JP2017095686A - Resin composition for infrared-blocking transparent member and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition with infrared-blocking performance having excellent moist heat resistance while maintaining high transparency.SOLUTION: A resin composition has, based on (A) 100 pts.wt. of a polycarbonate resin (A component), (B) 0.0001-0.2 pts.wt. of composite tungsten oxide fine particles (B component), the fine particles having an average particle diameter of 35-60 nm and represented by general formula MxWyOz (where, M is one or more element selected from H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I; W is tungsten; O is oxygen; 0.1≤x≤0.5, 0.5≤y≤1.5, 2.0≤z≤3.5).SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition containing composite tungsten oxide fine particles as an inorganic material having infrared absorption performance, a vehicle window member for automobiles and the like, a vehicle lamp, and a window member for building material comprising the polycarbonate resin composition. .

A transparent material having an infrared shielding performance has an effect of suppressing an increase in indoor temperature and an increase in the temperature of human sensation, and is expected to have an effect on reducing environmental load when used for window members for automobiles and building materials. In particular, imparting infrared ray shielding performance to a transparent resin has a great effect on reducing environmental burdens such as CO ₂ emission suppression from the viewpoint of weight reduction and thermal management. Therefore, there are several techniques for expressing infrared shielding performance. A method for providing an infrared shielding performance by providing a metal vapor deposition film as in Patent Document 1 has a high production cost. In addition to the high production cost of the thin film laminated film as in Patent Document 2, since the film is post-processed, the performance may be deteriorated when heat is applied. As a condition for reducing the cost, there is a material that is kneaded into a resin as in Patent Document 3, but there are many that impair transparency in order to exhibit infrared shielding performance. Furthermore, although there exists a thing which secures performance, maintaining transparency like patent document 4, an infrared shielding performance may deteriorate temporally, and the improvement of the moisture-and-heat-resistance of infrared shielding performance is calculated | required. Yes.

JP-A-7-187727 Japanese National Patent Publication No. 9-506837 JP 2008-44609 A JP 2011-168636 A

  An object of the present invention is to obtain a resin composition having an infrared shielding performance with good wet heat resistance while maintaining high transparency, and a molded product thereof.

  As a result of intensive studies to solve the above problems, the present inventors have blended the composite tungsten oxide fine particles having a specific particle diameter with the polycarbonate resin, thereby being excellent in heat and moisture resistance and having high infrared shielding performance and a high visible light region. It has been found that a polycarbonate resin composition exhibiting permeability and a molded product comprising the same can be obtained. That is, the above-mentioned problem is that (B) the general formula MxWyOz (where M is H, He, alkali metal, alkaline earth) with an average particle diameter of 35-60 nm with respect to 100 parts by weight of (A) polycarbonate resin (component A) Metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, 1 selected from Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I More than kinds of elements, W is tungsten, O is oxygen, 0.1 ≦ x ≦ 0.5, 0.5 ≦ y ≦ 1.5, 2.0 ≦ z ≦ 3.5) Resin containing 0.0001 to 0.2 parts by weight of fine particles (component B) It is achieved by Narubutsu.

Hereafter, the detail of each structural component of this invention is demonstrated.
(A component: polycarbonate resin)
The polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization 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.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropyl Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5 -Dibromo-4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) ) Fluorene and the like. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance.

As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
In producing a polycarbonate resin by interfacial polymerization of the above dihydric phenol and carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc., as necessary. May be used. The polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. A copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including an alicyclic group), and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

Examples of trifunctional or higher polyfunctional aromatic compounds include 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane. Can be used.
When a polyfunctional compound that produces a branched polycarbonate is included, the amount is 0.001-1 mol%, preferably 0.005-0.9 mol%, particularly preferably 0.01-0, in the total amount of aromatic polycarbonate. 0.8 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0.005% in the total amount of the aromatic polycarbonate. Those having 9 mol%, particularly preferably 0.01 to 0.8 mol% are preferred. Such a ratio can be calculated by ¹ H-NMR measurement.

  The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.
The reaction by the interfacial polymerization method is usually a reaction between a dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, pyridine and the like are used.
As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.

