JP5423636B2 - Manufacturing method of composite tungsten oxide fine particle-dispersed polycarbonate resin masterbatch, composite tungsten oxide fine particle-dispersed polycarbonate resin masterbatch obtained by the manufacturing method of the masterbatch, and molded body and laminate obtained using the masterbatch body - Google Patents

Description

  The present invention relates to a method for producing a master batch in which composite tungsten oxide fine particles are dispersed in a polycarbonate resin, a master batch obtained by the method for producing the master batch, and a molding obtained using the master batch. The present invention relates to a body and a laminate.

  From so-called opening parts such as window materials, door materials, etc. provided on mobile devices such as roof materials, wall materials, automobiles, trains, aircraft, etc. of various buildings, to the sun rays entering the interior of the buildings and mobile devices, In addition to visible light, ultraviolet rays and infrared rays are included. Among infrared rays contained in this solar ray, near infrared rays having a wavelength of 800 to 2500 nm are called heat rays, and cause the temperature inside the building to rise by entering the building or mobile device from the opening. become.

  In order to eliminate the temperature rise, in recent years, in the manufacturing and construction fields of various building and mobile equipment window materials, arcades, ceiling domes, carports, etc. The demand for a molded body having a heat ray shielding function that suppresses an internal temperature rise while maintaining the temperature is increasing rapidly. On the other hand, in response to the demand for the molded body having the heat ray shielding function, many proposals regarding the molded body having the heat ray shielding function have been made.

  For example, a heat ray shielding plate in which a heat ray reflective film formed by vapor-depositing a metal or metal oxide on a transparent resin film is bonded to a transparent molded body such as glass, an acrylic plate, or a polycarbonate plate has been proposed (Patent Documents 1, 2, And 3).

  On the other hand, many heat ray shielding plates have been proposed in which a metal or metal oxide is directly deposited on the surface of a transparent molded body.

  In addition, for example, heat ray shielding in which an organic near-infrared absorber typified by a phthalocyanine compound or an anthraquinone compound is incorporated into a thermoplastic transparent resin such as a polyethylene terephthalate resin, a polycarbonate resin, an acrylic resin, a polyethylene resin, or a polystyrene resin. Plates and films have been proposed (see, for example, Patent Documents 4 and 5).

  Furthermore, for example, a heat ray shielding plate in which inorganic particles such as titanium oxide having a heat ray reflecting function or mica coated with titanium oxide are kneaded into a transparent resin such as an acrylic resin or a polycarbonate resin has been proposed ( For example, see Patent Documents 6 and 7).

  Under such background art, the present applicants obtain a heat ray shielding coating solution containing hexaboride fine particles in various binders as a heat ray shielding component, and apply the coating solution to various molded bodies and then cure the resultant. And a masterbatch obtained by melt-kneading and dispersing hexaboride fine particles in a thermoplastic resin (see, for example, Patent Documents 8, 9, and 10).

  Furthermore, the present applicants expressed the general formula MxWyOz (where W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0) as a heat ray shielding component. Heat-shielding coating solution containing various composite tungsten oxide fine particles in various binders, heat-ray shielding film obtained by applying this coating solution to various molded bodies and curing, and composite tungsten oxide in thermoplastic resin A master batch obtained by melt-kneading and dispersing fine particles is disclosed (for example, see Patent Documents 11 and 12). Among them, in Patent Document 12, since the heat resistance of the dispersant contained in the masterbatch is low, when the masterbatch is kneaded and mixed with the same or different resin, the dispersant is thermally denatured, Dispersing ability of the dispersant deteriorates, which hinders dispersion of the heat ray shielding fine particles contained in the masterbatch, and does not provide the expected visible light transmission ability and heat ray shielding function. Was colored yellow to brown, and the heat ray shielding sheet material was yellowed, using a high heat resistant dispersant having a thermal decomposition temperature of 230 ° C. or higher, and the high heat resistant dispersant And it aimed at obtaining the high heat-resistant masterbatch by which the mixing ratio with heat ray shielding fine particles was controlled by the predetermined range.

  Furthermore, the present inventors have conceived a configuration in which an organometallic compound and a silane compound are uniformly adsorbed on the surface of the composite tungsten oxide fine particles to form a coating film. And by the said structure, the infrared shielding base material, the infrared shielding fine particle dispersion, etc. which applied the composite tungsten oxide fine particle suitable for the outdoor use purpose and excellent in water resistance and chemical stability were disclosed (for example, patent document 13). reference).

