composition, and a method for producing the same.
Another object of the present invention is to provide a resin composition and a molded article containing a layered crystal compound dispersed uniformly and having good physical properties.

  As a result of intensive investigations to achieve the above object, the present inventors have achieved high dispersibility in resins and excellent physical properties by using a specific fluoropolymer as an organic treatment agent for a layered inorganic compound. The inventors have found that a layered crystal compound having an effect can be obtained, and have completed the present invention.

Thus, according to the present invention,
(1) A layered crystal compound obtained by treating a layered inorganic compound with a fluoropolymer represented by the following general formula (I):
_{^{Rf 1 - (CH 2 CR 3}} Z 1) m - (CH 2 CR 4 Z 2) n -Rf 2 ··· (I)
(In general formula (I), Rf ¹ and Rf ² are each independently a polyfluoroalkyl group having 3 or more carbon atoms or a polyfluorooxaalkyl group having 3 or more carbon atoms. R ³ and R ⁴ are hydrogen atoms or Z ¹ is independently a hydrogen atom, a monovalent organic group or a halogen atom, Z ² is —CONR ⁵ R ⁶ , wherein R ⁵ and R ⁶ are each independently a hydrogen atom , An alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a sulfonic acid-containing alkyl group having 1 to 18 carbon atoms, or — [C (R ¹⁵ ) ₂ ] _q COR ¹⁶ (R ¹⁵ is independently Or a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹⁶ is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and q is an integer of 1 to 5). there, or R ⁵ and R ⁶ forming To a .m / n = 0 / 100~99 / 1 is a group constituting a ring with the adjacent nitrogen atom to form a divalent alkylene group or an ether group having 2 to 8 carbon atoms).;
(2) Z ¹ in the general formula (I) is —Si (R ⁷ ) ₃ , —OCOR ⁸ , —COOR ⁹ , —CON (R ¹⁰ ) R ¹¹ —N ⁺ (R ¹² ) ₃ X ⁻ , or —COOR _{^{11 -N + (R 12) 3}} X - in which (R ⁷ are each independently an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms .R ⁸ and R ⁹ are a hydrogen atom, a carbon An alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a sulfonic acid-containing alkyl group having 1 to 18 carbon atoms, — (CH ₂ ) ₃ —Si (R ¹³ ) ₃ or — (C (R ¹⁴ ₂ ) _p COR ¹³ (R ¹³ each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ¹⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) in and, p is an integer of 1 to 5.), R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms R ¹¹ is an alkylene group having 1 to 4 carbon atoms .R ¹² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms .X is a halogen atom.) (1) lamellar crystalline compound according ;
(3) a step of dispersing a layered inorganic compound in water or an organic solvent to prepare a dispersion; and a step of adding and stirring the fluoropolymer represented by the general formula (I) in the dispersion (1) The method for producing a layered crystal compound according to (1),
(4) A step of dispersing a layered inorganic compound in water or an organic solvent to prepare a dispersion; and a step of performing a reaction to produce the fluoropolymer represented by the general formula (I) in the dispersion A process for producing a layered crystal compound according to (1), which comprises:
(5) A resin composition comprising the layered crystal compound of (1) and a resin; and (6) Molded articles formed by molding the resin composition of (5).

Since the layered crystal compound of the present invention is obtained by treating the layered inorganic compound with the specific fluoropolymer, it has excellent dispersibility when mixed with a resin to form a resin composition, and has a linear expansion. The effect of improving physical properties such as reduction of the coefficient can be sufficiently exhibited.
According to the method for producing a layered crystal compound of the present invention, the layered crystal compound can be easily produced.
Since the resin composition and the molded product of the present invention contain the layered crystal compound of the present invention, the resin composition and the molded product contain a uniformly dispersed layered crystal compound and have good physical properties such as a low linear expansion coefficient.

  The layered crystal compound of the present invention is obtained by treating a layered inorganic compound with a specific fluoropolymer.

  The fluorine-containing polymer (hereinafter sometimes referred to as compound 1) has a main chain unit and a specific fluorine-containing group at the end of the molecule, and is represented by the following general formula (I).

(Compound 1)
_{^{Rf 1 - (CH 2 CR 3}} Z 1) m - (CH 2 CR 4 Z 2) n -Rf 2 ··· (I)

In the above general formula (I), the fluorine-containing groups Rf ¹ and Rf ² (hereinafter sometimes collectively referred to as terminal Rf groups) at both ends of the molecule are each independently 3 or more carbon atoms, preferably Is a polyfluoroalkyl group or polyfluorooxaalkyl group having 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms. The polyfluoroalkyl group refers to a substituent in which all or part of the hydrogen atoms bonded to the carbon atoms in the alkyl group having a linear, branched or cyclic skeleton are substituted with fluorine atoms. The polyfluorooxaalkyl group refers to a substituent having at least one etheric oxygen atom between carbon-carbon bonds in the polyfluoroalkyl group. The terminal Rf group may contain a halogen atom other than the fluorine atom. As another halogen atom, a chlorine atom is preferable. A thioetheric sulfur atom may be inserted between the carbon-carbon bonds in the terminal Rf group.

  The number of fluorine atoms in the terminal Rf group is obtained as ((number of fluorine atoms in Rf group) / (number of hydrogen atoms contained in corresponding alkyl group having the same carbon number as Rf group)) × 100 (%). The fluorine substitution rate is preferably 60% or more, and more preferably 80% or more. In particular, a fluorine atom is preferably bonded to the terminal carbon atom of the terminal Rf group, and a perfluoro group, that is, a group having a fluorine substitution rate of 100% is particularly preferable.

As the terminal Rf group, specifically, a group derived from a radical polymerization initiator described later, —CF ₂ CF ₂ CF ₃ , —CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , —CF (CF ₃ ) OCF _{2 CF 2 CF 3, - [} CF (CF 3) OCF 2] xCF 2 CF 3 (X is a positive integer), and the like.

The main chain unit — (CH ₂ CR ³ Z ¹ ) _m — and — (CH ₂ CR ⁴ Z ² ) _n — in Compound 1 can be an ethylenic polymer unit. R ³ and R ⁴ in the main chain unit of Compound 1 are a hydrogen atom or a methyl group.