  In addition, catalysts such as tertiary amines and quaternary ammonium salts can be used for promoting the reaction, and monofunctional phenols such as phenol, p-tert-butylphenol, p-cumylphenol, etc. as molecular weight regulators. Are preferably used. Furthermore, examples of monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol. These monofunctional phenols having a relatively long chain alkyl group are effective when improvement in fluidity and hydrolysis resistance is required.

The reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is usually preferably maintained at 10 or higher.
The reaction by the melting method is usually a transesterification reaction between a dihydric phenol and a carbonic acid diester, and the dihydric phenol and the carbonic acid diester are mixed in the presence of an inert gas and reacted at 120 to 350 ° C. under reduced pressure. The degree of vacuum is changed stepwise, and finally the phenols produced at 133 Pa or less are removed from the system. The reaction time is usually about 1 to 4 hours.
Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to accelerate the polymerization rate. Examples of the polymerization catalyst include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide, boron and aluminum hydroxides, Alkali metal salt, alkaline earth metal salt, quaternary ammonium salt, alkoxide of alkali metal or alkaline earth metal, organic acid salt of alkali metal or alkaline earth metal, zinc compound, boron compound, silicon compound, germanium compound, Examples thereof include catalysts usually used for esterification and transesterification of organic tin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. A catalyst may be used independently and may be used in combination of 2 or more types. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalents, per 1 mol of the raw material dihydric phenol. Selected by range.

  In the polymerization reaction, in order to reduce phenolic end groups, for example, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate, 2-ethoxycarbonylphenyl phenyl carbonate, etc. Compounds can be added.

Further, in the melt transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst. Further, it is used in a proportion of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, and particularly preferably 0.01 to 100 ppm with respect to the aromatic polycarbonate after polymerization. Preferred examples of the deactivator include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.
The details of reaction formats other than those described above are also well known in books and patent publications.

  The viscosity average molecular weight of the polycarbonate resin is preferably 14,000 to 100,000, more preferably 20,000 to 30,000, further preferably 22,000 to 28,000, and 23,000 to 26,000. Is particularly preferred. If the molecular weight is too low beyond the above range, the resistance to the hard coating agent tends to be insufficient, and if the molecular weight is too high beyond the above range, injection molding becomes difficult and cracks in the molded product and uneven shadows occur. It tends to occur. In the above preferred range, the resin composition of the present invention can reduce the uneven shadow of the molded product caused by the disturbance of the resin flow and has a hard coat layer in a molecular weight with sufficient resistance to the hard coat agent. This makes it possible to form a polycarbonate resin molded body. Furthermore, in a more preferable range, both the impact resistance and the moldability are excellent. The polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range.

The viscosity average molecular weight (M) of the polycarbonate resin is obtained by inserting the specific viscosity (η _sp ) obtained at 20 ° C. from a solution of 0.7 g of the polycarbonate resin in 100 ml of methylene chloride into the following equation.
η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  Examples of the polycarbonate resin according to the present invention include the following. That is, it consists of an aromatic polycarbonate (PC-i) having a viscosity average molecular weight of 70,000 to 300,000 and an aromatic polycarbonate (PC-ii) having a viscosity average molecular weight of 10,000 to 30,000. Aromatic polycarbonate having a molecular weight of 15,000 to 40,000, preferably 20,000 to 30,000 (hereinafter sometimes referred to as “high molecular weight component-containing aromatic polycarbonate”) can also be used.

  Such an aromatic polycarbonate containing a high molecular weight component increases the entropy elasticity of the polymer due to the presence of PC-i, and becomes more advantageous at the time of injection press molding suitable in the present invention. For example, appearance defects such as hesitation marks can be further reduced, and the condition range of injection press molding can be expanded accordingly. On the other hand, a low molecular weight component of the PC-ii component lowers the overall melt viscosity, promotes relaxation of the resin, and enables molding with lower strain. The same effect is also observed in a polycarbonate resin containing a branched component.

