Organic-inorganic composite composition and molded article made of the same

Abstract

To provide an organic inorganic composite composition having good transparency, mechanical properties, and low dielectric characteristics, and a molding composed of the same.SOLUTION: An organic inorganic composite composition contains a thermoplastic resin (A) and inorganic fine particles (B), in which when the total of the organic inorganic composite composition is 100 mass%, a content of the inorganic fine particles (B) is 8 mass% or less, and an average particle diameter of the inorganic fine particles (B) in the organic inorganic composite composition is 1-85 nm.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an organic-inorganic composite composition in which inorganic fine particles are dispersed in a thermoplastic resin, and to a molded article made of the same. [Background technology]

[0002] In recent years, the signal band of information and communication devices such as mobile phones has become increasingly higher in frequency. As radio waves become higher in frequency, the dielectric properties of dielectrics become important in reducing loss during high-frequency propagation. Since heat loss within a dielectric is proportional to the loss factor, which is expressed as the product of the dielectric constant and the dielectric loss tangent, low dielectric properties are required for materials that make up devices that handle high-frequency signals.

[0003] In general, the dielectric properties of a resin material are determined by the molecular structure of its constituent units, so one approach to lowering the dielectric constant is to design the molecular skeleton. However, there is a limit to how much the dielectric constant can be reduced by controlling the molecular skeleton, and changes to the molecular skeleton can cause problems such as changes in the strength of the resin molded product.

[0004] As another attempt to lower the dielectric constant, various methods of blending inorganic fillers have been proposed (Patent Document 1). Although this method can lower the dielectric constant to some extent by adding an inorganic filler with low dielectric properties, it requires the addition of a large amount of inorganic filler, which has problems such as reduced transparency and mechanical properties. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2010-129387 A Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, an object of the present invention is to provide an organic-inorganic composite composition having excellent transparency and a low dielectric constant without causing a decrease in the inherent mechanical properties of the resin by dispersing a very small amount of inorganic fine particles in a thermoplastic resin, and a molded article made of the same. [Means for solving the problem]

[0007] As a result of extensive research, the inventors have surprisingly found that an organic-inorganic composite composition in which a specific amount of inorganic fine particles having a specific particle size is blended with a thermoplastic resin has good transparency and low dielectric properties, and have thus completed the present invention. That is, according to the present invention, the following (Configuration 1) to (Configuration 10) are provided.

[0008] (Configuration 1) An organic-inorganic hybrid composition comprising a thermoplastic resin (A) and inorganic fine particles (B), characterized in that, when the entire organic-inorganic hybrid composition is taken as 100 mass%, the content of the inorganic fine particles (B) is 8 mass% or less, and the average particle diameter of the inorganic fine particles (B) in the organic-inorganic hybrid composition is 1 to 85 nm. (Configuration 2) Inorganic particles (B) are ZrO 2 (Zirconium oxide), TiO 2 (Titanium oxide), SnO 2 (Tin oxide), SiO 2 (Silicon oxide), Al 2 O 3 2. The organic-inorganic hybrid composition according to item 1, wherein the inorganic oxide is at least one selected from the group consisting of aluminum oxide, ZnO (zinc oxide), and MgO (magnesium oxide). (Configuration 3) 3. The organic-inorganic hybrid composition according to item 1 or 2 above, wherein the inorganic fine particles (B) are modified with a surface modifying agent. (Configuration 4) 4. The organic-inorganic hybrid composition according to item 3 above, wherein the surface modifier has an acidic functional group. (Configuration 5) 5. The organic-inorganic hybrid composition according to item 4 above, wherein the acidic functional group is at least one acidic functional group selected from the group consisting of a sulfonic acid group, a phosphonic acid group, a phosphinic acid group, and a carboxylic acid group. (Configuration 6) 6. The organic-inorganic hybrid composition according to any one of items 3 to 5 above, wherein the content of the surface modifier is 1 to 30% by mass relative to 100% by mass of the inorganic fine particles (B). (Configuration 7) 7. The organic-inorganic hybrid composition according to any one of items 1 to 6 above, wherein the thermoplastic resin (A) is an acrylic resin or a polycarbonate resin. (Configuration 8) Inorganic fine particles (B) are ZrO 2 8. The organic-inorganic hybrid composition according to any one of items 1 to 7 above, wherein the organic compound is (zirconium oxide). (Configuration 9) 9. A molded article obtained by using the organic-inorganic hybrid composition according to any one of items 1 to 8 above. (Configuration 10) 9. A film or sheet obtained by using the organic-inorganic hybrid composition according to any one of items 1 to 8 above. Effect of the Invention

[0009] The organic-inorganic hybrid composition of the present invention exhibits good transparency and low dielectric constant by adding a specific amount of inorganic fine particles having a specific particle size. [Brief description of the drawings]

[0010] [Figure 1] The photograph in FIG. 1 shows a TEM image of the organic-inorganic composite composition prepared in Example 4. [Diagram 2] The photograph in FIG. 2 shows a TEM image of the organic-inorganic composite composition prepared in Comparative Example 4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention is an organic-inorganic hybrid composition comprising a thermoplastic resin (A) and inorganic fine particles (B), characterized in that, when the entire organic-inorganic hybrid composition is taken as 100 mass%, the content of the inorganic fine particles (B) is 8 mass% or less, and the average particle diameter of the inorganic fine particles (B) is 1 to 85 nm.

