JP2005232264A - Resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition causing no increase in water absorption of its own and narrowing no selection of polymer kinds, and to provide a method for producing the resin composition. <P>SOLUTION: One version(1) of the resin composition comprises a layered inorganic compound, an organizing agent and a substantially nonpolar thermoplastic resin. In this version(1), the organizing agent and the substantially nonpolar thermoplastic resin are bound to each other via carbon-carbon covalent bond, and the ionic part of the organizing agent and the layered inorganic compound are ionically bound to each other. The other version(2) of the resin composition comprises a layered inorganic compound, an organizing agent, a substantially nonpolar thermoplastic resin and a polar group-bearing guest molecule. In this version(2), the organizing agent or the guest molecule and the substantially nonpolar thermoplastic resin are bound to each other via carbon-carbon covalent bond, and the ionic part of the organizing agent and the layered inorganic compound are ionically bound to each other, or the polar group of the guest molecule and the layered inorganic compound are bound to each other via hydrogen bond. The methods for producing these versions are also provided respectively. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resin composition and a method for producing the resin composition.

  With the increase in size and thickness of liquid crystal displays (hereinafter sometimes abbreviated as “LCD”), various optical members have been increased in size and thickness. Examples of the optical member include a light guide plate, a light diffusion sheet, and an optical lens. Due to the increase in size and thickness of the optical member, there is a problem of bending due to the weight of the optical member, and a high rigidity of the material of the optical member has been demanded.

  Examples of the method for improving the rigidity of the optical member include a method of adding an inorganic compound such as clay to the material. However, in the method of adding this inorganic compound to the material, it is necessary to improve the dispersibility of the inorganic compound in the material. To improve the dispersibility, a polymer having a polar group introduced is used. The material became easy to absorb water, which became a problem.

  As a conventional method, for example, “a functional group-containing polymer comprising an organized clay, two or more kinds of polymers, and a crosslinking agent, at least one of the two or more kinds of polymers having a functional group. , A resin composite characterized in that the functional group-containing polymer is cross-linked by the cross-linking agent (see Patent Document 1).

  In addition, “a clay mineral organically formed by ionic bonding of an organic onium ion having an unsaturated carbon chain of 6 or more carbon atoms, a polar group in the molecule, and the molecular length is the same as that of the organic onium ion. A guest molecule having a larger unsaturated carbon chain and a cross-linking agent capable of forming a cross-linking bond between the unsaturated bond of the organic onium ion and the unsaturated bond of the guest molecule. Is a clay composite characterized in that at least a part of the organic onium ion and the guest molecule enter, and a hydrogen bond is formed between the clay mineral and the polar group of the guest molecule. Material "is also disclosed (see Patent Document 2).

JP 11-181309 A (Claim 1) Japanese Patent Laid-Open No. 10-7418 (Claim 1)

  However, in the invention according to the above-mentioned Patent Document 1, since two or more kinds of polymers are used, compatibility between the polymers must be taken into consideration, and there is a problem that the range of selection of the type of polymer is narrowed. In addition, among the two or more types of polymers to be used, one type mainly contains oligomers, and thus has a problem of adversely affecting mechanical properties due to a plasticizing effect. Further, since the functional group-containing polymer is used, there is a problem that the water absorption rate of the resin composite increases.

  Moreover, in the invention which concerns on the above-mentioned patent document 2, there exists a problem of compatibility of a guest molecule and a polymer. Further, since the oligomer is mainly contained, there is a problem that the mechanical properties are adversely affected by the plasticizing effect.

  The present invention eliminates such conventional problems, has a low water absorption, does not significantly reduce light transmittance, and has excellent mechanical properties, and a method for producing such a resin composition The issue is to provide

As a structure of this invention which is a means for solving the above-mentioned subject,
Claim 1 includes a layered inorganic compound, an organic agent, and a substantially nonpolar thermoplastic resin, and the organic agent and the substantially nonpolar thermoplastic resin are carbon-carbon covalent bonds. A resin composition characterized in that the ionic portion in the organic agent and the layered inorganic compound are ion-bonded.
Claim 2 includes a layered inorganic compound, an organic agent, a substantially nonpolar thermoplastic resin, and a guest molecule having a polar group, and the organic agent or guest molecule is substantially nonpolar. The ionic part in the organic agent and the layered inorganic compound are ionically bonded or the polar group of the guest molecule and the layered inorganic compound are hydrogen bonded. It is a resin composition characterized by comprising,
According to a third aspect of the present invention, the organic agent and the substantially nonpolar thermoplastic resin, or the guest molecule and the substantially nonpolar thermoplastic resin form a covalent bond by a radical reaction. Or a method for producing a resin composition according to 2,
The resin according to claim 3, wherein the organic agent or the guest molecule having a polar group and the substantially nonpolar thermoplastic resin contain at least 10% by mass of a tertiary carbon atom. The method according to claim 3 or 4, wherein the organic agent or guest molecule contains a tertiary carbon atom or a carbon-carbon unsaturated bond. It is a manufacturing method.

  In the resin composition according to the present invention, the layered inorganic compound is dispersed in the resin composition in a state of being miniaturized to the nano order by being organically treated with an organic agent. Therefore, although the resin composition according to the present invention contains an inorganic compound, its transparency is maintained, increased, or slightly decreased as compared with the case where no inorganic compound is contained.