The side chains Z ¹ in the main chain unit — (CH ₂ CR ³ Z ¹ ) _m — are each independently a hydrogen atom, a monovalent organic group or a halogen atom, and can be appropriately selected depending on desired properties. Examples of preferred Z ¹ include —Si (R ⁷ ) ₃ , —OCOR ⁸ , —COOR ⁹ , —CON (R ¹⁰ ) R ¹¹ —N ⁺ (R ¹² ) ₃ X ⁻ , or —COOR ¹¹ —N ^+. (R ¹² ) ₃ X ^- is mentioned. Here, each R ⁷ is independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. R ⁸ and R ⁹ are each a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a sulfonic acid-containing alkyl group having 1 to 18 carbon atoms, — (CH ₂ ) ₃ —Si (R ¹³ ) ₃ , or — (C (R ¹⁴ ) ₂ ) _p COR ¹³ (R ¹³ is independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ¹⁴ is each Independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p is an integer of 1 to 5). R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹¹ is an alkylene group having 1 to 4 carbon atoms. R ¹² is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X is a halogen atom, preferably Cl, Br or I.

The side chain Z ² in the main chain unit — (CH ₂ CR ⁴ Z ² ) _n — is a group represented by —CONR ⁵ R ⁶ . R ⁵ and R ⁶ in Z ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a sulfonic acid-containing alkyl group having 1 to 18 carbon atoms, or — [C (R ¹⁵ ) ₂ ] _q COR ¹⁶ (R ¹⁵ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁶ is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. And q is an integer of 1 to 5. Alternatively, R ⁵ and R ⁶ may combine to form a divalent alkylene group having 2 to 8 carbon atoms or an ether group, and form a ring with the adjacent nitrogen atom.

Specific examples of the monomer having the group Z ¹ that can give the unit — (CH ₂ CR ³ Z ¹ ) _m — include vinyl acetate, vinyl propionate, (meth) acrylic acid, methyl (meth) acrylate, (meth ) Acrylic acid-tert-butyl, (meth) acrylic acid propyl, (meth) acrylic acid ethyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid-2-ethylhexyl, 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, trimethoxyvinylsilane, triethoxyvinylsilane, triisopropoxyvinylsilane, tri-tert-butoxyvinylsilane, diethoxymethylvinylsilane, diethylmethylvinylsilane, ethoxydiethylvinylsilane, trimethylvinylsilane, diacetyloxymethyl Nylsilane, triacetyloxyvinylsilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyldiacetyloxymethylsilane, 3- (meth) acryloyl Oxypropyldiethoxymethylsilane, 3- (meth) acryloyloxypropyltriacetyloxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, 3- (meth) acryloyloxypropyltrimethylsilane, 3- (meth) acryloyl Oxypropyltri-tert-butoxysilane, 3- (meth) acryloyloxypropylethoxydiethylsilane, 3- (meth) acryloyloxypropyldiethylmethylsilane, Tri-n-butyl ((meth) acryloyloxymethyl) ammonium chloride, dimethyl-n-butyl ((meth) acryloyloxymethyl) ammonium chloride, dimethyl-n-octyl ((meth) acryloyloxymethyl) ammonium chloride, dimethyl- n-dodecyl ((meth) acryloyloxymethyl) ammonium chloride, tri-n-butyl (2- (meth) acryloyloxyethyl) ammonium chloride, dimethyl-n-butyl (2- (meth) acryloyloxyethyl) ammonium chloride, Dimethyl-n-octyl (2- (meth) acryloyloxyethyl) ammonium chloride, dimethyl-n-dodecyl (2- (meth) acryloyloxyethyl) ammonium chloride, tri-n-butyl It can be exemplified Le (3- (meth) acryloyloxy propyl) ammonium chloride, dimethyl -n- butyl (3- (meth) acryloyloxy propyl) ammonium chloride, 3- (methacryloylamino) propyl trimethyl ammonium chloride or the like.

Specific examples of the monomer having the group Z ² that can give the unit — (CH ₂ CR ⁴ Z ² ) _n — include (meth) acrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, N-tert-octyl. Acrylamide, N-octadecylacrylamide, N-cyclohexyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-diphenylmethylacrylamide, N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, acroylmorpholine, N-hydroxymethyl Acrylamide, N-tris (hydroxymethyl) methylacrylamide, diacetoneacrylamide, N- (1,1-dimethyl-3-oxobutyl) acrylamide, N- (3- (N, N-dimethylamino) propyl) Examples include acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and 2-acrylamido-2-methylpropanesulfonic acid.

In the compound 1, the m / n composition ratio is in the range of m / n = 0/100 to 99/1, and can be appropriately adjusted according to the affinity with the layered inorganic compound to be used.
When the unit — (CH ₂ CR ³ Z ¹ ) _m — and the unit — (CH ₂ CR ⁴ Z ² ) _n — are present together in the compound 1, the mode of their presence is block copolymerization, alternating polymerization, random Any embodiment including copolymerization may be used.

  The number average molecular weight (Mn) of the compound 1 is preferably 500 to 1,000,000, more preferably 700 to 50 in order to express the characteristics of the fluorine segment such as a decrease in interfacial tension and aggregation of the terminal Rf group portion more significantly. 1,000 is more preferable. When Mn is in the above range, the production is easy, the aggregation effect of terminal Rf groups is relatively increased, and a molecular assembly by self-organization can be constructed. Therefore, a layered crystal compound having a high solvent repellency is used as a guest molecule. It is preferable because it can be incorporated and has sufficient affinity for a resin having low polarity.

  Compound 1 is an ethylenic monomer corresponding to the above-mentioned main chain unit using an organic peroxide containing a polyfluoroalkyl group or a polyfluorooxaalkyl group (hereinafter referred to as a fluorine-containing organic peroxide) as a radical polymerization initiator. It can be obtained by polymerizing monomers such as.

  As the fluorine-containing organic peroxide, Rf—CO—OO—OC—Rf, which is a compound obtained by peroxide bonding (—OO—) between two Rf groups at both molecular terminals exemplified above, can be used. The Rf groups bonded through these —OO— or —CO—OO—OC— may be the same as or different from each other.

Specific examples of the fluorine-containing organic peroxide include {—OC (═O) CF ₂ CF ₂ CF ₃ ] ₂ , {—OC (═O) CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ ] ₂ , { -OC (= O) CF (CF 3) OC 3 F 7] 2, {- OC (= O) [CF (CF 3) OCF 2] X CF 2 CF 3} 2 (X is a positive integer), and the like Can be mentioned.

  The organic peroxide containing the polyfluorooxaalkyl group and the fluorine-containing polymer having the group as a molecular end can also be synthesized according to the synthesis method described in JP-A No. 2003-155272.

