JP2005082774A - Resin composition, molded product and process for producing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition excellent in mechanical strengths, to provide a molded product and to provide a process for producing the resin composition. <P>SOLUTION: The resin composition comprises a thermoplastic resin and a layered crystalline compound treated with an organizing agent having a polar group, wherein the resin composition of 1 mm in thickness has a haze of 10% at most. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resin composition, a molded body, and a method for producing a resin composition.

  Conventionally, optical materials are composed of resin compositions corresponding to various physical properties. As this resin composition, for example, a resin composition comprising a layered crystal compound and a resin is generally used. In order to improve various physical properties of the resin composition having such a structure, it is known that a technique of forming a bond between the resin and the layered crystal compound is effective.

  For example, it is effective to add a polar group to the organic agent treating the layered crystal compound to form a covalent bond or a hydrogen bond between the organic agent and the resin. However, a layered crystal compound treated with an organic agent having a polar group has a strong bond (affinity) between the layered crystal compounds and is inferior in dispersibility, so that a highly transparent resin composition cannot be obtained. Therefore, it cannot be suitably used as an optical material.

  Examples of the technique relating to the resin composition used in the optical material as described above include the following techniques. For example, an inorganic filler containing the step of contacting an organic cation with a layered compound, a step of swelling the contacted product with an organic solvent, and a step of kneading the swollen product with an elastomer A method for producing an elastomer is disclosed (see Patent Document 1).

  In addition, when the following component (a) (crystalline thermoplastic resin 100 parts by weight) and (b) (layered silicate 0.05 to 30 parts by weight) are melt kneaded at the following composition ratio, component (a) 1.4 parts by weight or more of component (c) organic solvent is added to 100 parts by weight, at least one vent port is provided in the kneader, and the organic solvent is removed by holding at least one vent port under reduced pressure. , A method for producing a crystalline thermoplastic resin composition characterized in that the organic solvent content of the final composition is less than 1% by weight (as described in Patent Document 2) (Patent Document 2). reference).

  Furthermore, “a resin composite material comprising a polymer and an organized clay, and an organic substance contained in the organized clay is bonded to the clay other than at the end of the longest molecular chain” (described in Patent Document 3) As for the resin composite material, there is an example in which an example in which this resin composite material is manufactured by a biaxial kneading method is disclosed (see Patent Document 3).

  “A resin composition comprising an alicyclic structure-containing polymer, a layered compound, and an antioxidant, wherein the weight ratio of the alicyclic structure-containing polymer to the layered compound is 99.99 / 0.00. A resin composition characterized in that the content of the antioxidant in the composition is in the range of 0.1 to 10% by weight ”(as described in Patent Document 4). ), Is disclosed (see Patent Document 4).

JP 08-302025 A (Claim 1) JP 09-48856 A (Claim 1) JP 2000-136308 A (Claim 1, [0060]) JP 2001-181483 A (Claim 1)

  However, the inventions according to Patent Documents 1 and 2 described above are techniques related to elastomers and crystalline resins, and have a problem that a mechanical composition having high mechanical strength and high transparency cannot be obtained.

  In addition, in the invention according to Patent Document 3 described above, an example manufactured by a biaxial kneading method is disclosed, but even with this method, a resin composition having high mechanical strength and high transparency is obtained. There is a problem that can not be.

  Furthermore, in the invention according to the above-mentioned Patent Document 4, mechanical strength is still insufficient, and a method for improving transparency is not disclosed, and transparency is still insufficient.

  An object of the present invention is to solve such conventional problems and to provide a resin composition, a molded article, and a method for producing the resin composition, which are excellent in mechanical strength.

  In order to solve the above problems, the resin composition of the present invention is a resin composition comprising a thermoplastic resin and a layered crystal compound treated with an organic agent having a polar group, and having a thickness. The haze at 1 mm is at most 10%.

  In the resin composition of the present invention, the thermoplastic resin is preferably a polymer resin having an alicyclic structure.

  In the resin composition of the present invention, the thermoplastic resin preferably has a water absorption rate of at most 0.15%.

  Moreover, the molded article of the present invention is formed by molding the resin composition.

  Furthermore, the method for producing a resin composition of the present invention is characterized by having a step of bringing a layered crystal compound treated with an organic agent having a polar group into contact with a solvent.