  In the resin composition according to the present invention, a substantially nonpolar thermoplastic resin and an organic agent, or a substantially nonpolar thermoplastic resin and a guest molecule are bonded by a carbon-carbon covalent bond. Furthermore, the ionic part in the organic agent and the layered inorganic compound are ionically bonded, or the polar group in the guest molecule having a polar group and the layered inorganic compound are hydrogen bonded.

  Therefore, according to this invention, it is possible to provide a resin composition having good transparency and excellent heat resistance and mechanical properties.

  In addition, when an organic agent having a hydrocarbon group having a short carbon chain as a hydrophobic group is used, a substantially nonpolar thermoplastic resin is bonded to the surface of the layered inorganic compound near the surface of the layered inorganic compound. This also provides a resin composition in which a thermoplastic resin is firmly bonded to the surface of the layered inorganic compound.

  The resin composition according to the present invention can be produced by the following method.

  First, the layered inorganic compound is organically treated by a known method with an organic agent to form a layered inorganic compound. Next, the organically treated layered inorganic compound and a substantially nonpolar thermoplastic resin are mixed, and the thermoplastic resin and the organic agent are bonded by a carbon-carbon covalent bond. In some cases, the organically layered inorganic compound (A), a substantially nonpolar thermoplastic resin, and a guest molecule are mixed, and the guest molecule and the thermoplastic resin are covalently bonded with carbon-carbon. Or the guest molecule and the organic agent are bonded to the thermoplastic resin by a carbon-carbon covalent bond. The carbon-carbon covalent bond is, for example, obtained by radical reaction of tertiary carbon and carbon in the carbon-carbon unsaturated bond as shown in the following formula (1), or shown in the following formula (2). Thus, it can form by carrying out radical reaction of tertiary carbon.

  This tertiary carbon may be contained in the thermoplastic resin, or may be contained in the organic agent and / or the guest molecule.

[Resin composition]
The resin composition according to one embodiment of the present invention contains a layered inorganic compound, an organic agent, a substantially nonpolar thermoplastic resin, and / or a guest molecule having a polar group.

[Thermoplastic resin]
The thermoplastic resin in this invention is a substantially nonpolar thermoplastic resin. Examples of such thermoplastic resins include olefin resins, diene resins, hydrogenated diene resins, and alicyclic structure-containing polymers. Among these, an olefin resin and an alicyclic structure-containing polymer are preferable, and an alicyclic structure-containing polymer is particularly preferable. Here, “substantially non-polar” does not mean only when it does not have a polar group completely, and when the resin composition according to the present invention is used for an optical member, for example, the optical characteristics are impaired. It is allowed to have polar groups as much as possible to maintain the hydrophobicity to some extent.

  Examples of the olefin resin include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene. And a homopolymer such as 1-dodecene, or a copolymer. Specific examples of these polymers include homopolymers such as polyethylene, polypropylene, poly-1-butene, and poly-4-methyl-1-pentene, ethylene / propylene copolymers, and ethylene / 1-butene copolymers. Polymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / 1-decene copolymer, propylene / ethylene copolymer, Propylene / 1-butene copolymer, propylene / 4-methyl-1-pentene copolymer, propylene / 1-hexene copolymer, propylene / 1-octene copolymer, propylene / 1-decene copolymer, and Examples include a copolymer of the α-olefin and a cyclic olefin such as norbornene or tetracyclododecene.

  These olefin resins can be used alone or as a mixture of two or more. Among these olefin resins, polyethylene, polypropylene, poly-1-butene and the like have a high glass transition point, such as resins having a high crystallinity of 40% or more, or copolymers of α-olefin and cyclic olefin. Resins are preferred because of their excellent gas barrier properties.

  Among these, polyethylene and polypropylene are most preferable in terms of excellent moldability and rigidity. Polypropylene can be any of a homopolymer, a random copolymer with ethylene and / or 1-butene, and a block copolymer. From the viewpoint of the strength and gas barrier properties of a molded product, a block copolymer is used. It is preferable to use it. The polyolefin used in the present invention has an intrinsic viscosity measured in decalin at 135 ° C. of 0.01 to 20 dl / g, preferably 0.1 to 10 dl / g.

  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 the alicyclic structure-containing polymer composition or a molded product obtained from the composition, A cycloalkane structure is preferred. 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 in this range, an alicyclic structure-containing polymer composition having excellent heat resistance and flexibility or a molded body obtained from the alicyclic structure-containing polymer composition is obtained. 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. In addition, the alicyclic structure containing polymer used for this invention may contain repeating units other than the repeating unit containing an alicyclic structure.

  Specific examples of the alicyclic structure-containing polymer include (1) a norbornene polymer, (2) a monocyclic olefin polymer, (3) a cyclic conjugated diene polymer, and (4) a vinyl alicyclic ring. And a hydrocarbon-based polymer, and hydrogenated products thereof. Among these, norbornene-based polymers, cyclic conjugated diene-based polymers, hydrogenated products thereof, and mixtures thereof are preferable, and norbornene-based polymers are more preferable in terms of heat resistance and mechanical strength.