  In the preparation of the fluoropolymer, the amount of the fluorine-containing organic peroxide and the monomer that gives the main chain unit described above may be any ratio, and the mole of the fluorine-containing organic peroxide / monomer that gives the main chain unit. The ratio is preferably 1 / (0.1 to 5000), more preferably 1 / (0.1 to 3000), and most preferably 1 / (0.1 to 1000). In addition, it is preferable that the charge molar ratio of the monomer giving the main chain unit is in the above range because the production of the product due to the self-decomposition of the fluorine-containing organic peroxide is small and the yield of the fluoropolymer is high. .

  By adjusting the charging molar ratio of the fluorine-containing organic peroxide, the average molecular weight of the resulting fluoropolymer can be adjusted. That is, if the feed molar ratio of the fluorine-containing organic peroxide is increased with respect to the monomer giving the main chain unit, a fluorine-containing polymer having a small number average molecular weight can be obtained, and if the feed molar ratio is lowered, the number average molecular weight is obtained. A large fluorine-containing polymer can be obtained.

  The polymerization reaction can be carried out at normal pressure, and the reaction temperature is preferably -20 to 150 ° C, more preferably 0 to 100 ° C. When the reaction temperature is −20 ° C. or higher, the reaction time can be shortened, and when it is 150 ° C. or lower, the pressure during the reaction does not become too high and the reaction operation is easy. The reaction time is preferably 30 minutes to 20 hours, and the conditions are preferably set so that it is practically 1 to 10 hours.

  By reacting a fluorine-containing organic peroxide with a monomer under various reaction conditions, a fluorine-containing polymer can be obtained directly by a one-step reaction, but in order to carry out the reaction more smoothly, as a reaction solvent It is preferable to use an organic solvent.

  As the organic solvent, a halogenated aliphatic hydrocarbon solvent and a halogenated aromatic hydrocarbon solvent are particularly preferable. Specifically, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, 1,2-dichloroethane, dichlorobenzene, Trichlorobenzene, 2-chloro-1,2-dibromo-1,1,2-trifluoroethane, 1,2-dibromohexafluoropropane, 1,2-dibromotetrafluoroethane, 1,1-difluorotetrachloroethane, 1 , 2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1, 1,2-trichlorotrifluoroethane, 1,1,1 2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, tridecafluorohexane, 1,1,1,2,2,3 , 4, 5, 5, 5-decafluoropentane, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, heptafluorocyclopentane, benzotrifluoride, hexafluoroxylene, and pentafluorobenzene.

  Particularly industrially, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, tridecafluorohexane 1,1,1,2,2,3,4,5,5,5-decafluoropentane, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, heptafluorocyclopentane, and benzotrifluoride are preferred.

  A solvent may be used independently and may mix and use 2 or more types. When using a solvent, it is preferable that the density | concentration of the fluorine-containing organic peroxide in a solvent is 0.1-30 mass%. The fluoropolymer obtained after completion of the reaction can be purified by known methods such as reprecipitation, column chromatography, dialysis and the like.

  The fluorine-containing polymer used in the present invention may contain, together with compound 1, a compound in which the Rf group is introduced only at one end of the polymer produced in the polymerization step, and further, radical chain transfer. May contain a group derived from a solvent or the like or a group derived from a radical termination reaction by a disproportionation reaction introduced at one end.

  The layered inorganic compound used in the present invention is a compound having a polycrystalline layer structure in which the crystalline layer is in a state (layered) having a planarly arranged sheet structure and the sheet structure is repeated in the vertical direction. .

Examples of such layered inorganic compounds include transition metal dichalcogenides such as graphite, TiS ₂ , NbSe ₂ , and MoS ₂ ; divalent metal phosphorus chalcogenides such as CrPS ₄ ; and oxidation of transition metals such as MoO ₃ and V ₂ O _5. Oxyhalides such as FeOCl, VOCl and CrOCl; hydroxides such as Zn (OH) ₂ and Cu (OH) ₂ ; Zr (HPO ₄ ) ₂ .nH ₂ O, Ti (HPO ₄ ) ₃ .nH Phosphate such as ₂ O, Na (UO ₂ PO ₄ ) ₃ .nH ₂ O; Titanate such as Na ₂ Ti ₃ O ₇ , KTiNbO ₅ , Rb _X Mn _X Ti _2-X O ₄ (X is positive) Of uranium salts such as Na ₂ U ₂ O ₇ and K ₂ U ₂ O ₇ ; KV ₃ O ₈ , K ₃ V ₅ O ₁₄ , CaV ₆ O ₁₆ .nH ₂ O, Na (UO ₂ V ₃ O ₉₎ · nH ₂ vanadate O etc.; KNb ₃ O _3, niobate such K ₄ Nb ₆ O _{17 ; Na 2 W 4 O 13,} Ag 4 W 10 O 13 , etc. of _{tungstate; Mg 2 Mo 2 O 7,} Cs 2 Mo 5 O 16, Cs 2 Mo 7 O 22, molybdenum or the like Ag ₄ Mo ₁₀ O ₃₃ Acid salts: Montmorillonite, saponite, beidellite, hectorite, nontronite, stevensite, etc. List silicates such as lepidolite, baragonite, tetrasilicite, kaolinite, halloysite, dickite, H ₂ SiO ₅ , H ₂ Si ₁₄ O ₂₉ / 5H ₂ O, or minerals composed of this silicate be able to.

  Among these layered inorganic compounds, silicates, phosphates, and molybdates are preferable from the viewpoints of dispersibility in the resin, heat resistance of the resulting resin composition, and mechanical strength. Is particularly preferred.

  The size of the layered inorganic compound in the present invention is usually 1 nm to 100 μm, preferably 1 nm to 10 μm, more preferably 1 nm to 1 μm. When the size of the layered inorganic compound is in the above range, a composition exhibiting excellent durability can be obtained without causing thermal deformation, stress concentration, and the like.

  The aspect ratio of the layered inorganic compound of the present invention is preferably 30 or more. When the aspect ratio is 30 or more, the physical properties of the obtained resin composition can be greatly improved. The aspect ratio refers to the ratio of the major axis to the minor axis of the layered inorganic compound (major axis / minor axis). The major axis of the layered inorganic compound refers to the longest span length of the flat layered inorganic compound on the flat plate surface, and the minor axis refers to the thickness of the flat layered inorganic compound viewed from the side. . The measurement of the major axis, minor axis and average aspect ratio can be obtained by calculation after observing the compound with an electron microscope and determining the major axis and minor axis of the compound.