  According to the present invention, there is provided a resin composition comprising a thermoplastic resin and a layered crystal compound treated with an organic agent having a polar group, and the haze at a thickness of 1 mm is at most 10%. Therefore, it can be set as the resin composition excellent in mechanical strength. In the resin composition according to the present invention, the haze at a thickness of 1 mm is at most 10% because the layered crystal compound dispersed in the resin composition is fine and the layered crystal compound is in the resin composition. It shows that it is uniformly dispersed. Moreover, since the layered crystal compound dispersed in the resin composition has a polar group by the treatment with the organic agent, the layered crystal compound and the thermoplastic resin are firmly bonded in the resin composition. It is thought that it has been realized. Therefore, the resin composition according to the present invention has good transparency despite containing the layered crystal compound, and less scattering of light transmitted through the resin composition due to the presence of the giant particles. The mechanical strength of the resin composition itself can be increased.

[Resin composition]
A resin composition according to an embodiment of the present invention is a resin composition comprising a thermoplastic resin and a layered crystal compound treated with an organic agent having a polar group, and a haze at a thickness of 1 mm However, it is at most 10%. If the haze at a thickness of 1 mm exceeds 10%, the resin composition cannot obtain sufficient transparency and the mechanical strength becomes insufficient.

[Thermoplastic resin]
In the resin composition of the present invention, the water absorption of the thermoplastic resin is preferably at most 0.15%, more preferably at most 0.1%, particularly preferably at most 0.05%. Here, when the water absorption rate of the thermoplastic resin exceeds 0.15%, the performance may vary depending on the use environment. In addition, in order to make the water absorption rate of a thermoplastic resin into the said range, it can achieve by adjusting the kind or quantity of the polar group in a thermoplastic resin.

  Examples of the thermoplastic resin include a polymer resin having an alicyclic structure (hereinafter sometimes abbreviated as “alicyclic structure polymer”), a polyolefin resin, a polycarbonate resin, a polyester resin, and a polysulfone resin. And polyether polysulfone resins, polystyrene resins, polyvinyl alcohol resins, cellulose acetate resins, polyvinyl chloride resins, polyacrylate resins, and the like.

  Among these resins, an alicyclic structure polymer is particularly preferable from the viewpoint of high transparency and low birefringence. This alicyclic structure 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 polymer composition or a molded product obtained from the composition, a cycloalkane structure can be mentioned. Alkane structures are 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 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 polymer, Although it selects suitably according to the property, physical property, etc. of the resin composition obtained, Usually, 50 mass% As mentioned above, Preferably it is 70 mass% or more, More preferably, it is 90 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 polymer used for this invention may contain repeating units other than the repeating unit containing an alicyclic structure.

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

  Examples of the norbornene-based polymer (A) include ring-opening polymers of norbornene-based monomers, ring-opening copolymers of norbornene-based monomers and other monomers capable of ring-opening copolymerization with the norbornene-based monomers, 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 polymer composition.

Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and derivatives thereof (those having a substituent in the ring, the same shall apply hereinafter), tricyclo [4.3. 0 ^1,6 . 1 ^2,5 ] dodeca-3,7-diene (common name: dicyclopentadiene) and derivatives thereof, 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (conventional) 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 more of these substituents. Also 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 (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 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 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, copolymers such as block copolymers, and hydrides of aromatic rings thereof. Examples of the block copolymer include diblock, triblock or higher multiblock, and gradient block copolymer.

  In the present invention, since the affinity with an inorganic compound can be improved and the heat resistance can be improved without impairing the light transmittance of the molded product obtained from the resin composition, the thermoplastic resin to be used is used. Preferably has a polar group.

  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 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.

  Although there is no restriction | limiting in particular as a method to obtain the thermoplastic resin which has a polar group, When a thermoplastic resin is a norbornene-type polymer, for example, (1) Where selected from various norbornene-type monomers, 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, (2) selected from various norbornene-based monomers A method of copolymerizing a norbornene monomer having no polar group and a norbornene monomer having a polar group, (3) a norbornene monomer having no polar group selected from various norbornene monomers Polymer obtained by polymerization, and norbornene system having polar group obtained by the method of (1) or (2) And a method such as mixing and coalescence. The thermoplastic resin other than the norbornene polymer is the same as that of the norbornene polymer.