  Examples of the norbornene-based polymer (1) include a ring-opening polymer of a norbornene-based monomer, a ring-opening copolymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with the norbornene-based monomer, and these Examples include hydrides of ring-opening copolymers, addition polymers of norbornene monomers, and addition copolymers of norbornene monomers and other monomers copolymerizable with the norbornene monomers. Among these polymers and copolymers, a hydride of a ring-opening polymer of a norbornene monomer is particularly preferable from the viewpoint of heat resistance and mechanical strength of the resulting alicyclic structure-containing polymer composition.

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 [4.3. 0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene) and derivatives thereof, 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (Common name: metatetrahydrofluorene) and its derivatives, tetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] dodec-3-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 two or more of these substituents. Good.

As the norbornene-based monomer having these substituents, 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.

  These norbornene monomers used for producing the norbornene polymer (1) 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 monomer include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

  The hydride of the ring-opening polymer of the norbornene monomer is generally prepared by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to the polymerization liquid of the norbornene monomer to hydrogenate the carbon-carbon unsaturated bond. Can be manufactured.

  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 therewith, a structural unit derived from the norbornene monomer in the resulting addition copolymer and other copolymerizable monomers. The amount of each monomer used is selected so that the ratio of the structural unit derived from the monomer is 50:50 to 99: 1, preferably 70:30 to 97: 3, in mass ratio.

  Examples of the monocyclic olefin polymer (2) include addition polymers of cyclic olefin monomers having a single ring such as cyclohexene, cycloheptene, and cyclooctene.

  Examples of the cyclic conjugated diene polymer (3) 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 (4) include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane and their hydrides, vinyl aromatics such as styrene and α-methylstyrene. Hydrides obtained by hydrogenating aromatic moieties contained in polymers obtained by polymerizing aromatic hydrocarbon monomers, vinyl alicyclic hydrocarbon monomers or vinyl aromatic hydrocarbon monomers and these vinyl aromatic hydrocarbon monomers Examples thereof include random copolymers with other monomers copolymerizable with the monomers, copolymers such as block copolymers, and hydrogenated aromatic rings thereof. Examples of the block copolymer include diblock, triblock or higher multiblock, and gradient block copolymer.

  It is desirable that the alicyclic structure-containing polymer in this invention is substantially hydrophobic. In order for the alicyclic structure-containing polymer in the present invention to be substantially hydrophobic, it is desirable that the polymer does not contain a polar group. However, the polar group can improve the affinity with the layered inorganic compound, and can improve the heat resistance and mechanical strength of the resulting resin composition.

  Therefore, an alicyclic structure containing a polar group that can allow the alicyclic structure-containing polymer to be substantially hydrophobic while improving the heat resistance and mechanical strength of the resin composition. The content in the polymer is 0.8 mmol / g or less, preferably 0.5 mmol / g or less, more preferably 0.3 mmol / g or less. That is, when the polar group exceeds 0.8 mmol / g, the water absorption rate of the resin composition containing the alicyclic structure-containing polymer increases.

  Examples of the polar group include a hetero atom or an atomic group having a hetero atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a silicon atom, and a halogen atom. Among these heteroatoms, an oxygen atom and a nitrogen atom are preferable from the viewpoint of dispersibility and compatibility with an inorganic compound. Specific examples of the polar group include a hydroxyl group, a carboxyl group, an oxy group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyloxy group, a carbonyl group, an amino group, an ester group, a halogen group, a cyano group, and an amide group. , Imide group, silyl group, sulfone group, acid anhydride group and the like.

  The method for obtaining the alicyclic structure-containing polymer having a polar group is not particularly limited, but when it is a norbornene-based polymer that is a kind of alicyclic structure-containing polymer, for example, (1) various norbornene-based polymers A method of reacting (modifying) a compound having a polar group with an unmodified polymer obtained by polymerizing a norbornene-based monomer having no polar group, selected from monomers, (2) various norbornenes A method of copolymerizing a norbornene monomer having no polar group and a norbornene monomer having a polar group, selected from among the monomers, (3) selected from various norbornene monomers A polymer obtained by polymerizing a norbornene-based monomer having no polar group, and the polarity obtained by the method (1) or (2) And a method of mixing the norbornene-based polymer having a like. The alicyclic structure-containing polymer other than the norbornene polymer is the same as that of the norbornene polymer.

  In the present invention, a thermoplastic resin having a polar group may be used in combination with the alicyclic structure-containing polymer as long as the object of the present invention is not impaired. Examples of the thermoplastic resin having a polar group include a chlorinated product of a thermoplastic resin, a chlorosulfonated product, and a graft modified product of a polar group-containing unsaturated compound. Denatured products are preferred.

  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, methacrylic acid, α -Unsaturated carboxylic acid compounds such as ethyl acrylic acid, maleic acid, fumaric acid, itaconic acid; unsaturated carboxylic acid compounds such as maleic anhydride, chloromaleic anhydride, butenyl succinic anhydride; monomethyl maleate, dimethyl maleate, Unsaturated ester compounds such as glycidyl malate; unsaturated alcoholic compounds such as allyl alcohol, 2-allyl-6-methoxyphenol, 4-allyloxy-2-hydroxybenzophenone; chlorodimethylvinylsilane, tri Chill silylacetylene, 5-trimethylsilyl-1,3-cyclopentadiene, 3-trimethylsilylallyl alcohol, may be mentioned 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 inorganic compound. In order to efficiently copolymerize these polar group-containing unsaturated compounds, it is preferable to carry out a polymerization reaction in the presence of a general-purpose radical initiator. Examples of suitable radical initiators include organic peroxides, organic Examples include peresters.