  The step of treating the layered inorganic compound with the compound 1 to obtain a layered crystal compound can be any step of bringing them into contact with each other and mixing them. Specifically, the layered crystal compound of the present invention can be produced by the method for producing the layered crystal compound of the present invention described later.

  The layered crystal compound of the present invention may contain a dispersant in order to enhance dispersibility. Although it does not specifically limit as a dispersing agent, A fatty acid, surfactant, a coupling agent, etc. are mentioned. Examples of fatty acids include saturated fatty acids having 4 to 30 carbon atoms such as stearic acid, and unsaturated fatty acids having 4 to 30 carbon atoms such as oleic acid, linoleic acid, and linolenic acid. Examples of surfactants include anionic surfactants such as sodium stearate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and sodium dioctylsulfosuccinate; cationic surfactants such as N-laurylethanolamine and cetyltrimethylammonium chloride; polyoxy Nonionic surfactants such as ethylene nonyl phenyl ether, polyoxyethylene stearate, sorbitan stearate, polyoxyethylene sorbitan stearate; amphoteric surfactants such as alkylaminocarboxylic acid, hydroxyethyl imidazoline sulfate and imidazoline sulfonic acid Agents; fluorine-based surfactants; silicone-based surfactants; (meth) acrylic acid-based surfactants; and the like.

  As coupling agents, silane coupling agents such as γ-methacryloxypropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, hexamethyldisilazane; triisostearoyl isopropyl titanate, di (dioctyl) Phosphate) titanate coupling agents such as diisopropyl titanate; aluminate coupling agents such as monoisopropoxyaluminum monomethacrylate monooleyl acetoacetate and diisopropoxyaluminum monooleyl acetoacetate;

The layered crystal compound of the present invention can be produced by the following two production methods (hereinafter referred to as “production methods (1) and (2) of the present invention”, respectively):
(1) A method comprising a step of dispersing a layered inorganic compound in water or an organic solvent to prepare a dispersion; and a step of adding Compound 1 to the dispersion and stirring.
(2) A step of dispersing a layered inorganic compound in water or an organic solvent to prepare a dispersion; and a step of performing a reaction for producing Compound 1 in the dispersion.

<Production method (1) of the present invention>
In the production method (1) of the present invention, as a first step, a layered inorganic compound is dispersed in water or an organic solvent to prepare a dispersion. Although the density | concentration of the layered inorganic compound in a dispersion liquid will not be specifically limited if it is the range of the density | concentration which a layered inorganic compound can disperse | distribute, It is preferable that it is 1-15 mass%. In this case, using a layered inorganic compound that has been freeze-dried in advance is effective for easily producing a layered crystal compound.

  The solvent for dispersing the layered inorganic compound is not particularly limited as long as it is inert and liquid at room temperature. However, it is preferable to use a highly polar solvent from the viewpoint of dispersibility of the layered inorganic compound. For example, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and other protic solvents; sulfolane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, hexamethyl And aprotic solvents such as phosphoamide and N-methyl-2-pyrrolidone;

  In the production method (1) of the present invention, as the second step, compound 1 is added and mixed in the dispersion. Here, Compound 1 may be added directly to the dispersion, or Compound 1 may be dissolved in a solvent in advance to form a solution, and the solution may be added to the dispersion. Here, the solvent for preliminarily dissolving the compound 1 is not particularly limited as long as it is inert and liquid at room temperature, and is compatible with the solvent used for dispersing the layered inorganic compound. An excellent solvent is preferred.

  In the said 2nd process of the manufacturing method (1) of this invention, the compounding ratio of the compound 1 is 10-2,000 mass parts normally with respect to 100 mass parts of layered inorganic compounds, Preferably it is 50-1,000 masses. Parts, more preferably 100 to 500 parts by mass. When the compounding ratio of Compound 1 is less than the above range, the polarity of the surface of the layered inorganic compound is not lowered, so that the affinity with the resin becomes insufficient and it becomes difficult to uniformly disperse the layered crystal compound, which is not preferable. On the other hand, when the amount is larger than the above range, the fluorine content in the treated layered inorganic compound is increased, so that the affinity with the resin is lowered and it becomes difficult to uniformly disperse the layered crystal compound, which is preferable. Absent. The second step proceeds sufficiently at room temperature, but may be performed while heating. The maximum temperature when heating is preferably set to be equal to or lower than the decomposition point of the compound 1 to be used, and can be arbitrarily set within the range.

  The layered crystal compound of the present invention can be obtained by subjecting the solid produced in the mixture in the second step to operations such as separation from the mixture, washing, drying, and pulverization as necessary. When a solid does not form in the mixture, the obtained mixture is concentrated and dried to obtain a solid, which is pulverized as necessary to obtain the layered crystal compound of the present invention.

<Production method (2) of the present invention>
In the production method (2) of the present invention, as a first step, a layered inorganic compound is dispersed in water or an organic solvent to prepare a dispersion. As the solvent for dispersing the layered inorganic compound in this step, the same solvents as those exemplified in the first step of the production method (1) of the present invention can be used. From the viewpoint of properties, the above-described halogenated aliphatic hydrocarbon solvents and halogenated aromatic hydrocarbon solvents are preferable. Other conditions are the same as those in the first step of the production method (1) of the present invention.

  In the production method (2) of the present invention, as the second step, a reaction for producing Compound 1 is performed in the dispersion. Specifically, this reaction can be achieved by carrying out a polymerization reaction similar to the preparation method of Compound 1 described above except that the dispersion is used as a solvent. In this step, the blending ratio of the raw material of Compound 1 can be appropriately adjusted so that the amount of Compound 1 to be produced is the same as the preferable blending ratio in the production method (1) of the present invention.

  In the production methods (1) and (2), if necessary, a dispersant or the like, which is an optional component of the layered crystal compound described above, can be added at any stage of the process.

  Formation of the layered crystal compound of the present invention can be easily confirmed by measuring the position of (001) bottom reflection by X-ray diffraction. For example, when synthetic smectite-type clay is used as the layered inorganic compound, it has a bottom surface interval of 10Å in dehydrated state and 12 to 18１２ under normal temperature and humidity, but the layered crystal compound of the present invention has a bottom surface of 18Å or more. It can be seen that the layered inorganic compound is effectively treated from the interval. Thus, it is thought that the space | interval of bottom faces leaves | separates by forming the laminated structure in which the compound 1 entered between the layers of a layered inorganic compound.