[0012] The present invention will now be described in further detail.

[0013] <<Thermoplastic resin (A)>> Specific examples of the thermoplastic resin (A) include polyvinyl chloride resin, polystyrene resin, ABS resin, AS resin, acrylic resin, very low density polyethylene, low density polyethylene resin, linear low density polyethylene resin, medium density polyethylene resin, high density polyethylene resin, very high density polyethylene resin, polypropylene resin, polycarbonate resin, polyphenylene ether resin, nylon 6 resin, nylon 66 resin, aramid resin, polyacetal resin, polyester resin, polysulfone resin, polyacetal resin, polyetherimide resin, polyimide resin, polylactic acid resin, polyether ether ketone resin, polyphenylene sulfide resin, polyamide imide resin, liquid crystal polymer resin, polytetrafluoroethylene resin, polychlorotrifluoroethylene resin, polyvinylidene fluoride resin, vinylidene chloride resin, cyclic polyolefin resin, polyvinyl acetate resin, polyurethane resin, and copolymers and mixtures of various polymeric substances. These thermoplastic resins may be used alone or in combination of two or more.

[0014] Among the above thermoplastic resins, polyphenylene ether resin, polyphenylene sulfide resin, polystyrene resin, polyester resin, polycarbonate resin, acrylic resin, and cyclic polyolefin resin are preferred, polyester resin, polycarbonate resin, acrylic resin, and cyclic polyolefin resin are more preferred, and polycarbonate resin and acrylic resin are particularly preferred.

[0015] <Polycarbonate resin> The monomer used in the polycarbonate resin preferably used in the present invention may be any of aromatic diol compounds, aliphatic diol compounds, and alicyclic diol compounds, and examples thereof include the diol compounds described in WO 2004 / 111106 and WO 2011 / 021720, and oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol. These diol compounds may be used alone or in combination of two or more kinds.

[0016] The aromatic diol compound is preferably one containing a structural unit represented by the following formula (1).

[0017] [ka]

[0018] In the above formula (1), R 1 and R 2 R is independently at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. 1 and R 2 When there are a plurality of each of the above, they may be the same or different.

[0019] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0020] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, etc. An alkyl group having 1 to 6 carbon atoms is preferred.

[0021] Examples of the alkoxy group having 1 to 18 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, an octoxy group, etc. An alkoxy group having 1 to 6 carbon atoms is preferred.

[0022] Cycloalkyl groups having 6 to 20 carbon atoms include cyclohexyl and cyclooctyl groups. A cycloalkyl group having 6 to 12 carbon atoms is preferred.

[0023] Preferred examples of the cycloalkoxy group having 6 to 20 carbon atoms include a cyclohexyloxy group, a cyclooctyloxy group, etc. A cycloalkoxy group having 6 to 12 carbon atoms is preferred.

[0024] Examples of the alkenyl group having 2 to 10 carbon atoms include a methenyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, etc. An alkenyl group having 2 to 6 carbon atoms is preferred.

[0025] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, etc. Examples of the aryloxy group having 6 to 14 carbon atoms include a phenyloxy group, a naphthyloxy group, etc.

[0026] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenylethyl group, etc. Examples of the aralkyloxy group having 7 to 20 carbon atoms include a benzyloxy group, a phenylethyloxy group, etc.

[0027] e and f each independently represents an integer of 1 to 4.

[0028] W is a single bond or at least one group selected from the group consisting of groups represented by the following formula (2).

[0029] [ka]

[0030] In the above formula (2), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

[0031] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, etc. An alkyl group having 1 to 6 carbon atoms is preferred.

[0032] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group. These may be substituted. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and a butyl group.

[0033] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.

[0034] R 19 and R 20 are each independently a hydrogen atom, a halogen atom, or a group having 1 to 18 carbon atoms. It represents at least one group selected from the group consisting of an alkyl group, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are a plurality of groups, they may be the same or different.

[0035] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0036] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, etc. An alkyl group having 1 to 6 carbon atoms is preferred.

[0037] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. An alkoxy group having 1 to 6 carbon atoms is preferred.

[0038] Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group, a cyclooctyl group, etc. A cycloalkyl group having 6 to 12 carbon atoms is preferred.

[0039] Examples of the cycloalkoxy group having 6 to 20 carbon atoms include a cyclohexyloxy group, a cyclooctyl group, etc. A cycloalkoxy group having 6 to 12 carbon atoms is preferred.

[0040] Examples of the alkenyl group having 2 to 10 carbon atoms include a methenyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, etc. An alkyl group having 1 to 6 carbon atoms is preferred.

[0041] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, etc. Examples of the aryloxy group having 6 to 14 carbon atoms include a phenyloxy group, a naphthyloxy group, etc.

[0042] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenylethyl group, etc. Examples of the aralkyloxy group having 7 to 20 carbon atoms include a benzyloxy group, a phenylethyloxy group, etc.

[0043] g is an integer of 1 to 10, and preferably an integer of 1 to 6. h is an integer of 4 to 7, and preferably an integer of 4 to 5.