  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 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 inorganic compounds. 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 thermoplastic resin having a polar group used in the present invention preferably has a polar group content of at most 10 mmol / g, more preferably at most 5 mmol / g, more preferably at most 2.5 mmol / g. is there. The lower limit of the polar group content is 0.01 mmol / g. When the polar group content is within the above range, it is possible to achieve both improvement of the dispersibility of the inorganic compound and improvement of various physical properties such as water resistance of the obtained laminate.

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

  The molecular weight of the thermoplastic resin used in the present invention is not particularly limited, but the weight average molecular weight in terms of polystyrene is usually 5,000 to 500,000, preferably 8,000 to 200,000. Preferably, it is 10,000-100,000. 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 chromatographic method of cyclohexane solution or toluene solution.

  Further, the glass transition temperature (Tg) of the thermoplastic resin used 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 crystal compound]
The layered crystal compound 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 the layered crystal compound, the crystal layers are bonded to each other by van der Waals force or hydrogen bond force, and the cation is interposed between the crystal layers, and the negatively charged crystal layers are mutually connected. It can be roughly classified into those coupled by a weak electrostatic force through cations.

Specific examples of such layered crystal compounds include transition metal dichalcogenides such as graphite, TiS ₂ , NbSe ₂ and MoS ₂ ; transition metal dichalcogenides such as CrPS ₄ ; transitions such as MoO ₃ and V ₂ O _5. Metal oxides; 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 ) Phosphate such as ₃ · nH 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 ; Uranates 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 O _{Vanadate; KNb 3 O 3, K 4} Nb 6 niobate such _{O 17; Na 2 W 4 O} 13, Ag 4 tungstate such as _{W 10 O 13; Mg 2 Mo} 2 O 7, Cs 2 Molybdate such as Mo ₅ O ₁₆ , Cs ₂ Mo ₇ O ₂₂ , Ag ₄ Mo ₁₀ O ₃₃ ; montmorillonite, saponite, hydelite, hectorite, nontronite, stevensite, trioctahedral vermiculite, diocta polyhedral 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 silicates O etc. or Minerals composed of this silicate can be mentioned .

  Among these layered crystal 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, and silicates are particularly preferable. preferable.

Examples of the organic agent capable of organizing the layered crystal compound include cationic compounds such as ammonium salts and phosphonium salts, but the present invention uses a compound having a polar group in addition to the cationic part. Can be achieved. As the cationic compound, an ammonium salt represented by R ¹ R ² R ³ R ⁴ N ⁺ X ⁻ is preferable.

  Examples of the polar group include heteroatoms, atomic groups having heteroatoms, and the like. Examples of heteroatoms include oxygen atoms, nitrogen atoms, silicon atoms, and halogen atoms. Examples of the polar group 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, a sulfone group, and an isocyanate group.

In R ¹ R ² R ³ R ⁴ N ⁺ X ⁻ , R ¹ , R ² , R ³ , and R ⁴ may be the same or different and are each a saturated hydrocarbon having 1 to 30 carbon atoms. Represents a saturated hydrocarbon group having a group, an unsaturated hydrocarbon group, or a polar group in the side chain. Examples of the saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group. Groups, saturated aliphatic hydrocarbon groups such as dodecyl group, hexadecyl group and octadecyl group, unsaturated aliphatic hydrocarbon groups such as lauryl group and oleyl group, and aromatic hydrocarbon groups such as phenyl group and benzyl group. it can.

Examples of the saturated hydrocarbon group having a polar group in the side chain include a hydroxyl group-containing saturated hydrocarbon group such as a hydroxymethyl group and a hydroxyethyl group, a carboxy group-containing saturated hydrocarbon group such as a carboxymethyl group and a carboxyethyl group, and a mercaptomethyl group. And thiol group-containing saturated hydrocarbon groups such as mercaptoethyl groups. Examples of X ⁻ include anions such as Cl ⁻ , Br ⁻ , NO ₃ ⁻ , OH ⁻ , and CH ₃ COO ⁻ .

[Method for Producing Resin Composition]
The manufacturing method of the resin composition which concerns on one Embodiment of this invention has a process which makes the layered crystal compound processed with the organic agent which has a polar group contact a solvent.