  The resin composition of the present invention contains the layered crystal compound of the present invention and a resin. Although it does not specifically limit as said resin, Any of a thermoplastic resin, a thermosetting resin, and an ultraviolet curable resin may be sufficient.

  Examples of the thermoplastic resin include an alicyclic structure-containing polymer, a chain polyolefin resin, a polycarbonate resin, a polyester resin, a polysulfone resin, a polyether polysulfone resin, a polystyrene resin, a polyvinyl alcohol resin, and cellulose acetate. Resin, polyvinyl chloride resin, polyacrylate resin and the like. Examples of thermosetting resins include phenolic resins, urea resins, melamine resins, epoxy resins, urethane resins, silicon resins, and the like, and examples of ultraviolet curable resins include polysiloxane resins. be able to.

  Among these resins, for various reasons such as having various characteristics advantageous when used as an optical material, low water absorption, good mechanical, thermal, and physical properties can be obtained in combination with a layered crystal compound. Thermoplastic resins are preferred, and among the thermoplastic resins, polyacrylate resins and alicyclic structure-containing polymers are particularly preferred.

  A polyacrylate resin is a polymer containing an acrylate or methacrylate structure in its repeating unit. A homopolymer of a monomer containing an acrylate or methacrylate structure, which will be described later, and these monomers can be copolymerized with this monomer. Random copolymers with other monomers, copolymers such as block copolymers.

Examples of the monomer containing an acrylate structure include acrylate derivatives, such as methyl acrylate, ethyl acrylate, butyl acrylate, and acrylic acid.
Examples of the monomer having a methacrylate structure include methacrylate derivatives, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and methacrylic acid.
The monomer copolymerizable with the monomer having an acrylate or methacrylate structure is not particularly limited, and examples thereof include acrylamide derivatives such as acrylamide, methacrylamide, and N-methylolacrylamide; styrene, α-methylstyrene, vinyltoluene, and the like. Aromatic monomers; acrylonitrile, methacrylonitrile, vinyl acetate and the like can be mentioned.
These monomers used for producing the polyacrylate resin may be used alone or in combination of two or more.
As a method for producing the polyacrylate resin, a known radical polymerization method can be used. Examples of the method include a suspension polymerization method, a continuous bulk polymerization method, a solution polymerization method, a bag polymerization method, and the like. From the viewpoint of productivity, the continuous bulk polymerization method is preferable.
The polyacrylate resin can be obtained by polymerizing the monomer using a known polymerization initiator.

  The alicyclic structure-containing polymer is a polymer containing an alicyclic structure in the repeating unit of the polymer. Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure. From the viewpoint of the thermal stability of a resin composition containing an alicyclic structure-containing polymer or a molded product obtained from the composition. Then, a cycloalkane structure is preferable. Carbon number which forms an alicyclic structure is 4-30 normally, Preferably, it is 5-20, More preferably, it is 5-15. When the carbon number is within this range, the resin composition has excellent heat resistance and flexibility. This alicyclic structure may be present in either the main chain or the side chain of the polymer.

  There is no restriction | limiting in the content rate of the repeating unit containing the alicyclic structure in the said alicyclic structure containing polymer, Although it selects suitably according to the property, physical property, etc. of the resin composition obtained, Usually, 50 masses % Or more, preferably 70% by mass or more, more preferably 90% by mass or more. When the content ratio of this repeating unit is too small, the heat resistance of the resulting resin composition may be lowered, which is not desirable. The alicyclic structure-containing polymer may contain a repeating unit other than the repeating unit containing an alicyclic structure.

  Examples of the alicyclic structure-containing polymer contained in the resin composition of the present invention include a norbornene polymer (A), a monocyclic olefin polymer (B), a cyclic conjugated diene polymer (C), and vinyl. Examples thereof include alicyclic hydrocarbon polymers (D) and mixtures thereof. Among these polymers, the norbornene-based polymer (A) and the vinyl alicyclic hydrocarbon polymer (D) are preferable from the viewpoint of the heat resistance and mechanical strength of the obtained resin composition.

  Examples of the norbornene polymer (A) include a ring-opening polymer of a norbornene monomer and a hydride thereof, and a ring-opening copolymer of the norbornene monomer and another monomer capable of ring-opening copolymerization with the norbornene monomer. And addition products of norbornene monomers, addition copolymers of norbornene monomers with other monomers copolymerizable with the norbornene monomers, and the like. Can do. Among these polymers and copolymers, from the viewpoints of heat resistance and mechanical strength of the resulting alicyclic structure-containing polymer composition, a hydride of a ring-opening (co) polymer of a norbornene-based monomer is particularly preferable. .

Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and its derivatives (having substituents in the ring, the same shall apply hereinafter), tricyclo [5.2. 1.0 ^2,6] dec-3,8-diene (trivial name: dicyclopentadiene) and their derivatives, tetracyclo [9.2.1.0 ^2,10. 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (common name: metatetrahydrofluorene) and its derivatives, tetracyclo [6.2.1.1 ^3,6 . ^0,7 ] dodec-4-ene (common name: tetracyclododecene) and its derivatives.

  Examples of the substituent include an alkyl group, an alkylene group, a vinyl group, and an alkoxycarbonyl group. The norbornene-based monomer may have one or more of these substituents. Also good.

Examples of the norbornene-based monomer having these substituents include 9-methyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methoxycarbonyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-methoxycarbonyl-tetracyclo [6.2.1.1 ^3,6 . ^0,7 ] dodec-4-ene and the like.

  These norbornene monomers used for producing the norbornene polymer (A) may be used alone or in combination of two or more.

  The ring-opening polymer of the norbornene-based monomer or the ring-opening copolymer of the norbornene-based monomer and another monomer capable of ring-opening copolymerization with the norbornene-based monomer has the presence of a known ring-opening polymerization catalyst. It can be produced by polymerizing below.

  Examples of the other monomer capable of ring-opening copolymerization with the norbornene-based monomer include monocyclic olefin-based monomers such as cyclohexene, cycloheptene, and cyclooctene.

  The hydride of the ring-opening (co) polymer of the norbornene-based monomer is usually added to a reaction solution after the ring-opening polymerization of the norbornene-based monomer by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium, It can be produced by hydrogenating carbon-carbon unsaturated bonds.

  The addition polymer of the norbornene monomer or the addition copolymer of the norbornene monomer and another monomer copolymerizable with the norbornene monomer is polymerized in the presence of a known addition polymerization catalyst. Can be manufactured.