  The polar group content is determined by the rate of introduction of the polar group by the reaction of the compound having a polar group in the method (1), and the copolymerization ratio of the monomer having a polar group in the method (2). Thus, in the method of (3), it can be adjusted by the mixing ratio of the polymer having no polar group and the polymer having a polar group.

  Further, the molecular weight of the thermoplastic resin in the present invention is not particularly limited, but is a weight average molecular weight in terms of polystyrene, usually 5,000 to 500,000, preferably 8,000 to 200,000, more preferably. 10,000 to 100,000. When the weight average molecular weight is in this range, the molding processability of the resulting resin composition is improved, and the mechanical strength can be improved. This weight average molecular weight can be measured by gel permeation chromatography using cyclohexane or toluene as a solvent.

  Further, the glass transition temperature (Tg) of the thermoplastic resin in the present invention is not particularly limited, but is usually 80 ° C. or higher, preferably 130 to 250 ° C. 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.

[Layered inorganic compound]
The layered inorganic compound used in the present invention is a compound having a polycrystalline layer structure in which the compound is in a state (layered) having a sheet structure arranged in a plane and the sheet structure is repeated in the vertical direction. . In this layered inorganic compound, a crystal layer is bonded to each other by ionic bond or hydrogen bond force, and a cation is interposed between crystal layers, and a negatively charged crystal layer is mutually connected to the cation. Can be roughly divided into those coupled by a weak electrostatic force.

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 ; oxidation of transition metals such as MoO ₃ and V ₂ O _5. Oxyhalides such as FeOCl, VOCl, CrOCl; hydroxides such as Zn (OH) ₂ , 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 ; Na ₂ U Uranates such as 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 O Etc. Bana Emissions _salt; KNb ₃ O _{3, K 4} niobate such _{Nb 6 O 17; Na 2 W} 4 O 13, Ag 4 W tungstates such as _{10 O 13; Mg 2 Mo 2} O 7, Cs 2 Mo Molybdate such as ₅ O ₁₆ , Cs ₂ Mo ₇ O ₂₂ , Ag ₄ Mo ₁₀ O ₃₃ ; vermiculite, halloysite, dioctahedral vermiculite, muscovite, Fi logo bytes, biotite, lepidolite, Baragonaito, tetrasilicic chromite, kaolinite, halloysite, _{dickite, H 2 SiO 5, H 2} Si 14 O 29 · 5H 2 Consists of silicates such as O or this silicate Minerals to be used.

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

  The average value of the major axis of the layered inorganic compound is usually 0.01 to 30 μm, preferably 0.02 to 10 μm, more preferably 0.03 to 5 μm. When the average value of the major axis in the layered inorganic compound is within the above range, the heat resistance and mechanical strength of the resin composition and the molded article are particularly excellent.

  In the resin composition of the present invention, the layered inorganic compound is preferably present in a state of being subjected to an organic treatment with an organic agent. By performing the organic treatment, it is possible to reduce the attractive force between the layers of the layered inorganic compound, not the layered inorganic compound itself, to increase the interlayer distance and separate the layers to form fine plate-like particles. it can. In the resin composition of the present invention, the fine plate-like particles are dispersed in a matrix which is a substantially nonpolar thermoplastic resin.

  This organic treatment can be performed using, for example, an organic agent described later.

  For the organic treatment of the layered inorganic compound, for example, a layered inorganic compound is dispersed in water to prepare a layered inorganic compound dispersion, and the cationic surfactant is added to the dispersion, and the mixture is heated at room temperature or under heating. This can be done by stirring. The concentration of the layered inorganic compound in the layered inorganic compound dispersion at this time is preferably adjusted to 0.01 to 70% by mass.

  The compounding ratio of the layered inorganic compound is 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the substantially nonpolar thermoplastic resin. When the compounding quantity of a layered inorganic compound exceeds the said upper limit, the transparency of the alicyclic structure containing polymer composition obtained will be reduced.

[Organizing agent]
Examples of the organic agent include a cationic surfactant. Specific examples of the cationic ^{surfactant, R 1 R 2 R 3 R} 4 N + X - quaternary ammonium salt represented by may be mentioned.

In R ¹ R ² R ³ R ⁴ N ⁺ X ⁻ , R ¹ , R ² , R ³ and R ⁴ in the organic onium ion R ¹ R ² R ³ R ⁴ N ⁺ may be the same, It may be different and represents a saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms. Examples of the saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, and nonyl. Group, decyl group, dodecyl group, hexadecyl group, octadecyl group and other saturated aliphatic hydrocarbon groups; lauryl group, oleyl group and other unsaturated aliphatic hydrocarbon groups; phenyl group, benzyl group and other aromatic hydrocarbon groups Can be mentioned. Examples of X ⁻ include anions such as Cl ⁻ , Br ⁻ , NO ₃ ⁻ , OH ⁻ , and CH ₃ COO ⁻ .