As an aspect of this process,
(1) A mode of mixing a dispersion of an organically treated layered crystal compound dispersed in a solvent and a resin solution;
(2) A mode in which a resin is mixed in an organically treated layered crystal compound dispersion dispersed in a solvent;
(3) An embodiment in which the organically treated layered crystal compound dispersion dispersed in a solvent and the resin are melt-kneaded by reducing the pressure from the vent with a biaxial kneader.

  When the manufacturing method of the resin composition described above includes a step of bringing the layered crystal compound treated with the organic agent having a polar group into contact with a solvent, the haze can be set to 10% at most.

  The solvent used in the above production process is not particularly limited as long as it is inert to the polar part of the organophilic treatment agent and is liquid at room temperature. For example, aromatic hydrocarbons such as benzene, toluene and xylene, chain or cyclic aliphatic hydrocarbons such as heptane and cyclohexane, halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene and dichloromethane, dioxane, Ethers such as diethyl ether, ketones such as cyclohexanone and acetophenone, esters such as ethyl acetate and propiolactone, nitriles such as acetonitrile and benzonitrile, methanol, ethanol, n-propanol, isopropanol, n-butanol, Examples thereof include alcohols such as sec-butanol, nitrobenzene, sulfolane and the like. These can be used alone or as a mixture.

  Among them, a solvent that swells the organically treated layered crystal compound is particularly preferable. The swelling mentioned here refers to a phenomenon in which the organically treated layered silicate absorbs the organic solvent and increases its volume. The organically treated layered silicate and organic solvent having a swelling degree of 1 cc / g or more. The combination of is preferable. The swelling degree can be measured by the sedimentation volume method (clay handbook, page 513). Further, when the swellability of the organically treated layered silicate and the organic solvent is very good, the organically treated layered silicate swells indefinitely and does not settle, making measurement impossible. However, this state is the most preferred combination that swells very well.

  In the production method of the present invention, the amount of the layered crystal compound treated with the organic agent having a polar group and the solvent is not particularly limited, and when the total amount of the layered crystal compound and the solvent is 100 parts by mass, Is 0.01 to 90 parts by mass, preferably 1 to 40 parts by mass of a layered crystal compound.

[Molded body]
On the other hand, the molded body according to an embodiment of the present invention is formed by molding the resin composition. There is no restriction | limiting in particular as a shaping | molding method of a molded object, Solution casting method, melt extrusion molding method, press molding method, inflation molding method, injection molding method, blow molding method, stretch molding method etc. are mentioned.

  The molded product obtained in the present invention can be used for various applications. For example, (1) daily necessities such as windproof glass and window glass, (2) lenses used for automobile lamps, glasses, goggles, etc., (3) industrial parts such as camera parts, housings and containers of various instruments and devices, (4) Imaging system or projection system lens or mirror lens used in cameras, VTRs, copiers, OHPs, projections and printers, etc. (5) Magneto-optical disks, dye-based disks, compact discs for music, image music Information disc materials such as simultaneous recording / reproducing discs and memory discs, (6) Information recording / 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 waveguide films Information transfer parts such as connectors, (7) Light receiving element covers and prisms And the like of the optical components.

  When the molded body of the present invention is used in, for example, a liquid crystal display device, in general, a member such as a polarizing plate, a liquid crystal cell, and a retardation compensation plate such as a reflection plate or a retardation plate, if necessary, It is configured by combining and driving circuit.

  FIG. 1 shows a configuration example of a liquid crystal display device. In FIG. 1, 1 is a liquid crystal display device, 2 is a liquid crystal cell, 17 is a reflector, 21 is a liquid crystal substrate, 22 is a transparent conductive film, 23 is an alignment film, 24 is a liquid crystal, and 25 is a spacer. , 26 represents a sealing material, 31 represents an upper polarizing plate, and 32 represents a lower polarizing plate.

  FIG. 1 shows a schematic view of a reflective liquid crystal display device provided with a reflective plate 17, but the laminate of the present invention is not limited to the reflective type, and can be applied to a transmissive liquid crystal display device. be able to. In the transmissive liquid crystal display device, a backlight unit is arranged instead of the reflector.