  Examples of other monomers capable of addition copolymerization with norbornene-based monomers include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene and derivatives thereof; cyclobutene, cyclopentene, 3a, 5, 6, Examples include cycloolefins such as 7a-tetrahydro-4,7-methano-1H-indene and derivatives thereof; non-conjugated dienes such as 1,4-hexadiene and 4-methyl-1,4-hexadiene. Among these monomers, α-olefins, particularly ethylene is preferable.

  Other monomers copolymerizable with the norbornene-based monomer may be used alone or in combination of two or more.

  In addition copolymerization of a norbornene monomer and another monomer copolymerizable with this norbornene monomer, a structural unit derived from the norbornene monomer in the resulting addition copolymer, and addition copolymerization The amount of each monomer used is selected so that the proportion of structural units derived from other possible monomers is in the range of 50:50 to 99: 1, preferably 70:30 to 97: 3, by mass ratio. The

  Examples of the monocyclic olefin polymer (B) include addition polymers of monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

  Examples of the cyclic conjugated diene polymer (C) include 1,2- or 1,4-addition polymers of cyclic conjugated diene monomers such as cyclopentadiene and cyclohexadiene, and hydrides thereof.

  Examples of the vinyl alicyclic hydrocarbon polymer (D) include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane and their hydrides, styrene, α-methylstyrene, and the like. Hydrogenated products obtained by hydrogenating aromatic moieties contained in polymers obtained by polymerizing vinyl aromatic hydrocarbon monomers, vinyl alicyclic hydrocarbon monomers or vinyl aromatic hydrocarbon monomers, and these vinyl aromatic carbons. Examples thereof include random copolymers with other monomers copolymerizable with hydrogen-based monomers, and hydrides of copolymers such as block copolymers. Examples of the block copolymer include diblock, triblock or higher multiblock, and gradient block copolymer.

  The alicyclic structure-containing polymer preferably has a polar group for reasons such as high affinity with the layered crystal compound.

  Examples of the polar group include heteroatoms or atomic groups having heteroatoms. Examples of the heteroatoms include oxygen atoms, nitrogen atoms, silicon atoms, and halogen atoms. Among these heteroatoms, an oxygen atom and a nitrogen atom are preferable from the viewpoint of dispersibility and compatibility with the layered crystal compound. Specific examples include a carboxyl group, a carbonyloxycarbonyl group, an epoxy group, a hydroxy group, an oxy group, an ester group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group.

  The method for obtaining the alicyclic structure-containing polymer having a polar group is not particularly limited, but when the alicyclic structure-containing polymer is a norbornene-based polymer, for example, (I) among various norbornene-based monomers A method of reacting a compound having a polar group (modification reaction) with an unmodified polymer obtained by polymerizing a norbornene-based monomer having no polar group selected from (II), and (II) various norbornene-based monomers A method of copolymerizing a norbornene monomer having no polar group and a norbornene monomer having a polar group selected from among them, (III) a polar group selected from various norbornene monomers A polymer obtained by polymerizing a norbornene-based monomer having no polar group, and a nor group having a polar group obtained by the method (I) or (II) And a method such as mixing the Runen polymer. The alicyclic structure-containing polymer other than the norbornene polymer is the same as that of the norbornene polymer.

  As the alicyclic structure-containing polymer having a polar group, the alicyclic structure-containing polymer is chlorinated, the alicyclic structure-containing polymer is chlorosulfonated, and the alicyclic structure-containing polymer is polar. Examples include those obtained by graft modification with a group-containing unsaturated compound, and among them, those obtained by graft-modifying an alicyclic structure-containing polymer with a polar group-containing unsaturated compound are preferable.

  Examples of the polar group-containing unsaturated compound include unsaturated epoxy compounds such as glycidyl acrylate, glycidyl methacrylate, glycidyl p-styrylcarboxylate, allyl glycidyl ether, and glycidyl ether of 2-methylallyl glycidyl ether; acrylic acid and methacrylic acid , Α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, etc .; unsaturated carboxylic acid compounds; maleic anhydride, chloromaleic anhydride, butenyl succinic anhydride, etc .; monomethyl maleate, maleic acid Unsaturated ester compounds such as dimethyl and glycidyl malate; Unsaturated alcoholic compounds such as allyl alcohol, 2-allyl-6-methoxyphenol and 4-allyloxy-2-hydroxybenzophenone; Chlorodimethylvinylsila It can include trimethylsilylacetylene, 5-trimethylsilyl-1,3-cyclopentadiene, 3-trimethylsilylallyl alcohol, an unsaturated silane compounds such as trimethylsilyl methacrylate.

  Among these polar group-containing unsaturated compounds, unsaturated epoxy compounds and unsaturated carboxylic acid compounds are particularly preferable from the viewpoint of dispersibility of the layered crystal compound. In order to efficiently modify these polar group-containing unsaturated compounds, it is preferable to carry out a modification reaction in the presence of a general-purpose radical initiator. Examples of suitable radical initiators include organic peroxides, organic peroxides. Examples include esters.

  The polar group content of the alicyclic structure-containing polymer having a polar group is preferably at least 0.01 mmol / g, more specifically 0.01 to 0.8 mmol / g, more preferably 0. 0.01 to 0.5 mmol / g. When the polar group content is within the above range, both the improvement of the dispersibility of the layered crystal compound and the improvement of various physical properties such as water resistance can be achieved.

  In the method (I), the polar group content is determined by the introduction rate of the polar group by the reaction of the compound having a polar group, and in the method (II), by the copolymerization ratio of the monomer having a polar group, In the method (III), it can be adjusted by the mixing ratio of the polymer having no polar group and the polymer containing the polar group.

  Although there is no restriction | limiting in particular in the molecular weight of a thermoplastic resin, The mass mean molecular weight of polystyrene conversion is 5,000-500,000 normally, Preferably, 8,000-200,000, More preferably, 10,000- 100,000. When the mass average molecular weight is in this range, the molding processability of the obtained resin composition becomes good, and the mechanical strength can be improved. This mass average molecular weight can be measured by gel permeation chromatograph method of cyclohexane solution or toluene solution.

  Furthermore, although there is no restriction | limiting in particular also in the glass transition temperature (Tg) of a thermoplastic resin, Usually, it is 80 degreeC or more, Preferably, it is 130-250 degreeC. When the glass transition temperature is in this range, the obtained resin composition can withstand use at high temperatures, and does not cause thermal deformation, stress concentration, or the like, and can have excellent durability.