[0044] Examples of the aromatic diol compound represented by the above formula (1) include 4,4'-biphenol, 3,3',5,5'-tetrafluoro-4,4'-biphenol, α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (hereinafter sometimes abbreviated as "BPM"), α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, and α,α'-bis(4-hydroxyphenyl)-m-bis(1,1,1,3,3,3-hexafluoroisopropyl)benzene. Zene, 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter sometimes abbreviated as "BPZ"), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "BPTMC"), 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "BPOCTMC"), 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1, 1-Bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(3-fluoro-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)perfluorocyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-diphenylsulfide, 4,4'-dihydroxy-3,3'-diphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenylsulfone, 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes abbreviated as "BPA"), 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter sometimes abbreviated as "BPC"), 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane (hereinafter sometimes abbreviated as "BP26XA"), 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2 -Bis(4-hydroxyphenyl)butane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(3-methyl-4-hydroxyphenyl)decane, 1,1-bis(2,3-dimethyl-4-hydroxyphenyl)decane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 2,2-bis(4-hydroxyphenyl)butane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(3-methyl-4-hydroxyphenyl)decane, 1,1-bis(2,3-dimethyl-4-hydroxyphenyl)decane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, Bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (hereinafter sometimes abbreviated as "BPAF"), 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane, 7,7'-dimethyl-6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane, 7,7'-diphenyl-6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane, 2,2-bis(4-hydroxy-3-methylphenyl)-1,1,1,3,3,3-hexafluoropropane (hereinafter sometimes abbreviated as "BPAF"), 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3-fluoro-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, and 2,2-bis(3,5-difluoro-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, and 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane. These aromatic diol compounds may be used alone or in combination of two or more.

[0045] Aliphatic diol compounds include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl-1, Examples of the aliphatic diol compounds include 3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, 1,2-octyl glycol, 2-ethyl-1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, etc. These aliphatic diol compounds may be used alone or in combination of two or more kinds.

[0046] Examples of the alicyclic diol compound include isosorbide, cyclohexanedimethanol, tricyclodecane dimethanol, adamantanediol, pentacyclopentadecanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 3,9-bis(2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, 3,9-bis(2-hydroxy-1,1-diethylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane, and 3,9-bis(2-hydroxy-1,1-dipropylethyl)-2,4,8,10-tetraoxaspiro(5.5)undecane. These alicyclic diol compounds may be used alone or in combination of two or more.

[0047] <Production method of polycarbonate resin> The polycarbonate resin preferably used in the present invention is obtained by reacting the diol compound with a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. In the case of interfacial polycondensation, a terminal terminator of a monohydric phenol is usually used. In addition, it may be a branched polycarbonate obtained by polymerizing a trifunctional component, or a copolymerized polycarbonate obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and a vinyl monomer.

[0048] In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine, is used. As the solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. In addition, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction. In this case, the reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours.

[0049] The transesterification reaction using, for example, a carbonic acid diester as a carbonate precursor is carried out by a method in which a predetermined ratio of aromatic dihydroxy components is heated and stirred with a carbonic acid diester under an inert gas atmosphere, and the alcohol or phenols produced are distilled off. The reaction temperature varies depending on the boiling point of the alcohol or phenols produced, but is usually in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning of the reaction and distilling off the alcohol or phenols produced. In order to promote the reaction, a catalyst usually used in transesterification reactions can also be used. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among these, diphenyl carbonate is particularly preferred.

[0050] Monofunctional phenols that are commonly used as end terminators can be used. In particular, in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as end terminators to adjust molecular weight, and the obtained polycarbonate resin has excellent thermal stability compared to those that are not, since the ends are blocked by groups based on monofunctional phenols. Specific examples of the monofunctional phenols include phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, and p-long chain alkylphenol.

[0051] Polycarbonate resins can be copolymerized with fatty acids as necessary, such as 1,10-dodecanedioic acid (DDDA), adipic acid, hexanedioic acid, isophthalic acid, 1,3-benzenedicarboxylic acid, terephthalic acid, 1,4-benzenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 3-hydroxybenzoic acid (mHBA), and 4-hydroxybenzoic acid (pHBA).

[0052] The polycarbonate resin includes polyester carbonates copolymerized with aromatic or aliphatic (including alicyclic) difunctional carboxylic acids. The aliphatic difunctional carboxylic acids are preferably α,ω-dicarboxylic acids. Examples of the aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane diacid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These carboxylic acids may be copolymerized to the extent that the purpose is not hindered. The polycarbonate resin of the present invention may also be copolymerized with a structural unit containing a polyorganosiloxane unit, if necessary.

[0053] Polycarbonate resins can be copolymerized with a structural unit containing a trifunctional or higher polyfunctional aromatic compound to form a branched polycarbonate, if necessary. Examples of trifunctional or higher polyfunctional aromatic compounds used in branched polycarbonates include 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and trisphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. The constituent units derived from such polyfunctional aromatic compounds preferably account for 0.03 to 1.5 mol %, more preferably 0.1 to 1.2 mol %, and particularly preferably 0.2 to 1.0 mol %, of a total of 100 mol %, including the constituent units from other divalent components.

[0054] The branched structural unit may be derived not only from a polyfunctional aromatic compound, but also from a side reaction occurring during a polymerization reaction by a melt transesterification method without using a polyfunctional aromatic compound. 1 It can be calculated by H-NMR measurement.