  The liquid crystal display device 1 includes a liquid crystal cell 2 and polarizing plates 31 and 32. In the liquid crystal cell 2, two liquid crystal substrates 21 on which a transparent conductive film 22 made of an ITO (indium oxide / tin) film and an alignment film 23 are formed are arranged to face each other. A liquid crystal 24 is sealed together with spacers 25 such as plastic beads dispersed in an appropriate number in a space sealed by a sealing material 26 formed on both end surfaces 21. Further, the upper polarizing plate 31 is attached to the lower polarizing plate 32, and the reflection plate 17 is laminated on the lower polarizing plate 32.

  In the case of a reflective liquid crystal display device, although two polarizing plates 31 and 32 are provided in FIG. 1, the reflective liquid crystal display device may be composed of only the upper polarizing plate 31. Examples of the material of the polarizer film include a multi-halogen polarizing film, a dye polarizing film, and a metal polarizing film, and any film can be used as the polarizer layer for the polarizing plates 31 and 32.

  The spacer 25 is a member for keeping the gap between the alignment films 23, that is, the gap between cells constant, and usually plastic beads, silica spheres, or the like are used. As the transparent conductive film 22, an ITO film is usually used. The alignment film 23 determines the display performance of the liquid crystal display device, and a polyimide resin is usually used as this material.

According to this embodiment as described above, the following effects are obtained.
(1) A resin composition comprising a thermoplastic resin and a layered crystal compound treated with an organic agent having a polar group, and the haze at a thickness of 1 mm is at most 10%. It can be set as the resin composition excellent in mechanical strength.

  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. In the present specification, “part” means part by mass unless otherwise specified.

[Production Example 1]
(Norbornene polymer 1 (no polar group))
In a nitrogen atmosphere, 500 parts of dehydrated cyclohexane, 0.82 part of 1-hexene, 0.15 part of dibutyl ether and 0.30 part of triisobutylaluminum were mixed in a reactor at room temperature, and then maintained at 45 ° C. while maintaining tetracyclo [4.4.0.1 ^{2 , 5.1 7,10} ] -dodec-3-ene (tetracyclododecene, hereinafter abbreviated as “TCD”), 80 parts, and 7,8-benzotricyclo [4.3.0.1 ^2,5 ] deca-3 -120 parts of ene (methanotetrahydrofluorene, hereinafter abbreviated as "MTF") and 80 parts of tungsten hexachloride (0.7 mass% toluene solution) were continuously added and polymerized over 2 hours.

  To the polymerization solution, 1.06 part of butyl glycidyl ether and 0.52 part of isopropyl alcohol were added to inactivate the polymerization catalyst, and the polymerization reaction was stopped to obtain a reaction solution containing a ring-opening polymer.

  Next, 270 parts of cyclohexane is added to 100 parts of the reaction solution containing the obtained ring-opening polymer, and 5 parts of a nickel-alumina catalyst (manufactured by JGC Chemical Co., Ltd.) is added as a hydrogenation catalyst. The reaction solution containing 20% by mass of TCD / MTF ring-opening copolymer hydride was obtained by pressurizing, heating to 200 ° C. with stirring, and reacting for 4 hours.

  After removing the hydrogenation catalyst by filtration, an antioxidant (manufactured by Ciba Specialty Chemicals Co., Ltd .: Irganox 1010) is added to the resulting solution to make 0.1 part with respect to 100 parts of the polymer and dissolved. It was.

  Next, using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.) at a temperature of 270 ° C. and a pressure of 1 kPa or less, the hydride is melted from the extruder into a strand while removing cyclohexane and other volatile components. Extruded, cooled and pelletized to collect pellets. The hydrogenated ring-opening copolymer containing no polar group had a weight average molecular weight of 34,000, a hydrogenation rate of 99.9%, and a Tg of 160 ° C.

[Production Example 2]
(Norbornene polymer 2 (with polar group))
In a nitrogen atmosphere, 500 parts of dehydrated cyclohexane, 0.82 part of 1-hexene, 0.15 part of dibutyl ether, and 0.30 part of triisobutylaluminum were mixed in a reactor at room temperature, and then maintained at 45 ° C. while maintaining 8-ethylidene-tetracyclo [ 4.4.0.1 ^2,5 .1 ^7,10] - (hereinafter abbreviated as "ETCD") dodeca-3-ene and 100 parts of a tungsten hexachloride (0.7 wt% toluene solution) 40 parts, over 2 hours Continuously added and polymerized.