Organic onium ions R ¹ R ² R ³ R ⁴ N ⁺ include hexyl ammonium ion, octyl ammonium ion, 2-ethylhexyl ammonium ion, dodecyl ammonium ion, lauryl ammonium ion, octadecyl ammonium ion, stearyl ammonium ion, dioctyl dimethyl ammonium ion , Trioctylammonium ion, distearyldimethylammonium ion, stearyltrimethylammonium ion, ammonium laurate ion, or the like can be used.

In the resin composition according to the present invention, when the substantially nonpolar thermoplastic resin and the organic agent form a carbon-carbon covalent bond, a tertiary carbon atom is present in the molecular structure of the thermoplastic resin. Is contained, the organic onium ion in the cationic surfactant preferably has an unsaturated carbon chain having 6 or more carbon atoms. When the number of carbon atoms is less than 6, the hydrophilicity of the organic onium ion may increase and the compatibility with the guest molecule may decrease.
Examples of the organic onium ion having an unsaturated carbon chain having 6 or more carbon atoms include ammonium salts of alkenylamine. Examples of the alkenylamine include 1-hexenylamine, 1-dodecenylamine, 9-octadecenylamine (also referred to as oleylamine), 9,12-octadecadienylamine (also referred to as linoleamine), 9,12,15-octadeca Examples include trienylamine and linoleylamine (also called linoleylamine).

[Guest molecule]
The guest molecule has a polar group in the molecule. This polar group is one in which electrons are localized in the molecule of the guest molecule, causing a charge bias, and does not include completely polarized ions. Therefore, onium ions are not included in the polar group.

  Examples of the polar group possessed by the guest molecule include one or more selected from the group consisting of a hydroxyl group, a halogen group, a carboxyl group, an anhydrous carboxyl group, a thiol group, an epoxy group, and an amino group.

  The guest molecule preferably has a molecular weight of 100 to 1,000. When the molecular weight is less than 100, the crosslinking point in the guest molecule may be buried in the organic agent and the carbon-carbon covalent bond formation reaction with the substantially nonpolar thermoplastic resin may not easily occur. On the other hand, when the molecular weight exceeds 1,000, even if the substantially non-polar thermoplastic resin and the guest molecule form a carbon-carbon covalent bond, the free rotation part in the guest molecule becomes large, and finally It may not be possible to expect improvement in mechanical properties of the resin composition obtained.

  When the guest molecule is blended, the blending ratio is 3 to 20% by mass, preferably 5 to 20% by mass with respect to the layered inorganic compound. When the amount of guest molecules exceeds the upper limit, the physical properties of the resulting resin composition tend to be lowered. The compounding ratio of the layered inorganic compound is 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the substantially nonpolar thermoplastic resin. When the compounding quantity of a layered inorganic compound exceeds the said upper limit, the transparency of the alicyclic structure containing polymer composition obtained will be reduced.

  Suitable guest molecules have a structure similar to the hydrophobic portion in thermoplastics where the nonpolar portion present in the molecule is substantially nonpolar. For example, when the substantially non-polar thermoplastic resin is an olefin resin such as polyethylene and polypropylene, the nonpolar portion in the guest molecule is preferably a linear alkyl group. For example, when the substantially non-polar thermoplastic resin is an alicyclic structure-containing polymer, it is preferable that the guest molecule also has a nonpolar portion having an alicyclic structure.

  In order for the guest molecule to be bonded with a substantially non-polar thermoplastic resin and a carbon-carbon covalent bond, the guest molecule needs to have a crosslinking point. In this case, the thermoplastic resin preferably has tertiary carbon as a crosslinking point. In this case, the crosslinking point in the guest molecule is an unsaturated bond or a tertiary carbon.

  As a suitable example of the guest molecule having a polar group, a nonpolar portion and a crosslinking point as described above, for example, when the substantially nonpolar thermoplastic resin is an olefin resin, isobutyric acid, methacrylic acid, acrylic acid, and Oleic acid and the like. For example, when the substantially nonpolar thermoplastic resin is an alicyclic structure-containing polymer, ethyltetracyclododecanecarboxylic acid (formula (3)),

エチルテトラシクロドデカンアルコール（式（４））、

Ethyltetracyclododecane alcohol (formula (4)),

ビニルテトラシクロドデカンカルボン酸（式（５））、

Vinyltetracyclododecanecarboxylic acid (formula (5)),

ビニルテトラシクロドデカンアルコール（式（６））等を挙げることができる。

Examples thereof include vinyl tetracyclododecane alcohol (formula (6)).

  The resin composition of the present invention comprises (1) a layered inorganic compound, an organic agent, and a substantially nonpolar thermoplastic resin, and the organic agent and a substantially nonpolar thermoplastic resin; Are bonded by a carbon-carbon covalent bond, and an ionic part in the organic agent and the layered inorganic compound are ion bonded, or (2) a layered inorganic compound, an organic agent, substantially nonpolar And a guest molecule having a polar group, wherein the organic agent or guest molecule and a substantially nonpolar thermoplastic resin are bonded by a carbon-carbon covalent bond, The ionic part in the organic agent and the layered inorganic compound are ion-bonded or the polar group of the guest molecule and the layered inorganic compound are hydrogen-bonded.