[0055] (viscosity average molecular weight) The viscosity average molecular weight of the polycarbonate resin preferably used in the present invention is preferably 15,000 to 40,000, more preferably 16,000 to 39,000, and even more preferably 17,000 to 38,000. Within the above range, practical mechanical strength is easily obtained in many fields, and since the resin has a suitable melt viscosity during molding, problems such as thermal deterioration are suppressed, and the melt viscosity difference with the polycarbonate resin mixed as required is small, resulting in good kneadability. Furthermore, the efficiency of the water washing step during resin production is good, resulting in excellent productivity.

[0056] The viscosity average molecular weight of the polycarbonate resin in the present invention is calculated by first calculating the specific viscosity (η SP ) was measured at 20°C using an Ostwald viscometer from a solution of 0.7 g of resin in 100 ml of methylene chloride. Specific viscosity (η SP )=(tt 0 ) / t 0 [t 0 is the time it takes for methylene chloride to fall, and t is the time it takes for the sample solution to fall] The specific viscosity (η SP ) and the viscosity average molecular weight Mv was calculated using the following formula: η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 Mv 0.83 c=0.7

[0057] (Glass transition temperature: Tg) The glass transition temperature (Tg) of the polycarbonate resin is preferably 90 to 180° C., more preferably 100 to 160° C. If the Tg is within the above range, the heat resistance stability and moldability are good when used as a molded product, which is preferable. The glass transition temperature (Tg) is measured using a 2910-type DSC manufactured by TA Instruments Japan Co., Ltd. at a heating rate of 20° C. / min.

[0058] <Acrylic resin> Examples of monomers suitable for use in the acrylic resin of the present invention include the following compounds. For example, methyl methacrylate, methyl acrylate, methacrylic acid, acrylic acid, benzyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Examples of the acrylate include acrylate, acrylic (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, cyclopentyl methacrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, cycloheptyl methacrylate, cycloheptyl acrylate, cyclooctyl methacrylate, cyclooctyl acrylate, cyclododecyl methacrylate, and cyclododecyl acrylate.

[0059] These may be used by polymerizing alone or by polymerizing two or more kinds. In particular, it is preferable to contain methyl methacrylate and / or methyl acrylate. As the monomer components, it is preferable to contain 50 to 99 mol% of methyl methacrylate and 1 to 50 mol% of methyl acrylate, more preferably 60 to 99 mol% of methyl methacrylate and 1 to 40 mol% of methyl acrylate, and even more preferably 70 to 99 mol% of methyl methacrylate and 1 to 30 mol% of methyl acrylate. When the monomer component contains more than 99 mol% of methyl methacrylate, the thermal decomposition resistance is poor and molding defects such as silver may occur during molding. When the monomer component contains less than 50 mol% of methyl methacrylate, the heat distortion temperature may decrease. In addition, other monomers that can be polymerized with these acrylic monomers, such as olefin monomers and vinyl monomers, may be used in combination in an amount of 0 to 30 mass%.

[0060] (molecular weight) The molecular weight of the acrylic resin is not particularly limited, but as long as the weight average molecular weight is in the range of 30,000 to 300,000, defects in appearance such as flow unevenness do not occur during molding. It is possible to provide molded products having excellent mechanical properties and heat resistance.

[0061] (Glass transition temperature: Tg) The glass transition temperature (Tg) of the acrylic resin preferably used in the present invention is preferably 90 to 150° C., more preferably 95 to 145° C., and even more preferably 100 to 140° C. A Tg of 90 to 150° C. is preferable since it provides good heat resistance stability and moldability. The glass transition temperature (Tg) is measured using a 2910-type DSC manufactured by TA Instruments Japan Co., Ltd. at a heating rate of 20° C. / min.

[0062] <<Inorganic fine particles>> The inorganic fine particles used in the present invention are not particularly limited, but may be ZrO 2 (Zirconium oxide), TiO 2 (Titanium oxide), SnO 2(Tin oxide), SiO 2 (Silicon oxide), Al 2 O 3 (aluminum oxide), ZnO (zinc oxide), MgO (magnesium oxide), etc. can be exemplified. Among them, ZrO 2 (Zirconium oxide) is preferred.

[0063] In the present invention, when the entire organic-inorganic composite composition is taken as 100% by mass, the content of inorganic fine particles is 8% by mass or less, preferably 6% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, particularly preferably 2% by mass or less, and most preferably 1% by mass or less. The lower limit is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, and most preferably 0.3% by mass or more. If the content of inorganic fine particles exceeds 8% by mass, it is not preferable because it adversely affects transparency and low dielectric constant.

[0064] <Surface modifier> The inorganic fine particles may be modified with a surface modifier as necessary. The surface modifier of the inorganic fine particles in the present invention is not particularly limited as long as it can ensure the dispersibility of the inorganic fine particles in the thermoplastic resin to be composited, but it is preferable that it has an acidic functional group, and it is particularly preferable that it has an acidic functional group of any of sulfonic acid group, phosphonic acid group, phosphinic acid group, and carboxylic acid group because it is excellent in surface modification. Representative specific examples of the surface modifier are shown below, but the surface modifier of the present invention is not limited thereto. They may be used alone, or a plurality of types may be mixed and used. It is desirable to select and use appropriately for the purpose of improving the dispersibility of the fine particles in the thermoplastic resin or not adversely affecting the dielectric constant.

[0065] Examples of sulfonic acids include alkylsulfonic acids such as butanesulfonic acid, hexanesulfonic acid, and dodecanesulfonic acid, and arylsulfonic acids such as benzenesulfonic acid, methylbenzenesulfonic acid, and dodecylbenzenesulfonic acid. Among these, arylsulfonic acids are preferred in view of dispersibility in resins and the effect of improving the refractive index.