  In the resin composition of the present invention, the blending ratio of the layered crystal compound and the resin can be appropriately adjusted according to the purpose, but the content of the layered crystal compound in the obtained composition is usually 0.1 to 70% by mass. , Preferably 1 to 60% by mass, more preferably 5 to 50% by mass. In addition, content of the layered crystal compound in a composition can be calculated | required by measuring the heating residue (ash content) of a resin composition.

  The method for preparing the resin composition of the present invention is not particularly limited, but a method of simply kneading the layered crystal compound and the resin, or a mixture of the layered crystal compound and the monomer constituting the resin is prepared, and the monomer is polymerized. Further, a kneading method and the like may be mentioned as necessary.

  Various additives may be added to the resin composition of the present invention as desired. Examples of the additive to be used include phenolic and phosphorus antioxidants, antistatic agents, ultraviolet absorbers, rubbery polymers, petroleum resins, and different thermoplastic resins. For the purpose of improving moldability and physical properties, for example, fibrous fillers such as glass fibers and carbon fibers; particulate fillers such as silica, alumina and calcium carbonate; tetrakis [2- (3,5-di- -T-butyl-4-hydroxyphenyl) ethylpropionate] antioxidants such as methane and 2,6-di-t-butyl-4-methylphenol; Antistatic agents, lubricants, flame retardants, pigments, dyes, antiblocking agents, and the like may be added. In general, in order to avoid elution from a polymer, these additives are preferably those having a higher molecular weight. The addition amount of an additive is not specifically limited, It can add in the range according to the objective.

  The molded body of the present invention is formed by molding the resin composition of the present invention. The molding method of the molded body of the present invention is not particularly limited, and a solution casting method, a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, a stretch molding method, and the like can be employed.

  The molded article of the present invention can be used for various applications to which a resin having excellent physical properties such as dimensional stability can be adapted. Specifically, (1) daily goods such as windproof glass and window glass, (2) Lenses used in car lamps, glasses, goggles, etc. (3) Camera parts, housings and containers for various instruments and devices, industrial parts such as containers, (4) Cameras, VTRs, copiers, OHP, projections, printers, etc. (5) Information disc materials such as magneto-optical discs, dye-type discs, music compact discs, simultaneous recording / reproducing discs for image music, and memory discs, etc. Information recording and information display fields such as antireflection films, liquid crystal display element substrates, diffusion plates, light guide plates and forward scattering plates, and optical fibers and optical waveguides Irumu and information transfer part of the connector or the like, and the like various optical components, including (7) for receiving the element cover and a prism or the like.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited to these. In the following examples, “part” and “%” are based on mass unless otherwise specified. Further, the molecular weight of the fluoropolymer, the interlayer distance of the layered inorganic compound, the linear expansion coefficient of the molded product, and the ash content of the resin composition were measured as follows (A) to (D), respectively.

(A) Molecular weight of fluoropolymer Measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

(B) Measurement of interlaminar distance of layered crystal compound The interlaminar distance of the layered crystal compound portion is an analysis peak derived from (001) plane bottom reflection of the layered crystal compound using a Rigaku Electric wide-angle X-ray analyzer (RINT2000). Calculated from

(C) Measurement of linear expansion coefficient The produced molded body (film) having a thickness of 100 μm was cut into a width of 5 mm and a length of 15 mm, and a linear expansion coefficient was measured using a thermomechanical analyzer (trade name: TMA / SDTA840) manufactured by METTLER TOLEDO. Was measured. In this invention, after measuring in the temperature range from 30 degreeC to 100 degreeC by the temperature increase rate of 10 degree-C / min under nitrogen stream, the average value in the range of 50-80 degreeC was made into the linear expansion coefficient.

(D) Measurement of ash content An approximately 1.5 g sample was weighed, and the organic component was decomposed by heating the sample at a temperature of 650 ° C. for 2 hours in a nitrogen atmosphere, and the amount of residue was calculated.

(Production Example 1) Production of fluoropolymer A four-necked flask equipped with a condenser, a thermometer, a stirrer, and a dropping funnel was added with a fluorinated solvent AK-225 (trade name, manufactured by Asahi Glass, 1,1-dichloro-2, 2,3,3,3-pentafluoropropane: mixture of 1,3-dichloro-1,2,2,3,3, -pentafluoropropane = 1: 1.35) and 1.51 parts of acryloylmorpholine (10 mmol) was charged, the temperature of the reaction vessel was adjusted to 45 ° C., and then 6.58 parts of diperfluoro-2-methyl-3-oxahexanoyl peroxide / AK-225 10% by mass solution (initiator amount: 1 mmol) Was added dropwise over 5 minutes. After completion of the dropwise addition, the mixture was reacted in a nitrogen stream at 45 ° C. for 5 hours, and then the resulting product was concentrated to 5 ml, reprecipitated with hexane, and dried to obtain 0.99 parts of a fluoropolymer. It was. The number average molecular weight of the obtained fluoropolymer was 8,900.

Example 1
50 parts of saponite (long average value: 0.05 μm, aspect ratio: 50) which is a layered inorganic compound was uniformly dispersed in 1000 parts of distilled water at 60 ° C. to obtain a saponite dispersion. Next, while stirring the saponite dispersion, a solution prepared by dissolving 100 parts of the fluoropolymer obtained in Production Example 1 in 100 parts of distilled water was slowly added, and stirring was continued at 60 ° C. for 3 hours. After completion of the stirring, distilled water was removed under reduced pressure to obtain a solid. Subsequently, residual moisture was further removed by freeze-drying to obtain 146.8 parts of a fluoropolymer-treated saponite (layered crystal compound 1). When the interlayer distance of the obtained fluoropolymer-treated saponite was measured using a wide-angle X-ray analyzer as described above, no peak was observed in the vicinity of 2 to 10 °. The interlayer distance was 45 mm or more. Moreover, the ash content of the obtained fluoropolymer-treated saponite was 33%.

  Next, the fluorine-containing polymer-treated saponite and norbornene-based polymer (trade name: ARTON FX4726, glass transition temperature 125 ° C., manufactured by JSR) obtained previously, and the ash content of the obtained resin composition are 7, 14, respectively. Premixing was performed using a Henschel mixer so as to be 21, 28, or 35% by mass. The obtained mixture was kneaded using a biaxial kneader (Toshiba Machine, TEM-35B, screw diameter 37 mm, L / D = 32, screw rotation speed 150 rpm, resin temperature 240 ° C., field rate 10 kg / hour), Resin compositions 1 to 5 were obtained by extruding the resin composition into strands, cooling with water, cutting with a pelletizer, and pelletizing. Subsequently, the obtained resin composition was melted at a molten resin temperature of 240 ° C. and a T-die width of 350 mm using a T-die type film melt extruder having a resin melt kneader equipped with a 10 μm polymer filter and a 65 mmφ screw. Films 1 to 5 having different ash contents were obtained by extrusion molding of a film having a thickness of 100 μm under the molding conditions described above. The result of having measured the linear expansion coefficient of the obtained films 1-5 is shown in FIG. In the obtained film, the higher the ash content, the lower the linear expansion coefficient, and it was confirmed that the film had excellent performance.