  In the resin composition according to the present invention, the combination in which the substantially nonpolar thermoplastic resin and the organic agent or guest molecule form a carbon-carbon covalent bond is not particularly limited. It is preferable to form a carbon-carbon covalent bond between the tertiary carbon atom of the nonpolar thermoplastic resin and the nonpolar part of the organic agent or guest molecule. As a result, the substantially non-polar thermoplastic resin can be strongly anchored to the inorganic layered compound, and the resulting resin composition has properties close to those of an inorganic material such as heat resistance, high rigidity, and high elastic modulus. be able to.

  The carbon-carbon covalent bond combination includes (a) carbon-carbon sharing between the tertiary carbon atom in the substantially nonpolar thermoplastic resin and the tertiary carbon atom of the organic agent or guest molecule. (B) a carbon-carbon covalent bond between a tertiary carbon atom in the substantially nonpolar thermoplastic resin and a carbon atom having an unsaturated bond of the organic agent or guest molecule.

  The resin composition according to the present invention includes an organic agent or a guest molecule having a polar group and a substantially nonpolar thermoplastic resin bonded by a carbon-carbon covalent bond, and ions in the organic agent. It is necessary that the polar group of the guest molecule having an ionic bond or a polar group between the portion and the layered inorganic compound and the layered inorganic compound are hydrogen bonded.

As a method for confirming these bonds, (a) a method in which a chemical bond produced by the reaction is detected by an analytical method such as nuclear magnetic resonance (NMR) or infrared spectroscopy (IR);
(B) A method for confirming a change in solubility. For example, a method for confirming that the obtained resin composition is solubilized in a solvent in which the raw layered inorganic compound is not dissolved; (c) a method by extraction;

[Production of resin composition]
The method for producing the resin composition of the present invention is not particularly limited, but the organic agent and the substantially nonpolar thermoplastic resin, or the guest molecule and the substantially nonpolar thermoplastic resin are shared by radical reaction. It is preferable to form a bond (hereinafter referred to as “production method of the present invention”). By doing so, the substantially non-polar thermoplastic resin and the layered inorganic compound interact strongly, thereby improving physical properties, particularly heat resistance.

  Examples of the substantially nonpolar thermoplastic resin, the organic agent, and the guest molecule used in the production method of the present invention include the same as those described for the resin composition of the present invention. Among them, those having at least a tertiary carbon atom or a carbon-carbon unsaturated bond are preferable. By having at least a tertiary carbon atom or a carbon-carbon unsaturated bond, it becomes a crosslinking point and contributes to the bond with the resin, and the interaction between the layered inorganic compound and the resin can be strengthened and the physical properties can be improved. .

  In the production method of the present invention, a layered inorganic compound organically treated with an organic agent, a substantially nonpolar thermoplastic resin, an organic peroxide, and / or a guest molecule are mixed.

  As an aspect of mixing, (i) a layered inorganic compound organically treated with an organic agent, a substantially nonpolar thermoplastic resin, an organic peroxide, and / or a guest molecule is mixed with a Brabender, an extruder, a roll. (Ii) a layered inorganic compound organically treated with an organic agent, a substantially nonpolar thermoplastic resin, an organic peroxide, and / or a guest molecule in an organic solvent. The method of mixing is mentioned. Of these, the method (ii) is preferred because it can improve the dispersibility of the layered inorganic compound organically treated with the organic agent.

  Examples of the method for organically treating the layered inorganic compound with an organic agent include known methods, specifically, the method described in the column of the resin composition of the present invention.

  In the production method of the present invention, the organic agent or the guest molecule having a polar group and the practically nonpolar thermoplastic resin may contain at least 10% by mass of a tertiary carbon atom as the charged amount. preferable. If the tertiary carbon atom content is less than 10% by mass, the thermoplastic resin and the layered inorganic compound may be insufficiently crosslinked. The tertiary carbon content can be calculated from the structure of the monomer constituting the resin if it is a thermoplastic resin, and from the respective structures if it is an organic agent and guest molecule.

  The organic peroxide is not particularly limited as long as it generates a radical to be added to an unsaturated bond and can generate a radical by extracting hydrogen from tertiary carbon.

  Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, and the like.

  Among these, preferred organic peroxides include peroxyketals, dialkyl peroxides, peroxyesters and the like that have the ability to add to unsaturated bonds and the ability to extract hydrogen.

  Peroxyketals include 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t- Butylperoxy) -methylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane, n-butyl-4,4-di- (t-butylper And oxy) valerate and 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane.

  Dialkyl peroxides include di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumylper Examples thereof include oxado, di-t-hexyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3.

  Peroxyesters include cumylperoxyneodecanate, 1,1,3,3-tetramethylbutylperoxyneodecanate, 1-cyclohexyl-1-methylethylperoxyneodecanate, and t-hexylperoxyneoate. Decanate, t-butyl peroxyneodecanate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate, 2, 5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyiso Butyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanate, t-butylperoxylaur , 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butyl Peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-hexylperoxyacetate, t-butylperoxy-3-methylbenzoate, t-hexylperoxybenzoate, etc. It is done.

In the production method of the present invention, when the method (ii) is performed, the organic solvent to be used is not particularly limited, but an aromatic hydrocarbon organic solvent is preferable.
Further, in the case of carrying out by the above method (ii), the layered inorganic compound organically treated with an organic agent during mixing is a dispersion obtained by dispersing this in an organic solvent, a substantially nonpolar thermoplastic resin. Is preferably used as a dispersion by dispersing in an organic solvent.