(B component: composite tungsten oxide fine particles)
The composite tungsten oxide fine particles have a general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, One or more elements selected from V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.1 ≦ x ≦ 0.5, 0.5 ≦ y ≦ 1.5, 2.0 ≦ z ≦ 3.5), M is preferably an alkali metal, and more preferably Cs. An average particle diameter is 35-60 nm, 38-55 nm is preferable and 42-50 nm is more preferable. When the average particle diameter is smaller than 35 nm, the heat and moisture resistance of the infrared shielding performance is lowered, and when it exceeds 60 nm, the haze is increased, so that it is difficult to use as a transparent application. Here, the average particle diameter is an average particle diameter calculated by the Scherrer method from the measurement result of the half width of the X-ray diffraction measurement.

In addition, it is not preferable to add zinc oxide fine particles because the molding heat resistance of the resin composition is lowered.
Content of B component is 0.0001-0.2 weight part with respect to 100 weight part of A component, Preferably it is 0.001-0.1 weight part, More preferably, it is 0.004-0.01 weight part. Parts by weight. When the content is less than 0.0001 part by weight, the effect of infrared shielding performance is not sufficiently exhibited. When the content exceeds 0.2 part by weight, the total light transmittance can be maintained when producing an injection molded product or a sheet molded product. It becomes difficult.

(C component: heat stabilizer)
The resin composition of the present invention preferably contains a heat stabilizer as the C component. The heat stabilizer is at least one heat selected from the group consisting of phosphorus stabilizers (C-1 component), hindered phenol stabilizers (C-2 component), and sulfur stabilizers (C-3 component). Stabilizers are preferred. The content of component C is preferably 0.0002 to 0.8 parts by weight, more preferably 0.001 to 0.7 parts by weight, and 0.01 to 0 parts per 100 parts by weight of component A. More preferably, it is 1 part by weight. If the content is less than 0.0002 parts by weight, it is difficult to exhibit the effect of thermal stability, and if it exceeds 0.8 parts by weight, it becomes difficult to maintain the hue stability during molding when used in combination with composite tungsten.

(C-1 component: phosphorus stabilizer)
Phosphorus stabilizers are already widely known as thermal stabilizers for aromatic polycarbonates. In the present invention, the phosphorus stabilizer increases its thermal stability to the extent that the resin composition can withstand extremely severe heat loads. Examples of phosphorus stabilizers include phosphite compounds and phosphonites.

  Here, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite , Diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (diethylphenyl) ) Phosphite, Tris (di-iso-propylphenyl) phosphite, Tris (di-n-butylphenyl) phosphite, Tris (2,4-di-tert-butylphenyl) Sphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Examples include bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and the like.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and the like.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphospho Knight, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, Bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2, -Di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butyl) Phenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphospho Knight, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butyl) More preferred is phenyl) -phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

(C-2 component: hindered phenol stabilizer)
Examples of the hindered phenol-based stabilizer include α-tocopherol, butylhydroxytoluene, sinapir alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel). Propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N , N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′- Methylene bis (4-ethyl-6-tert-butylphenol), 4,4′-methylene bis (2,6- Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′- Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert- Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) -5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl) -6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'- Di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodiethyl Nbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di- tert-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Anurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [methylene-3- (3 ′, 5′-di-tert -Butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. The said hindered phenol type stabilizer can be used individually or in combination of 2 or more types. The content of the hindered phenol-based stabilizer is preferably 0.0002 to 0.8 part by weight, more preferably 0.0005 to 0.45 part by weight, with respect to 100 parts by weight of the component A, and 0.002 to 0.005. 25 parts by weight is more preferable, and 0.005 to 0.15 parts by weight is particularly preferable.

(C-3 component: sulfur stabilizer)
As sulfur compounds, dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate), pentaerythritol tetrakis ( 3-dodecylthiopropionate), pentaerythritol tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol tetrakis (3-stearylthiopropionate), etc. It is done. These may be used alone or in combination of two or more.