(Example 2)
In a four-necked flask equipped with a condenser, a thermometer, a stirrer, and a dropping funnel, 50 parts of a fluorinated solvent AK-225 (trade name, manufactured by Asahi Glass Co., Ltd.), 1.41 parts (10 mmol) of acryloylmorpholine, and saponite (a layered inorganic compound) (Long average value: 0.05 μm, aspect ratio: 50) 0.7 part was charged, the reaction vessel was adjusted to 45 ° C., and then AK-225 10 of diperfluoro-2-methyl-3-oxahexanoyl peroxide 6.58 parts by mass (initiator amount: 1 mmol) was added dropwise over 5 minutes. After completion of the dropwise addition, the mixture was reacted at 45 ° C. for 5 hours in a nitrogen stream, and then the obtained product was concentrated to 5 ml, reprecipitated with hexane, and dried to obtain a fluorinated polymer-treated saponite (layered crystal compound). 2) 2.09 parts were obtained. The obtained fluoropolymer-treated saponite was dispersed in tetrahydrofuran, and the supernatant was recovered using a centrifuge. Then, when the molecular weight of the fluoropolymer contained in the obtained supernatant liquid was measured, the number average molecular weight was 6,500. Further, when the interlayer distance of the obtained fluoropolymer-treated saponite was measured using a wide-angle X-ray analyzer as described above, no peak was observed in the vicinity of 2 to 10 °. The interlayer distance was 45 mm or more. Moreover, the ash content of the obtained fluoropolymer-treated saponite was 38% by mass.

  Next, the fluorine-containing polymer-treated saponite and polyacrylate resin (trade name: Acripet V, Vicat softening point 100 ° C., manufactured by Mitsubishi Rayon Co., Ltd.) obtained above are used, and the ash content of the obtained film is 7, 14, 21 respectively. , 28 or 35% by mass, and toluene was added thereto to obtain a mixture having a resin concentration of 15% by mass. This mixture was mixed until uniform using a paint shaker to obtain a coating solution. Using the resulting coating solution, a film 6 to 10 having different ash content is obtained by coating on a glass plate so that the dry film thickness is 100 μm, and drying at room temperature for 2 days and further at 80 ° C. for 2 days. It was. When the linear expansion coefficient of the obtained films 6 to 10 was measured, as in Example 1, in the obtained film, the higher the ash content, the lower the linear expansion coefficient, and the film having excellent performance. Was confirmed.

(Comparative Example 1)
Fluorite-polymer-treated saponite (layered crystalline compound 2) used in Example 2 was converted to lucentite SAN (product of Co-op Chemical, ash content: 70% by mass) which is a saponite treated with dimethylhexadecyloctadecyl ammonium chloride. Except for the change, the same operations as in Example 2 were performed to obtain films 11 to 15 having a thickness of 100 μm and different ash contents. When the linear expansion coefficients of the obtained films 11 to 15 were measured, a phenomenon was observed in which improvement in the linear expansion coefficient was not observed as the amount of the organically treated saponite increased.

FIG. 1 is a graph showing the relationship between the amount of ash in the molded body and the linear expansion coefficient in Examples and Comparative Examples.

Claims (6)

A layered crystal compound obtained by treating a layered inorganic compound with a fluorine-containing polymer represented by the following general formula (I):
_{^{Rf 1 - (CH 2 CR 3}} Z 1) m - (CH 2 CR 4 Z 2) n -Rf 2 ··· (I)
(In general formula (I), Rf ¹ and Rf ² are each independently a polyfluoroalkyl group having 3 or more carbon atoms or a polyfluorooxaalkyl group having 3 or more carbon atoms. R ³ and R ⁴ are hydrogen atoms or Z ¹ is independently a hydrogen atom, a monovalent organic group or a halogen atom, Z ² is —CONR ⁵ R ⁶ , wherein R ⁵ and R ⁶ are each independently a hydrogen atom , An alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a sulfonic acid-containing alkyl group having 1 to 18 carbon atoms, or — [C (R ¹⁵ ) ₂ ] _q COR ¹⁶ (R ¹⁵ is independently Or a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹⁶ is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and q is an integer of 1 to 5). there, or R ⁵ and R ⁶ forming To a .m / n = 0 / 100~99 / 1 is a group constituting a ring with the adjacent nitrogen atom to form a divalent alkylene group or an ether group having 2 to 8 carbon atoms.). Z ¹ in the general formula (I) is —Si (R ⁷ ) ₃ , —OCOR ⁸ , —COOR ⁹ , —CON (R ¹⁰ ) R ¹¹ —N ⁺ (R ¹² ) ₃ X ⁻ , or —COOR ¹¹ —N. ⁺ (R ¹² ) ₃ X ^— (R ⁷ is each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. R ⁸ and R ⁹ are each a hydrogen atom, 18 alkyl groups, hydroxyalkyl groups having 2 to 6 carbon atoms, sulfonic acid-containing alkyl groups having 1 to 18 carbon atoms, — (CH ₂ ) ₃ —Si (R ¹³ ) ₃ or — (C (R ¹⁴ ) ₂ ) _p COR ¹³ (R ¹³ is each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, R ¹⁴ is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, p is an integer of 1 to 5.), R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms .R ¹¹ Is an alkylene group having 1 to 4 carbon atoms .R ¹² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms .X is a halogen atom.) According to claim 1 layered crystal compound according. A step of dispersing a layered inorganic compound in water or an organic solvent to prepare a dispersion; and a step of adding and stirring the fluoropolymer represented by the general formula (I) in the dispersion. The method for producing a layered crystal compound according to claim 1. Including a step of dispersing a layered inorganic compound in water or an organic solvent to prepare a dispersion; and a step of performing a reaction in the dispersion to produce the fluoropolymer represented by the general formula (I). The method for producing a layered crystal compound according to claim 1.   A resin composition comprising the layered crystal compound according to claim 1 and a resin.   The molded object formed by shape | molding the resin composition of Claim 5.

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