  In the case of carrying out by the method (ii), there is no particular limitation on the apparatus for mixing and dispersing, and a known mixing and dispersing apparatus may be used.

  In the case of carrying out by the above method (ii), a layered inorganic compound organically treated with an organic agent, a substantially nonpolar thermoplastic resin, an organic peroxide, and / or a guest molecule are mixed in an organic solvent. It is preferable to provide a step of removing the solvent after preparing the mixed solution. The apparatus for removing the solvent is not particularly limited, and a known dryer such as a vacuum dryer or a thin film dryer may be used. The drying temperature is 100 to 350 ° C.

  In the case where the method (ii) is performed, the resin composition from which the solvent has been removed may be further melt-kneaded using a twin screw extruder or the like, in which case a thin film dryer is used as the dryer. It is also possible to continuously melt and knead the resin composition in a molten state discharged from the thin film dryer as it is supplied to the kneading zone of the twin screw extruder.

[Operation and effect of resin composition]
The operation and effect of the resin composition described above will be described below. 1 and 2 show conceptual diagrams of a resin composition according to the present invention. 1 and 2, 11 is a resin composition, 12 is a substantially nonpolar thermoplastic resin, 13 is a layered inorganic compound, 14 is an organic agent, and 15 is a guest molecule.

  In FIG. 1, a substantially nonpolar thermoplastic resin 12 and an organic agent 15 are cross-linked. The term “crosslinking” as used herein refers to a carbon-carbon covalent bond as shown in the above formula (1) or formula (2). This organic agent 14 restrains the layered inorganic compound 13. FIG. 2 shows a state in which the substantially nonpolar thermoplastic resin 12 and the guest molecule 15 are cross-linked. This guest molecule 15 is in a state of hydrogen bonding on the layered inorganic compound 13 in addition to the organic agent 14.

  Here, the layered inorganic compound 13 is organicized with the organic agent 14. Here, the layered inorganic compound is a compound having a polycrystalline layer structure in which the repetition of the sheet structure is observed in the straight direction (layered) having a sheet structure in which the inorganic compounds are arranged in a plane. The organic agent 15 is inserted (intercalated) between the layers of the layered inorganic compound, and the inorganic compound is dispersed at the nanometer level. This organic agent 15 is presumed to be bonded to the surface of the dispersed inorganic compound by exchanging cations.

  The organic agent 14 is bonded to the substantially nonpolar thermoplastic resin 12 by a carbon-carbon covalent bond. Therefore, the substantially nonpolar thermoplastic resin 12 is in a state of being firmly bonded to the layered inorganic compound 13.

  In the resin composition according to the present invention, the organically treated layered inorganic compound having a nano-order particle size is dispersed in a substantially non-polar thermoplastic resin. In addition, it has a light transmission performance equivalent to or higher than that of a thermoplastic resin containing no inorganic substance. In addition, a substantially non-polar thermoplastic resin is formed on the surface of the organically treated layered inorganic compound, since the ionic part in the organic agent and the ionic bond or the polar group in the guest molecule are hydrogen bonded. The nonpolar thermoplastic resin is constrained by the layered inorganic compound organically treated by the organic agent, and therefore the resin composition according to the present invention is excellent in heat resistance and mechanical properties.

[Molded body]
Various molded bodies are manufactured by molding the resin composition according to the present invention. Examples of the molded body include a backlight for LCD, a light guide plate for front light, and a light guide for which light transmission particularly in a long optical path is required. (A light diffusing agent is further added to the resin composition of the present invention), optical films, optical lenses, and the like. Examples of the optical lens include an Fθ lens for a laser beam printer, an imaging lens such as a camera or a mobile phone with a camera, a pickup lens for an optical information recording apparatus, and glasses.

  As a molding method of this molded body, a known molding method can be adopted according to various molded bodies.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited to the content of the Example.

(Production Example 1) Production Example of Smectite (o-SMT (DMDSA)) Organized with Dimethyldistearylammonium Ion Synthetic Smectite (Kunimine Kogyo Co., Ltd., Product Name Smecton SA, Average Major Diameter 0.05 μm) 100 parts by mass A smectite dispersion was prepared by uniformly dispersing in 1,000 parts by mass of distilled water at 0 ° C. Next, while stirring the smectite dispersion, a solution prepared by dissolving 100 parts by mass of dimethyl distearyl ammonium chloride (the content of tertiary carbon atom is 0% by mass) in 7,000 parts by mass of distilled water was slowly added. Stirring was continued at 60 ° C. for 3 hours, followed by filtration to separate a solid. This solid was washed twice with distilled water at 60 ° C. Water was removed by freeze-drying method to obtain smectite treated with dimethyl distearyl ammonium ion.

(Production Example 2) Production Example of Smectite Organized with Oleylammonium Ion ((o-SMT (OA))) Synthetic smectite (Kunimine Kogyo Co., Ltd., product name Smecton SA, average major axis 0.05 μm) 100 parts by mass A smectite dispersion was prepared by uniformly dispersing in 1000 parts by mass of distilled water at 0 ° C. Next, 50 parts by mass of oleylamine hydrochloride (the content of tertiary carbon atoms is 0% by mass) was slowly added to 7000 parts by mass of distilled water at 60 ° C., and stirring was continued at 60 ° C. for 3 hours. The solid was separated by filtration. This solid was washed twice with distilled water at 60 ° C. Water was removed by freeze-drying to obtain smectite treated with oleylammonium ions.