(D component: UV absorber)
The resin composition of the present invention may be used without being coated. In such a case, it is preferable to add an ultraviolet absorber because good light resistance may be required.
As the ultraviolet absorber, in the benzophenone series, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2- Hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4 ′ -Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4- Hydroxy-2-methoxyphenyl) Examples include methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

  In the benzotriazole series, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-Dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3 , 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2- Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 Di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- ( 2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4 -One), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxy) Copolymerization of ethylphenyl) -2H-benzotriazole with vinyl monomer copolymerizable with the monomer And 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a copolymer of vinyl monomer copolymerizable with the monomer, 2-hydroxyphenyl-2H-benzotriazole skeleton A polymer having

  In the hydroxyphenyl triazine series, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) -1,3,5-triazin-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol Illustrated. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

In the cyclic imino ester system, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazin-4-one) And 2,2′-p, p′-diphenylenebis (3,1-benzoxazin-4-one) and the like.
In the case of cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenylacryloyl) oxy ] Methyl) propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene and the like.

Furthermore, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylic acid ester. The
Among the above compounds, in the present invention, a compound represented by any one of the following formulas (1), (2) and (3) is more preferably used.

The said ultraviolet absorber can be used individually or in combination of 2 or more types.
The content of component D is preferably 0.1 to 2 parts by weight, more preferably 0.12 to 1.5 parts by weight, and still more preferably 0.15 to 1 part by weight with respect to 100 parts by weight of component A. It is. If the content of component D is less than 0.1 part by weight, sufficient light resistance may not be exhibited, and if it is more than 2 parts by weight, it is not preferable from the viewpoint of poor appearance due to gas generation or deterioration of physical properties.

(E component: mold release agent)
The polycarbonate resin composition of the present invention preferably further contains a release agent for the purpose of improving productivity during molding and reducing distortion of the molded product. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound ( And fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like. Among these, fatty acid esters are preferable as a release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, as carbon number of this alcohol, it is the range of 3-32, More preferably, it is the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid . Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.

  The above aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats such as beef tallow and lard and vegetable oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Accordingly, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used.

  The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). However, partial esters are more preferably full esters because they usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less, more preferably 4 to 20 and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially zero. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially zero. These characteristics can be obtained by a method defined in JIS K 0070.

  The content of component E is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.05 to 0.5 parts by weight with respect to 100 parts by weight of component A. is there. In such a range, the polycarbonate resin composition has good release properties and release properties. In particular, such an amount of fatty acid ester provides a polycarbonate resin composition having good release properties and roll release properties without impairing good hue.

(Other ingredients)
(1) Dye and Pigment The resin composition of the present invention can provide molded products containing various dyes and pigments and exhibiting various design properties. As dyes and pigments used in the present invention, perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, Examples thereof include dioxazine dyes, isoindolinone dyes, phthalocyanine dyes, carbon black, titanium oxide, zinc oxide, zinc sulfide, calcium carbonate, metal oxide fine particles, and metal nitride fine particles. Furthermore, the polycarbonate resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. As the metallic pigment, aluminum powder is suitable. Further, by blending a fluorescent brightening agent or other fluorescent dye that emits light, a better design effect utilizing the luminescent color can be imparted. Examples of the fluorescent dye (including a fluorescent brightening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin.

  Since the resin composition of the present invention has an infrared shielding performance with good moisture and heat resistance while maintaining high transparency, the industrial effect exerted by the resin composition is exceptional.

  Although the form which this inventor implements collects the preferable range of each said requirement, the representative example is described in the following Example, for example. Of course, the present invention is not limited to these forms.

  The present invention will be described more specifically with reference to the following examples. In the following, “part” means “part by weight” and “%” means “% by weight” unless otherwise specified.