[0066] Examples of the phosphonic acid include alkyl phosphonic acids such as propane phosphonic acid, and aryl phosphonic acids such as benzene phosphonic acid. Among these, aryl phosphonic acids are preferred in view of dispersibility in resins and the effect of improving the refractive index.

[0067] Examples of the phosphinic acid include alkylphosphinic acids such as dimethylphosphinic acid, diethylphosphinic acid, and di(2-ethylhexyl)phosphinic acid, and arylphosphinic acids such as phenylphosphinic acid and diphenylphosphinic acid. Among these, arylphosphinic acids are preferred in terms of dispersibility in resins and solvents, with phenylphosphinic acid and diphenylphosphinic acid being more preferred, and diphenylphosphinic acid being particularly preferred.

[0068] Carboxylic acids include butanoic acid, isobutanoic acid, methacrylic acid, hexanoic acid, and octanoic acid. Examples of the aryl carboxylic acid include alkyl carboxylic acids such as oleic acid, linoleic acid, and lauric acid, and aryl carboxylic acids such as benzoic acid, hydroxybenzoic acid, and phenoxybenzoic acid. Among these, in consideration of dispersibility in resins and solvents, aryl carboxylic acids are preferred, phenoxybenzoic acid having a phenoxy group at the ortho, meta, or para position is more preferred, and paraphenoxybenzoic acid is particularly preferred.

[0069] <Surface modification method> The surface modification of inorganic fine particles in the present invention is carried out, for example, by the following process. That is, a surface modifier having an acidic functional group is added to a mixture of a transparent aqueous dispersion in which hydrophilic inorganic fine particles having an average particle size of about 20 nm or less are dispersed, and methanol, and then the water and methanol are removed by azeotropy and replaced with an organic solvent such as toluene, dichloromethane, or chloroform to prepare a dispersion in which the surface-modified inorganic fine particles are dispersed. The solvent is then completely distilled off to obtain a white powder of the surface-modified inorganic fine particles.

[0070] In the inorganic fine particles modified with a surface modifier, the content of the surface modifier is preferably 1 to 30 mass % relative to the inorganic fine particles, more preferably 5 to 28 mass %, and even more preferably 10 to 25 mass %, in consideration of the effect on dispersibility in thermoplastic resins and dielectric properties. From the viewpoint of dispersibility in thermoplastic resins, the higher the content of the surface modifier, the better. It is desirable to appropriately adjust the content of the surface modifier according to the dispersibility and dielectric properties.

[0071] <Method of producing organic-inorganic composite composition> The method for blending inorganic fine particles with a thermoplastic resin is not particularly limited, but the following methods can be mentioned.

[0072] (Melting method) In this method, a thermoplastic resin and inorganic fine particles are dry-blended, and then melt-kneaded to obtain an organic-inorganic composite composition.

[0073] (Solvent dispersion method) In this method, a thermoplastic resin and inorganic fine particles are dissolved or dispersed in a solvent and mixed, and then the solvent is evaporated to obtain an organic-inorganic composite composition.

[0074] (Polymerization dispersion method) This method comprises dispersing inorganic fine particles in a polymerization reaction liquid containing a monomer, and then carrying out a normal polymerization operation to obtain an organic-inorganic hybrid composition in which the inorganic fine particles are uniformly dispersed.

[0075] Among these, the solvent dispersion method is preferred from the viewpoint of improving the dispersibility of the fine particles in the obtained organic-inorganic composite composition and from the viewpoint of productivity. The composition obtained by the solvent dispersion method may be directly molded into a cast film, or may be melt-processed, such as extrusion or molding, into a molded product.

[0076] In the case of the solvent dispersion method, the solvent to be used may be selected as appropriate from those in which the thermoplastic resin and inorganic fine particles can be dissolved or dispersed, and the type of the solvent is not particularly limited. For example, the solvent is selected in consideration of the solubility parameters and polarity of the thermoplastic resin and inorganic fine particles. For example, methylene chloride, chloroform, toluene, tetrahydrofuran, etc. can be used as the solvent.

[0077] The inorganic fine particles may be mixed as a solid into a solution in which a thermoplastic resin is dissolved in a solvent, or a dispersion in which the inorganic fine particles are dispersed in advance in a solvent may be mixed.

[0078] The amount of the solvent used is not particularly limited, but may be selected so that the thermoplastic resin and the inorganic fine particles can be completely dissolved or dispersed. For example, it is preferable to use 100 to 10,000 parts by mass of the solvent per 100 parts by mass of the thermoplastic resin or the inorganic fine particles.

[0079] The organic / inorganic hybrid composition of the present invention may contain additives such as a heat stabilizer, a plasticizer, a light stabilizer, a polymerized metal deactivator, a flame retardant, a lubricant, an antistatic agent, a surfactant, an antibacterial agent, an ultraviolet absorber, and a mold release agent, as required.

[0080] (Molding method) The organic / inorganic composite composition of the present invention can be molded by a general molding method for thermoplastic resins, such as injection molding, extrusion molding, compression molding, and solvent casting. The organic / inorganic composite composition of the present invention has excellent transparency and dielectric properties, and can be used as various molded products. In particular, it can be advantageously used as a molded product suitable for optical components such as optical lenses, optical disks, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, evaporated plastic reflectors, and displays, electric / electronic components such as front panels and exteriors of personal computers and mobile phones, and film antennas, automotive applications such as automobile headlamps and windows, or functional material applications, and is particularly suitable for optical components and electric / electronic components that take advantage of the transparency and low dielectric properties.