(Examples 1-4, Comparative Examples 1-4)
Hydrogenation of a ring-opening copolymer of ethylidenetetracyclododecane (hereinafter abbreviated as “ETD”) and tetracyclododecene (hereinafter abbreviated as “TCD”), which is a kind of alicyclic structure-containing polymer. (Copolymerization ratio is ETD / TCD = 60/40, tertiary carbon atom content is 44 mass%) (hereinafter abbreviated as “COP”) and polypropylene (manufactured by Nippon Polychem, “MA2”, 3 The content of secondary carbon atoms is 29 mass% (hereinafter abbreviated as “PP”) and smectite (hereinafter referred to as “o-SMT (DMDSA) treated with dimethyl distearyl ammonium ion obtained in Production Example 1”. ) ”, Smectite treated with oleylammonium ion obtained in Production Example 2 (hereinafter abbreviated as“ o-SMT (OA) ”), and ethyl tetracycline as a guest molecule. Table 1 shows dodecanecarboxylic acid (molecular weight 234, tertiary carbon atom content is 41 mass%), dicumyl peroxide, and oleic acid (molecular weight, tertiary carbon atom content is 0 mass%). After mixing in toluene and adding dropwise to isopropyl alcohol, the mixture was filtered and vacuum dried at 100 ° C. to obtain a resin composition.

(Reference example (polymer only))
A hydrogenated product (COP) and polypropylene (PP) of a ring-opening copolymer of ETD and TCD, which are a kind of alicyclic structure-containing polymer, were used as reference examples.

[Evaluation methods and results]
The resin composition was press-molded at a molding temperature of 200 ° C. to obtain a molded body having a thickness of 1 mm. Each molded body was evaluated for haze, total light transmittance, Vicat cut softening point, and tensile modulus. The evaluation method is as described below.

<Measurement of haze>
Based on the method of JIS K7105, it measured using the turbidimeter (NDH-300A, Nippon Denshoku Industries Co., Ltd.). The smaller the haze, the higher the transparency.

<Total light transmittance>
Using the resin compositions obtained in Examples, Comparative Examples, and Reference Examples, the total light transmittance was measured according to JIS K7105, a turbidimeter (NDH-300A, Nippon Denshoku). It was measured by an industrial company.

<Bickat softening point>
Using the resin compositions obtained in Examples, Comparative Examples, and Reference Examples, the measurement was performed with an HDT tester (manufactured by Toyo Seiki Seisakusyo) in accordance with JIS K7206.

<Tensile test>
Using the resin compositions obtained in Examples, Comparative Examples, and Reference Examples, tensile tests were performed under the following conditions. The results are shown in Table 2.

Test method: ISO 527 compliant
Measurement items: strength, elongation, elastic modulus
Test conditions: Elastic modulus measurement ... Test speed 1mm / min
Distance between marked lines ... 50mm
Distance between chucks ... 115mm
Strength, elongation measurement ... Test speed 50mm / min
Distance between chucks ... 115mm
Number of measurements ... n = 5
Test environment: 23 ± 2 ℃, 50 ± 5% RH
Testing machine: Instron 4302

  According to Table 2, it was found that the example had higher total light transmittance and higher Vicat cut softening point than the comparative example. Therefore, it was found that the transparency is good and the water absorption rate does not increase, so the Vicat cut softening point is also high.

  Moreover, according to this Table 2, it turned out that an Example has a large tensile elasticity modulus compared with a comparative example. Therefore, it turned out that rigidity is high.

FIG. 1 is a conceptual diagram of a resin composition according to an embodiment of the present invention. FIG. 2 is a conceptual diagram of a resin composition according to an embodiment of the present invention.

Explanation of symbols

11 Resin Composition 12 Substantially Nonpolar Thermoplastic Resin 13 Layered Inorganic Compound 14 Organizing Agent 15 Guest Molecule

Claims (5)

A layered inorganic compound, an organic agent, and a substantially nonpolar thermoplastic resin,
The organic agent and a substantially nonpolar thermoplastic resin are bonded by a carbon-carbon covalent bond,
A resin composition comprising an ionic portion in the organic agent and an ion-bonded layered inorganic compound. A layered inorganic compound, an organic agent, a substantially nonpolar thermoplastic resin, and a guest molecule having a polar group,
The organic agent or guest molecule and a substantially nonpolar thermoplastic resin are bonded by a carbon-carbon covalent bond,
A resin composition, wherein an ionic part in the organic agent and the layered inorganic compound are ion-bonded or a polar group of the guest molecule and the layered inorganic compound are hydrogen-bonded.   The resin according to claim 1 or 2, wherein the organic agent and the substantially nonpolar thermoplastic resin, or the guest molecule and the substantially nonpolar thermoplastic resin form a covalent bond by a radical reaction. A method for producing the composition.   The method for producing a resin composition according to claim 3, wherein the organomolecule or the guest molecule having a polar group and the substantially nonpolar thermoplastic resin contain at least 10% by mass of a tertiary carbon atom. . The method for producing a resin composition according to claim 3 or 4, wherein the organic agent or guest molecule contains a tertiary carbon atom or a carbon-carbon unsaturated bond.

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