(1) Preparation of resin composition (1-1) Raw material used (component A)
A-1: A polycarbonate resin powder baffle with a molecular weight of 24,200 obtained by the following production method was equipped with a three-stage six-blade stirrer and a reflux condenser. In this reaction vessel, 45.6 parts of bisphenol A, 2.78 mol% of p-tert-butylphenol with respect to bisphenol A, 265 parts of dichloromethane, and 200 parts of water were added, and nitrogen purge was performed to remove oxygen in the reaction vessel. Went. At this stage, the content in the reaction vessel was less than 80% of the vessel capacity. Next, about 80 parts of an aqueous solution for supplying 0.09 part of sodium hydrosulfite and 21.8 parts of sodium hydroxide was supplied to the suspension, and bisphenol A was dissolved at 15 ° C. Under stirring, 23.35 parts of phosgene was fed into the mixture over 30 minutes. Thereafter, 0.016 part of triethylamine (0.08 mol% with respect to bisphenol A) was added and stirred for 60 minutes to complete the reaction. Thereafter, the reaction mixture was allowed to stand and the organic phase was separated. Methylene chloride is added to a dichloromethane solution of the obtained polycarbonate resin to obtain a solution having a concentration of 14% by weight, and 0.5% hydroxylation is performed using a centrifugal extractor with a porous plate (KCC centrifugal extractor manufactured by Kawasaki Engineering Co., Ltd.). A sodium aqueous solution was supplied at a flow rate of 1,000 ml / min and an organic phase was supplied at a flow rate of 1,000 ml / min. After treatment at a condition of 3,500 rpm, the organic phase was acidified with hydrochloric acid, and then washed with water repeatedly. When the conductivity was almost the same as that of ion-exchanged water, methylene chloride was evaporated to obtain a polycarbonate resin powder.

(B component)
B-1: Cs _0.33 WO _{3 having} an average particle diameter of 30 nm, about 23% by weight, and a heat ray absorbent comprising an organic dispersion resin (YMDS-874, manufactured by Sumitomo Metal Mining Co., Ltd.)
B-2: Cs _0.33 WO _{3 having} an average particle diameter of 35 nm, about 23% by weight, and a heat ray absorbent comprising an organic dispersion resin B-3: Cs _0.33 WO _{3 having} an average particle diameter of 40 nm, about 23% by weight, and organic dispersion Heat ray absorbent B-4 made of resin: Cs _0.33 WO _{3 having} an average particle diameter of 44 nm of about 23% by weight and heat ray absorbent B-5 made of organic dispersion resin: Cs _0.33 WO _{3 having} an average particle diameter of 50 nm Heat ray absorbent B-6 consisting of 23% by weight and an organic dispersion resin: Cs _0.33 WO _{3 having} an average particle diameter of 80 nm and about 23% by weight and heat ray absorbent consisting of an organic dispersion resin

(C component)
C-1: Phosphorus stabilizer (manufactured by Clariant Japan Co., Ltd .: P-EPQ)
C-2: A hindered phenol-based stabilizer (manufactured by BASF Japan Ltd .: IRGANOX 1076)
C-3: Sulfur-based stabilizer: (manufactured by BASF Japan Ltd .: IRGANOX L115)
(D component)
D-1: Benzotriazine-based ultraviolet absorber (manufactured by BASF Japan Ltd .: Tinuvin 1577ED)
D-2: Benzotriazole-based ultraviolet absorber (Kemipro Kasei Co., Ltd .: Chemisorb 79)
(E component)
E-1: Fatty acid full ester (manufactured by Cognis Japan Co., Ltd .: VPG861)
E-2: Fatty acid partial ester (Riken Vitamin Co., Ltd .: Riquemar S-100A)

(2) Preparation of test piece (2-1) Production of resin composition Each component shown in Table 1 is weighed and mixed in the proportions shown in Table 1 and mixed in a blender, and then a vent type twin screw extruder is used. And kneaded to obtain pellets of the polycarbonate resin composition. The content of the B component is the amount of _{Cs 0.33} WO _3, which is an inorganic ultraviolet absorbing material contained in the B-1 to B-5 shown in parentheses. (The numbers outside the parentheses represent parts by weight in the resin composition of B-1 to B-5.) Additives added to the polycarbonate resin are pre- After preparing as a preliminary mixture, the whole was mixed with a blender. The vent type twin screw extruder used was TEX30α (completely meshing, rotating in the same direction, two-thread screw) manufactured by Nippon Steel Works. The kneading zone was of one type before the vent opening. The extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 280 ° C. from the first supply port to the die part. The above resin composition was produced in an atmosphere in which clean air passed through a HEPA filter was circulated, and with great care so that no foreign matter was mixed during the operation.

(2-2) Test piece preparation method After the obtained pellets were dried at 110 to 120 ° C. for 6 hours in a hot air circulation dryer, the injection molding machine [SG260M-HP manufactured by Sumitomo Heavy Industries, Ltd.] A plate having a width of 150 mm, a length of 150 mm, a thickness of 2 mm, and a thickness of 5 mm, and a width of 50 mm × length of 50 mm × thickness of 18 mm, which is a test piece for evaluation, was formed under conditions of a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C.