[0081] (Particle size) In the organic-inorganic hybrid composition, the inorganic fine particles have an average particle size of 1 to 85 nm, preferably 2 to 80 nm, more preferably 3 to 75 nm, further preferably 5 to 72 nm, and particularly preferably 10 to 70 nm. If the average particle size of the inorganic fine particles exceeds the upper limit, it is not preferable because it adversely affects transparency and low dielectric constant. EXAMPLES

[0082] The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following examples and comparative examples, the methods for measuring the various properties are as follows.

[0083] <Evaluation method> (viscosity average molecular weight) The specific viscosity (η SP ) was measured at 20°C using an Ostwald viscometer from a solution of 0.7 g of sample dissolved in 100 ml of methylene chloride. Specific viscosity (η SP )=(tt 0 ) / t 0 [t 0 is the time it takes for methylene chloride to fall, and t is the time it takes for the sample solution to fall] The specific viscosity (η SP) and the viscosity average molecular weight Mv was calculated using the following formula: η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 Mv 0.83 c=0.7

[0084] (Glass transition temperature (Tg)) Using 8 mg of sample, measurements were performed using a thermal analysis system DSC-2910 manufactured by TA Instruments Co., Ltd. under conditions of nitrogen atmosphere (nitrogen flow rate: 40 ml / min) and heating rate: 20°C / min in accordance with JIS K7121.

[0085] (Total light transmittance, haze) The total light transmittance and haze of the obtained film were measured using a haze meter (product name: NDH-3000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0086] (Average particle size) The organic-inorganic composite film was cut using a microtome (EM UC6, manufactured by Leica Microsystems) to prepare ultrathin sections, which were attached to a grid (EM FINE GRID No. 2632 F-200-CU 100PC / CA, manufactured by JEOL Ltd.) and observed at an accelerating voltage of 200 kV using a transmission electron microscope TEM JEM-2100, manufactured by JEOL Ltd. The observation magnification was 10,000 times.

[0087] The obtained micrographs were subjected to particle analysis using image analysis software WinROOF Ver.6.6 (Mitani Shoji Co., Ltd.), and the average size and particle size distribution (frequency distribution) of the inorganic fine particles in the sample slices were obtained. Here, the maximum major axis (the length when two arbitrary points on the outer contour of the particle are selected so that the length between them is the maximum) was used as the size of each particle. The same analysis was performed on five sample slices, and the average value was used as the value for each sample.

[0088] (Dielectric constant and dielectric loss tangent) The film of the organic-inorganic composite composition was measured for relative permittivity and dielectric loss tangent at 1, 5, and 10 GHz using a KEYCOM dielectric constant meter (network analyzer: Anritsu MS4622B) with a cavity resonator.

[0089] <Polycarbonate resin> PC-1: 4179 parts of 25% sodium hydroxide aqueous solution and 9404 parts of ion-exchanged water were charged into a reactor equipped with a thermometer, a stirrer and a reflux condenser, 1,988 parts of 2,2-bis(4-hydroxyphenyl)propane (BPA) and 3.98 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved therein, 7,401 parts of methylene chloride was added, and 1,000 parts of phosgene was blown in over about 70 minutes at 15 to 25° C. under stirring. After the blowing of phosgene was completed, 697 parts of 25% sodium hydroxide aqueous solution and 16.9 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 2.20 parts of triethylamine was added, and the mixture was further stirred at 28 to 33° C. for 1 hour to complete the reaction.

[0090] After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with water. When the washings became neutral, the organic phase was washed with hydrochloric acid acid water. After that, it was repeatedly washed with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was put into a kneader filled with warm water, and the methylene chloride was evaporated while stirring. After dehydration, it was dried at 100°C for 12 hours in a hot air circulation dryer to obtain a resin powder. The viscosity average molecular weight of the obtained resin was 37,500, and the glass transition temperature was 155°C.

[0091] PC-2: 8,523 parts of ion-exchanged water and 3787 parts of 25% sodium hydroxide aqueous solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and 901 parts of BPA and 1,010 parts of 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC) as dihydric phenols and 5.73 parts of hydrosulfite were dissolved therein. Then, 6708 parts of methylene chloride were added, and 1,000 parts of FH were blown in at 16 to 24°C for 70 minutes while stirring. 631 parts of 25% sodium hydroxide aqueous solution were added, and 45.0 parts of p-tert-butylphenol were added as a terminal terminator. The mixture was stirred to an emulsified state, and then stirred vigorously again. Under such stirring, 2.0 parts of triethylamine was added when the reaction liquid was at 28°C, and the reaction was terminated by continuing stirring at a temperature of 26 to 31°C for 1 hour. The subsequent operations were performed in the same manner as in Example 1, and a resin powder was obtained. The resulting resin had a viscosity average molecular weight of 20,000 and a glass transition temperature of 130°C.