JP-A 61-277437 Japanese Patent Laid-Open No. 10-146919 Japanese Patent Laid-Open No. 2001-179887 JP-A-6-256541 JP-A-6-264050 JP-A-2-173060 JP-A-5-78544 JP 2000-96034 A JP 2000-169765 A JP 2004-59875 A International Publication 2005 / 87680A1 JP 2008-24902 A JP 2008-291109 A

However, as a result of further studies by the present inventors, the following problems have been clarified.
The heat ray reflective film formed by vapor-depositing a metal or a metal oxide on a transparent resin film as described in Patent Documents 1, 2, and 3 is very expensive in itself. Furthermore, the manufacture of a heat ray shielding plate in which the heat ray reflective film is adhered to a transparent molded body requires complicated steps such as an adhesion step. For this reason, the said heat ray shielding board will become further expensive. In addition, the heat ray shielding plate has a drawback in that the transparent molded body and the film are peeled off due to a change with time because the adhesiveness between the transparent molded body and the heat ray reflective film is not good.

  On the other hand, when manufacturing a heat ray shielding plate by directly depositing metal or metal oxide on the surface of a transparent molded body, a device that requires high vacuum and high-precision atmosphere control is required. Have the problem of being poor.

  To a heat ray shielding plate and film in which an organic near-infrared absorber typified by a phthalocyanine compound or an anthraquinone compound is kneaded into a thermoplastic transparent resin such as polyethylene terephthalate resin as described in Patent Documents 4 and 5. In order to provide sufficient heat ray shielding ability, a large amount of near infrared absorber must be blended. However, when a large amount of near-infrared absorbing agent is added to the heat ray shielding plate and the film, there is a problem that the visible light transmission function is deteriorated. Moreover, since an organic compound is used as a near-infrared absorber, it is difficult to apply weather resistance to buildings and vehicle window materials that are constantly exposed to direct sunlight, and is not necessarily suitable. It was.

  Inorganic particles such as titanium oxide having a heat ray reflecting function or mica coated with titanium oxide are kneaded into a transparent resin such as acrylic resin and polycarbonate resin as described in Patent Documents 6 to 10 Also in a heat ray shielding board, in order to ensure a heat ray shielding function, it is necessary to add a large amount of particles having a heat ray reflecting function. As a result, there is a problem that the visible light transmission ability decreases with an increase in the amount of particles having a heat ray reflecting function. However, if the amount of particles having a heat ray reflecting function is reduced, the visible light transmitting function is enhanced, but this time the heat ray shielding function is lowered. After all, there was a problem that it was difficult to satisfy both the heat ray shielding function and the visible light transmission function at the same time. In addition, when a large amount of particles having a heat ray reflecting function is added, there is a problem from the strength aspect that physical properties, in particular, impact strength and toughness, of the transparent resin constituting the molded body are lowered.

  The present applicants disclosed in Patent Documents 11 and 12, as a heat ray shielding component, a heat ray shielding coating solution containing composite tungsten oxide fine particles represented by the general formula MxWyOz in various binders, and various moldings of this coating solution. A heat ray shielding film obtained by curing after application to the body, and a master batch obtained by melting and kneading the composite tungsten oxide fine particles in a thermoplastic resin and dispersing them were proposed. Here, the infrared shielding material is basically used outdoors because of its characteristics, and high weather resistance is often required. However, according to the study by the present inventors, in some optical members (film, resin sheet, etc.) containing the composite tungsten oxide fine particles, depending on the method of use, water vapor or water in the air gradually enters the matrix. A problem was found that the surface of the composite tungsten oxide fine particles penetrated and the surface of the composite tungsten oxide fine particles was decomposed, and the heat ray shielding function was lowered.

The composite tungsten oxide fine particles having excellent chemical stability in which the organometallic compound and the silane compound are uniformly adsorbed on the surface of the composite tungsten oxide fine particles disclosed by the present inventors as Patent Document 13. In the surface coating treatment step, a metal alkoxide such as alkoxysilane is hydrolyzed and subjected to a polycondensation reaction by a sol-gel method, whereby a film is formed on the surface of the composite tungsten oxide fine particles.
However, the surface of the composite tungsten oxide fine particles is decomposed due to the influence of water used in the hydrolysis reaction described above. For this reason, the heat ray shielding function of the surface-coated composite tungsten oxide fine particles obtained is impaired to the same extent as the heat ray shielding function of the composite tungsten oxide fine particles deteriorated by water vapor or water in the air without performing the surface coating treatment. There is a problem such as.