(3) Evaluation item (3-1) Change in infrared shielding performance after wet heat resistance test A 50 mm square test piece was cut out from a test piece of each thickness. The initial total transmission of solar energy (Tts) was calculated based on ISO13837 using a spectroscopic light measuring device U-4100 manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 1. Next, the test piece was subjected to a wet heat treatment for 40 hours at 120 ° C. and 95% Rh using a pressure cooker tester TPC-412 (manufactured by ESPEC Co., Ltd.), and Tts was calculated in the same manner as described above. . The difference between Tts after the pressure cooker and the initial Tts was calculated and used as the amount of change (ΔTts) in the infrared shielding performance after the wet heat resistance test. The results are shown in Table 1.

(3-2) Total light transmittance and haze A 50 mm square test piece was cut out from the test piece, and the total light transmittance and haze were measured according to ISO 13468 using a Haze Meter HR-100 manufactured by Murakami Color Research Laboratory. It was measured. The results are shown in Table 1.

  As is apparent from the above, according to the present invention, by adding composite tungsten oxide fine particles having a specific average particle diameter to polycarbonate, a resin composition having an infrared shielding performance with good moisture and heat resistance while maintaining high transparency. And it turns out that the molded article consisting thereof is obtained.

  The present invention provides a polycarbonate resin molded article suitable for a vehicle glazing material, particularly a back door window, a sunroof, and a roof panel. However, the molded product of the present invention is not limited to a vehicle glazing material because of its unique characteristics. Window glass for construction machinery, windows for buildings, houses, and greenhouses, roofs for garages and arcades, lighting lenses, traffic light lenses, optical equipment lenses, mirrors, glasses, goggles, noise barriers, motorcycle windshields Can be used for a wide range of applications such as nameplates, solar cell covers or solar cell substrates, display device covers, touch panels, and parts for game machines (such as pachinko machines) (circuit covers, chassis, pachinko ball conveyance guides, etc.) . Therefore, the polycarbonate resin molded body of the present invention is useful for various applications such as various electronic / electrical equipment, OA equipment, vehicle parts, machine parts, other agricultural materials, fishery materials, transport containers, packaging containers, playground equipment and miscellaneous goods. The industrial effects that it plays are exceptional.

Claims (10)

  (A) General formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element) with (B) an average particle size of 35-60 nm with respect to 100 parts by weight of polycarbonate resin (component A) Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb One or more elements selected from Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, W is tungsten, O is oxygen, composite tungsten oxide fine particles (component B) represented by 0.1 ≦ x ≦ 0.5, 0.5 ≦ y ≦ 1.5, 2.0 ≦ z ≦ 3.5) ) A resin composition containing 0.0001 to 0.2 parts by weight.   2. The resin composition according to claim 1, comprising 0.0002 to 0.8 parts by weight of (C) a heat stabilizer (C component) with respect to 100 parts by weight of component A. 3.   The C component is at least one heat stabilizer selected from the group consisting of a phosphorus stabilizer (C-1 component), a hindered phenol stabilizer (C-2 component), and a sulfur stabilizer (C-3 component). The resin composition according to claim 2, wherein:   The resin composition according to any one of claims 1 to 3, further comprising 0.1 to 2 parts by weight of (D) an ultraviolet absorber (component D) with respect to 100 parts by weight of the component A.   The resin composition according to any one of claims 1 to 4, comprising 0.005 to 2 parts by weight of (E) a release agent (E component) with respect to 100 parts by weight of the A component.   The film and molded article which consist of a resin composition in any one of Claims 1-5.   The molded article according to claim 6, wherein the visible light transmittance defined by ISO 9050 is 40% or more and the haze defined by ISO 9050 is 3 or less.   The molded article according to claim 6 or 7, wherein the thickness is 2 to 20 mm.   A molded product obtained by subjecting the surface of the molded product according to any one of claims 6 to 8 to a hard coat treatment.   The molded article according to any one of claims 6 to 9, wherein the molded article is a vehicle window member, a vehicle lamp, or a building material window member.