[0092] PC-3: 22,380 parts of ion-exchanged water and 3844 parts of 48% sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and 3,984 parts of BPC as a dihydric phenol and 7.53 parts of hydrosulfite were dissolved therein. Then, 13,210 parts of methylene chloride were added, and 2,000 parts of FH were blown in at 16 to 24°C while stirring for 60 minutes. 640 parts of 48% sodium hydroxide solution were added, and 93.2 parts of p-tert-butylphenol were added as an end terminator. The mixture was stirred to an emulsified state, and then stirred vigorously again. Under such stirring, 3.24 parts of triethylamine were added when the reaction liquid was at 28°C, and the reaction was terminated by continuing stirring at a temperature of 26 to 31°C for 1 hour. The subsequent operations were the same as those in Example 1, and a resin powder was obtained. The viscosity average molecular weight of the obtained resin was 26,900, and the glass transition temperature was 120°C.

[0093] <Acrylic resin> PMMA-1: Mitsubishi Rayon Acrypet VH-001 (copolymer acrylic resin of methyl methacrylate and methyl acrylate).

[0094] <Inorganic fine particles> NP-1: In a 2 L eggplant flask equipped with a stirrer tip, 3.84 g of paraphenoxybenzoic acid was placed as a surface modifier, and 300 mL of methanol and 700 mL of chloroform were added to dissolve the surface. 2 37.2 g of aqueous dispersion (Sakai Chemical Industry Co., Ltd.: SZR-W) was added dropwise over 15 minutes. The mixture was stirred at room temperature for 1 hour, and then the solvent was distilled off using a rotary evaporator until the volume was about 200 mL. The distillation was performed by reducing the pressure to a level that did not cause bumping in the liquid phase. 300 mL of methanol and 700 mL of chloroform were added to the mixture to again make a transparent dispersion with no interface, and the solvent was distilled off again until the volume was about 200 mL. This operation was repeated three times to obtain a powdery solid.

[0095] 500 mL of methylene chloride was added to the obtained solid, and a transparent dispersion with no interface was obtained again. The solvent was distilled off until the remaining volume was about 100 mL. By repeating this operation three times, the water / methanol / chloroform mixed solvent was replaced with only methylene chloride, and ZrO 2 A methylene chloride dispersion of fine particles was obtained. The methylene chloride dispersion was then vacuum dried at room temperature for 24 hours to remove the methylene chloride, and then further dried at 120°C for 48 hours to obtain surface-modified ZrO 2 The powder was obtained (ZrO containing 24 mass% of surface modifier). 2 fine particles).

[0096] NP-2: Surface-modified ZrO in the same manner as NP-1, except that 1.34 g of diphenylphosphinic acid was used as the surface modifier. 2 The powder was obtained (ZrO containing 10 mass% of surface modifier). 2 fine particles).

[0097] <Production of Organic-Inorganic Composite Composition> The thermoplastic resin and inorganic particles were mixed using the solvent dispersion method (A) or the melt kneading method (B). The film was formed using the solvent casting method (C) or the melt extrusion method (D).

[0098] [Example 1] A methylene chloride solution of PC-1 as a thermoplastic resin and a methylene chloride dispersion of NP-1 as inorganic fine particles were prepared, and then the two were mixed to obtain a uniform PC-1 / NP-1 methylene chloride dispersion (solvent dispersion method: A). Next, the PC-1 / NP-1 methylene chloride dispersion was dried at 25°C for 12 hours and 80°C for 4 hours to distill off the methylene chloride, and then further dried at 100°C for 24 hours to obtain a cast film of the organic-inorganic composite composition (solvent cast method: C). Various evaluations were performed using the cast film, and the results are shown in Table 1.

[0099] [Example 2] A methylene chloride solution of PC-1 as a thermoplastic resin and a methylene chloride dispersion of NP-1 as inorganic fine particles were prepared, and then the two were mixed to obtain a uniform PC-1 / NP-1 methylene chloride dispersion (solvent dispersion method: A). Next, this solution was dropped into warm water in a kneader with an isolation chamber and a foreign matter removal port in the bearing part, and the mixture was flaked while distilling off the methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder. The powder was melt-kneaded using a 15 mmφ twin-screw extruder (KZW15-25MG) manufactured by Technovel Co., Ltd., with both the cylinder and die temperatures at 350°C, to obtain pellets of an organic-inorganic composite composition of PC-1 / NP-1. The obtained pellets were dried in a hot air circulation dryer at 90°C for 6 hours. The 15 mmφ twin-screw extruder manufactured by Technovel Co., Ltd. was equipped with a T-die with a width of 150 mm and a lip width of 500 μm and a film take-up device, and the obtained pellets were molded into a film at 350°C to obtain an extruded film (melt extrusion method: D). Various evaluations were performed on the obtained film. The evaluation results are shown in Table 1.

[0100] [Example 3] The same procedure as in Example 1 was carried out, except that PC-2 was used as the thermoplastic resin. The results are shown in Table 1.

[0101] [Example 4] The same procedure as in Example 1 was carried out, except that PC-2 was used as the thermoplastic resin and NP-2 was used as the inorganic fine particles. The results are shown in Table 1.

[0102] [Example 5] The same operation as in Example 4 was carried out, except that the content of the inorganic fine particles was changed to 5.0% by mass. The results are shown in Table 1.

[0103] [Example 6] Except for using PC-3 as the thermoplastic resin, the same procedure as in Example 1 was carried out. The results are shown in Table 1.

[0104] [Example 7] The same procedure as in Example 1 was carried out except that PMMA-1 was used as the thermoplastic resin. The results are shown in Table 1.