  To the polymerization solution, 1.06 part of butyl glycidyl ether and 0.52 part of isopropyl alcohol were added to inactivate the polymerization catalyst, and the polymerization reaction was stopped to obtain a reaction solution containing a ring-opening polymer.

  Next, 270 parts of cyclohexane is added to 100 parts of the reaction solution containing the obtained ring-opening polymer, and 5 parts of a nickel-alumina catalyst (manufactured by JGC Chemical Co., Ltd.) is added as a hydrogenation catalyst. A reaction solution containing 20% by mass of a hydrogenated ETCD ring-opening copolymer was obtained by applying pressure, heating to 200 ° C. with stirring, and reacting for 4 hours.

  After removing the hydrogenation catalyst by filtration, an antioxidant (manufactured by Ciba Specialty Chemicals Co., Ltd .: Irganox 1010) is added to the resulting solution to make 0.1 part with respect to 100 parts of the polymer and dissolved. It was.

  Next, using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.) at a temperature of 270 ° C. and a pressure of 1 kPa or less, the hydride is melted from the extruder into a strand while removing cyclohexane and other volatile components. Extruded, cooled and pelletized to collect pellets. The ETCD ring-opening copolymer hydride having no polar group had a weight average molecular weight of 40,000, a hydrogenation rate of 99.9%, and a Tg of 138 ° C.

Next, 10 parts of maleic anhydride, 3 parts of dicumyl peroxide, and 230 parts of tert-butylbenzene were mixed with 100 parts of the obtained ETCD ring-opening polymer hydride, and 135 ° C for 6 hours in an autoclave. After the reaction, precipitation was made by adding it in a large amount of isopropyl alcohol, and the resin was recovered by filtration. The recovered resin was dried at 100 ° C. and 1 Torr or less for 48 hours to obtain 105 parts of a maleic anhydride-modified polymer. The resulting maleic anhydride-modified polymer had a weight average molecular weight of 65,000, Tg of 135 ° C., and ¹ H-NMR measurement. The amount of maleic anhydride modification was 0.45 mmol / g.

[Production Example 3]
(Organization treatment of saponite (treatment with an organic agent having a polar group))
100 parts of saponite (long average value: 0.05 μm) as a layered crystal 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 obtained by dissolving 20 parts of dodecyldihydroxyethylmethylammonium chloride in 300 parts of distilled water was slowly added, and stirring was continued at 60 ° C. for 3 hours. I took it out.

  The obtained solid was added to 500 parts of distilled water at 60 ° C. and redispersed, and then the solid was taken out again by filtration. After redispersion and filtration were repeated three times, water was removed by freeze-drying to obtain an organically treated saponite.

[Production Example 4]
(Organization treatment of saponite (treatment with an organic agent having no polar group))
100 parts of saponite (long average value: 0.05 μm) as a layered crystal compound was uniformly dispersed in 1000 parts of distilled water at 60 ° C. to obtain a saponite dispersion.

  Next, while stirring the saponite dispersion, slowly add a solution obtained by dissolving 20 parts of dimethyl distearyl ammonium chloride in 300 parts of distilled water and continue stirring at 60 ° C. for 3 hours, and then take out the solid matter by filtration. It was.

  The obtained solid was added to 500 parts of distilled water at 60 ° C. and redispersed, and then the solid was taken out again by filtration. After redispersion and filtration were repeated three times, water was removed by freeze-drying to obtain an organically treated saponite.

[Example 1]
In a solution obtained by dispersing 5 parts of the organically treated saponite obtained in Production Example 3 in 100 parts of tetrahydrofuran, 140 parts of norbornene polymer having no polar group obtained in Production Example 1 and polar group obtained in Production Example 2 A solution prepared by dissolving 25 parts of the norbornene-based polymer 25 in 300 parts of toluene is mixed, and the mixed solution is mixed with a high-speed swirling disperser (manufactured by Tokushu Kika Kogyo Co., Ltd .: Filmix FM80-50) at a tip speed of 20 m Distributed processing at a rate of / sec.