  In addition, in the surface coating treatment step, condensation between excess metal alkoxides easily occurs, and the generated oligomer reacts across a plurality of fine particles. For this reason, the surface-coated composite tungsten oxide fine particles obtained are in a state of being firmly condensed with each other. In order to eliminate this aggregation state, it is necessary to perform a wet pulverization treatment using a medium stirring mill. At this time, the surface coating of the composite tungsten oxide fine particles may be damaged or the surface coating may be peeled off. For this reason, there is also a problem that it is not always possible to suppress a decrease in the heat ray shielding function during outdoor use.

  The present invention has been made under the above circumstances. The problem to be solved is a method for producing a masterbatch in which composite tungsten oxide fine particles that are difficult to lose the heat ray shielding function in the surface coating process are dispersed in the polycarbonate resin, and the production of the masterbatch. It is providing the masterbatch obtained by the method, and the molded object and laminated body obtained by using the said masterbatch.

The present inventor has intensively studied for the purpose of solving the above problems. Then, a silane compound having a siloxane bond and having at least one silicon atom having a silanol group (Si—OH) is added to and mixed with the dispersion liquid in which the composite tungsten oxide fine particles are dispersed in a solvent. Then, a step of obtaining a dispersion of surface-coated composite tungsten oxide fine particles coated with a polycondensate of a silane compound obtained by adding a catalyst,
An aggregation inhibitor having a functional group that is compatible with the polycarbonate resin and has a functional group adsorbed on the surface of the surface-coated composite tungsten oxide fine particles is added to the dispersion, and then the organic solvent is volatilized from the dispersion. A step of obtaining a surface-coated composite tungsten oxide fine particle powder,
A step of melt-kneading the surface-coated composite tungsten oxide fine particle powder with a polycarbonate resin to obtain a master batch in which the surface-coated composite tungsten oxide fine particles are dispersed. Came up with a masterbatch dispersed in polycarbonate resin.

  Then, the master batch in which the composite tungsten oxide fine particles are dispersed in the polycarbonate resin is diluted and melt-kneaded with a polycarbonate resin and a different kind of thermoplastic resin compatible with the polycarbonate resin. The present inventors have found that a heat ray shielding molded body with improved shielding function loss can be obtained, and have reached the present invention.

That is, the first invention for solving the above-described problem is
In an organic solvent, the 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, V , Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0), in which the composite tungsten oxide fine particles are dispersed, the siloxane bond is present, and at least one silicon atom has a silanol group (Si—OH). Adding a silane compound having
Adding a catalyst to the dispersion to which the silane compound is added, and obtaining a dispersion of the surface-coated composite tungsten oxide fine particles coated with the condensation product of the silane compound;
From the hydroxyl group, glycidyl group, carboxyl group, or amino group that is compatible with the polycarbonate resin and adsorbed on the surface of the surface-coated composite tungsten oxide fine particles in the dispersion liquid of the surface-coated composite tungsten oxide fine particles. After adding the aggregation inhibitor having at least one selected functional group, the organic solvent is volatilized from the dispersion liquid of the surface-coated composite tungsten oxide fine particles, and the powder of the surface-coated composite tungsten oxide fine particles is obtained. Obtaining a step;
A step of melt-kneading the powder of the surface-coated composite tungsten oxide fine particles with a polycarbonate resin to obtain a polycarbonate resin master batch in which the surface-coated composite tungsten oxide fine particles are dispersed. This is a method for producing a composite tungsten oxide fine particle-dispersed polycarbonate resin master batch.
The second invention is
The composite tungsten oxidation according to the first invention, wherein the anti-aggregation agent is a polymer compound containing at least one functional group selected from a hydroxyl group, a glycidyl group, a carboxyl group, or an amino group. This is a method for producing a fine particle-dispersed polycarbonate resin master batch.
The third invention is
The composite tungsten according to any one of the first and second inventions, wherein an addition amount of the aggregation inhibitor is 1.0 to 50 parts by weight with respect to 1 part by weight of the composite tungsten oxide. It is a manufacturing method of an oxide particle dispersion polycarbonate resin masterbatch.
The fourth invention is:
The molecular weight of the silane compound is 100 to 100,000. The method for producing a composite tungsten oxide fine particle dispersed polycarbonate resin masterbatch according to any one of the first to third inventions.
The fifth invention is:
The composite according to any one of the first to fourth inventions, wherein the addition amount of the silane compound is 0.1 to 10.0 parts by weight with respect to 1 part by weight of the composite tungsten oxide. This is a method for producing a tungsten oxide fine particle-dispersed polycarbonate resin master batch.
The sixth invention is:
The primary particle size of the composite tungsten oxide fine particles is 1 nm or more and 200 nm or less, and the method for producing a composite tungsten oxide fine particle-dispersed polycarbonate resin masterbatch according to any one of the first to fifth inventions It is.
The seventh invention
A composite tungsten oxide fine particle-dispersed polycarbonate resin master produced by the production method according to any one of the first to sixth inventions, wherein the surface-coated composite tungsten oxide fine particles are dispersed in a polycarbonate resin. It is a batch.
The eighth invention
It is obtained by diluting, melting and kneading a masterbatch described in the seventh invention with a polycarbonate resin or a different kind of thermoplastic resin compatible with the polycarbonate resin, and molding the masterbatch into a predetermined shape. It is a molded body.
The ninth invention
A molded product comprising at least one coating layer selected from a hard coat layer and an antireflection layer on one or both sides of the molded product according to the eighth invention.
The tenth invention is
A molded body according to an eighth aspect of the present invention is a laminated body characterized by being laminated on another transparent molded body.