[0105] [Comparative Example 1] A methylene chloride solution of PC-1 was prepared as a thermoplastic resin, and dried at 25°C for 12 hours and 80°C for 4 hours to remove the methylene chloride, and then dried at 100°C for 24 hours to obtain a cast film. Various evaluations were performed using the cast film, and the results are shown in Table 1.

[0106] [Comparative Example 2] After dry blending pellets of PC-1 as a thermoplastic resin and powder of NP-1 as inorganic fine particles, the pellets were melt-kneaded at cylinder and die temperatures of 350°C using a 15mmφ twin-screw extruder (KZW15-25MG) manufactured by Technovel Co., Ltd. to obtain pellets of an organic-inorganic composite composition of PC-1 / NP-1 (melt-kneading method: B). The obtained pellets were dried at 90°C for 6 hours using a hot air circulation dryer. A T-die with a width of 150 mm and a lip width of 500 μm and a film take-up device were attached to a 15mmφ twin-screw extruder manufactured by Technovel Co., Ltd., and the obtained pellets were molded into a film at 350°C to obtain an extruded film. Various evaluations were performed on the obtained film. The evaluation results are shown in Table 1.

[0107] [Comparative Example 3] Except for using PC-2 as the thermoplastic resin, the same procedure as in Comparative Example 1 was carried out. The results are shown in Table 1.

[0108] [Comparative Example 4] PC-2 was used as the thermoplastic resin, and the melt mixing temperature and film forming temperature were set at 280°C. Other than that, the same operation as in Comparative Example 2 was performed. The results are shown in Table 1.

[0109] [Comparative Example 5] The same operations as in Example 1 were carried out, except that PC-2 was used as the thermoplastic resin and the content of the inorganic fine particles was changed to 10.0 mass %. The results are shown in Table 1.

[0110] [Comparative Example 6] Except for using PC-3 as the thermoplastic resin, the same procedure as in Comparative Example 1 was carried out. The results are shown in Table 1.

[0111] [Comparative Example 7] Except for using PMMA-1 as the thermoplastic resin, the same procedure as in Comparative Example 1 was carried out. The results are shown in Table 1.

[0112] [Table 1]

[0113] The organic-inorganic composite compositions in which the particle diameter of the inorganic fine particles is relatively small as in Examples 1 to 7 showed a low dielectric constant compared to the case of the thermoplastic resin alone as in Comparative Examples 1, 3, 6, and 7. On the other hand, the organic-inorganic composite compositions in which the particle diameter of the inorganic fine particles is relatively large as in Comparative Examples 2 and 4, and the inorganic fine particles in Comparative Example 5 showed a low dielectric constant. When the particle content was high, the low dielectric constant was not achieved and the transparency was also deteriorated.

[0114] Fig. 1 shows a TEM image of the organic-inorganic composite composition obtained in Example 4. The composition had high transparency and the inorganic fine particles were uniformly dispersed. On the other hand, Fig. 2 shows a TEM image of the organic-inorganic composite composition obtained in Comparative Example 4. The composition had low transparency and the inorganic fine particles were aggregated. [Industrial Applicability]

[0115] The organic-inorganic composite composition of the present invention is excellent in that it exhibits a low dielectric constant without impairing the inherent transparency of thermoplastic resins by adding a very small amount of inorganic fine particles having a specific particle size, and therefore the molded articles, films and sheets obtained by using the present invention can be used in various fields.

Claims

1. The organic-inorganic composite composition contains a thermoplastic resin (A) and inorganic fine particles (B), the thermoplastic resin (A) being an acrylic resin or a polycarbonate resin, the polycarbonate resin being a polycarbonate resin obtained by using, as an aromatic diol, 2,2-bis(4-hydroxyphenyl)propane or 2,2-bis(4-hydroxy-3-methylphenyl)propane alone or in combination, and the inorganic fine particles (B) being ZrO ２ (Zirconium oxide), TiO ２ (Titanium oxide), SnO ２ (Tin oxide), SiO ２ (Silicon oxide), Al ２ O ３ the inorganic fine particles (B) are at least one selected from the group consisting of aluminum oxide, zinc oxide, and magnesium oxide; the inorganic fine particles (B) are modified with a surface modifier, the surface modifier having an acidic functional group; when the entire organic-inorganic hybrid composition is taken as 100 mass%, the content of the inorganic fine particles (B) is 6 mass% or less and 0.01 mass% or more; and the average particle diameter of the inorganic fine particles (B) in the organic-inorganic hybrid composition is 1 to 85 nm.

2. 2. The organic-inorganic hybrid composition according to claim 1, wherein the acidic functional group is at least one acidic functional group selected from the group consisting of a sulfonic acid group, a phosphonic acid group, a phosphinic acid group, and a carboxylic acid group.

3. 3. The organic-inorganic hybrid composition according to claim 1, wherein the content of the surface modifier is 1 to 30% by mass based on 100% by mass of the inorganic fine particles (B).

4. The inorganic fine particles (B) are ZrO ２ The organic-inorganic hybrid composition according to any one of claims 1 to 3, wherein the organic-inorganic hybrid composition is (zirconium oxide).

5. A molded article obtained by using the organic-inorganic hybrid composition according to any one of claims 1 to 4.

6. A film or sheet obtained by using the organic-inorganic hybrid composition according to any one of claims 1 to 4.

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