  Next, a hydride is extruded from the extruder in a molten state in a molten state while removing toluene as a solvent at a temperature of 270 ° C. and a pressure of 1 kPa or less using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.), pelletized after cooling. By collecting the pellets, a norbornene polymer composition 1 was obtained. The water absorption rate of the norbornene polymer of the composition was 0.08%.

Next, a sample having a thickness of 1 mm was prepared by hot pressing the obtained norbornene-based polymer composition 1 at 200 ° C., and the haze of the molded body was measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.). However, the haze was 4.0%. Moreover, when the heat distortion temperature and gas barrier property of the obtained norbornene polymer composition 1 were measured, the heat distortion temperature (according to ASTM D-648) was 174 ° C., and the gas barrier property (according to ASTM D-3985-81). ) Was 30 ml · mm / m ² · day.

[Example 2]
A mixture obtained by adding 10 parts of tetrahydrofuran to 10 parts of the organically treated saponite obtained in Production Example 3, and 70 parts of norbornene polymer having no polar group obtained in Production Example 1 and the polar group obtained in Production Example 2 Contains a mixture of 20 parts of norbornene polymer 2 with 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 / Time), the resin composition was extruded into a strand while removing the solvent from the vent under reduced pressure, cooled with water, cut with a pelletizer, and pelletized to obtain a norbornene polymer composition 2. The water absorption of the norbornene polymer of the composition was 0.10%.

Next, a sample having a thickness of 1 mm was prepared by hot pressing the obtained norbornene-based polymer composition 2 at 200 ° C., and the haze of the molded body was measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.). However, the haze was 2.5%. Moreover, when the heat distortion temperature and gas barrier property of the obtained norbornene polymer composition 2 were measured, the heat distortion temperature (according to ASTM D-648) was 176 ° C., and the gas barrier property (according to ASTM D-3985-81). ) Was 22 ml · mm / m ² · day.

[Comparative Example 1]
Mixture obtained by adding 10 parts of tetrahydrofuran to 10 parts of the organically treated saponite obtained in Production Example 4, and 70 parts of norbornene polymer having no polar group obtained in Production Example 1 and the polar group obtained in Production Example 2 Contains a mixture of 20 parts of norbornene polymer 2 with 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 / Time), the resin composition was extruded into a strand while removing the solvent from the vent under reduced pressure, cooled with water, cut with a pelletizer, and pelletized to obtain a norbornene polymer composition 3. The water absorption of the norbornene polymer of the composition was 0.10%.

Next, a sample having a thickness of 1 mm was prepared by hot pressing the obtained norbornene-based polymer composition 3 at 200 ° C., and the haze of the molded body was measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.). However, the haze was 2.2%. Further, when the thermal deformation temperature and gas barrier property of the obtained norbornene polymer composition 3 were measured, the thermal deformation temperature (according to ASTM D-648) was 144 ° C., and the gas barrier property (according to ASTM D-3985-81). ) Was 62 ml · mm / m ² · day.

[Comparative Example 2]
10 parts of organically treated saponite obtained in Production Example 3, 70 parts of norbornene polymer 1 having no polar group obtained in Production Example 1, and 20 parts of polar group-containing norbornene polymer 2 obtained in Production Example 2 Using a twin-screw 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) Then, the mixture was cooled with water, cut with a pelletizer, and pelletized to obtain a norbornene polymer composition 4.

Next, the obtained norbornene polymer composition 4 was hot-pressed at 200 ° C. to prepare a sample having a thickness of 1 mm, and the haze of the molded body was measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.). However, the haze was 17.0%. Moreover, when the thermal deformation temperature and gas barrier property of the obtained norbornene polymer composition 4 were measured, the thermal deformation temperature (according to ASTM D-648) was 152 ° C., and the gas barrier property (according to ASTM D-3985-81). ) Was 55 ml · mm / m ² · day.

[Example 3]
The pellet obtained in Example 1 was dried at 70 ° C. for 2 hours using a hot air dryer in which air was circulated, and then the pellet was screwed to a single screw extruder (manufactured by Nippon Steel Works, cylinder inner diameter: 50 mm). Using a screw L / D = 28), a film having a thickness of 200 μm was prepared from a coat hanger type T die having a width of 650 mm by melt extrusion at a molten resin temperature of 280 ° C.

  A liquid crystal substrate was prepared by forming an ITO (indium oxide / tin) film having a thickness of 0.16 μm at 40 ° C. on one surface of the obtained substrate by ion plating. Next, a transparent electrode was patterned on the liquid crystal substrate by photolithography to form a transparent electrode pattern. Then, after an alignment film was printed on the transparent electrode base pattern, alignment treatment was performed by rotational rubbing using a rayon cloth so as to obtain a STN mode liquid crystal with a twist of 250 degrees. The counter substrate was produced in the same manner.

An ultraviolet curable sealing resin mixed with 1.0% by mass of glass fiber was prepared, and the ultraviolet curable sealing resin was printed on the peripheral portion of one substrate. On the other substrate, resin beads having a predetermined diameter were dispersed at a rate of 200 pieces / mm ² . Then, both substrates were bonded and the sealing resin was cured by ultraviolet irradiation. Thereafter, a mixed liquid crystal in which a predetermined amount of a chiral agent was mixed with an ester nematic liquid crystal with n = 0.14 was vacuum-injected and sealed with an ultraviolet curable resin.

And after hardening by ultraviolet irradiation, it heat-processed and completed the liquid crystal cell. Next, when a liquid crystal display device as shown in FIG. 1 was produced and the display state was observed, the display state of the liquid crystal display device was good. The luminance of the liquid crystal display device was 200 cd / m ² .

  Next, after leaving the produced liquid crystal cell alone for 60 hours at 60 ° C. and 80% humidity, a liquid crystal display device as shown in FIG. 1 was produced again and the display state was observed. The condition was good.

[Comparative Example 3]
The pellet obtained in Comparative Example 1 was subjected to the same operation as in Example 3 to obtain Comparative Example Liquid Crystal Cell 1. Next, when a liquid crystal display device as shown in FIG. 1 was produced and the display state was observed, the display state of the liquid crystal display device was good. The luminance of the liquid crystal display device was 195 cd / m ² .

  Next, after only the comparative example liquid crystal cell 1 was allowed to stand for 200 hours under conditions of 60 ° C. and 80% humidity, a liquid crystal display device as shown in FIG. 1 was produced again and the display state was observed. It was noticeable.

[Comparative Example 4]
The pellet obtained in Comparative Example 2 was subjected to the same operation as in Example 3 to obtain Comparative Example Liquid Crystal Cell 2. Next, when a liquid crystal display device as shown in FIG. 1 was produced and the display state was observed, the luminance unevenness of the liquid crystal display device was noticeable. When the luminance of the liquid crystal display device was measured, it was as extremely low as 110 cd / m ² .

  When the above Examples 1 and 2 are compared with Comparative Examples 1 and 2, the resin compositions according to the examples are excellent in terms of the heat distortion temperature, and therefore are resistant to external thermal shocks, etc. It can be seen that the mechanical strength is excellent. Moreover, it turns out that it is excellent also in gas barrier property.

  Further, when Example 3 is compared with Comparative Examples 3 and 4, it can be seen that the liquid crystal display device according to the example is excellent in terms of luminance and display state, and thus has excellent optical characteristics.

FIG. 1 shows a cross-sectional view of a liquid crystal display device according to an embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Liquid crystal display device 2 Liquid crystal cell 17 Reflector 21 Liquid crystal substrate 22 Transparent conductive film 23 Alignment film 24 Liquid crystal 25 Spacer 26 Sealing material 31 Upper polarizing plate 32 Lower polarizing plate

Claims (5)

A resin composition comprising a thermoplastic resin and a layered crystal compound treated with an organic agent having a polar group,
A resin composition having a haze at a thickness of 1 mm of at most 10%.   The resin composition according to claim 1, wherein the thermoplastic resin is a polymer resin having an alicyclic structure.   The resin composition according to claim 1 or 2, wherein the thermoplastic resin has a water absorption rate of at most 0.15%.   A molded article obtained by molding the resin composition according to any one of claims 1 to 3. The method for producing a resin composition according to claim 1, further comprising a step of contacting the layered crystal compound treated with the organic agent having a polar group with a solvent.

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