  A masterbatch produced by the method of producing a masterbatch in which the composite tungsten oxide fine particles according to the present invention are dispersed in a polycarbonate resin is diluted with a polycarbonate resin or a different thermoplastic resin having compatibility with the polycarbonate resin. -By molding by melting and kneading to produce a molded body and a laminated body, it was possible to produce a molded body and a laminated body having excellent weather resistance.

  Hereinafter, it was obtained by a manufacturing method of a master batch (in the present invention, sometimes referred to as “master batch”) in which composite tungsten oxide fine particles are dispersed in a polycarbonate resin, and a manufacturing method of the master batch. The master batch, and the molded body and laminate obtained using the master batch will be described in detail.

1. Method for Producing Masterbatch in which Composite Tungsten Oxide Fine Particles are Dispersed in Polycarbonate Resin Regarding the method for producing a masterbatch according to the present invention, first, individual raw materials will be explained, and then production steps and operations will be explained.

(1) Composite tungsten oxide fine particles (in the present invention, the symbol “(A)” may be added)
The composite tungsten oxide fine particles (A) used in the present invention are components that exhibit a heat ray shielding effect, and have a general formula MxWyOz (where M element 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, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is Tungsten, O is oxygen, and is a composite tungsten oxide fine particle represented by 0.001 ≦ x / y ≦ 1.1, 2.2 ≦ z / y ≦ 3.0).

  The composite tungsten oxide fine particles (A) are excellent in durability when they have a hexagonal, tetragonal or cubic crystal structure. Therefore, the composite tungsten oxide fine particles (A) preferably include one or more crystal structures selected from the hexagonal crystal, tetragonal crystal, and cubic crystal. For example, in the case of composite tungsten oxide fine particles (A) having a hexagonal crystal structure, preferable M elements include Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. Examples thereof include composite tungsten oxide fine particles containing one or more selected elements.

When the M element is one or more elements selected from the elements Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn, the addition amount x of the M element to be added Is preferably from 0.001 to 1.1 in terms of x / y, more preferably from 0.30 to 0.36. This is because the value of x / y calculated theoretically from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained with addition amounts around this value.
On the other hand, the abundance Z of oxygen is preferably 2.2 or more and 3.0 or less in terms of z / y.

From the above, examples of preferred compositions include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like. However, if x, y, and z are within the above ranges, useful near-infrared absorption characteristics can be obtained.
The composite tungsten oxide fine particles (A) can be produced, for example, by the method described in International Publication No. 2005/037932.

If importance is placed on reducing light scattering by the composite tungsten oxide fine particles (A), the dispersed particle diameter of the composite tungsten oxide fine particles (A) is 200 nm or less, preferably 100 nm or less. The reason is that if the dispersed particle size is small, the scattering of light in the visible light region having a wavelength of 400 nm to 780 nm due to geometric scattering or Mie scattering is reduced. As a result of the light scattering being reduced, it can be avoided that the heat ray shielding film becomes like frosted glass and clear transparency cannot be obtained. This is because when the dispersed particle diameter is 200 nm or less, geometrical scattering and Mie scattering due to the composite tungsten oxide fine particles (A) are reduced, and a Rayleigh scattering region is obtained.
In the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the transparency is improved as the dispersed particle diameter is reduced. Furthermore, when the dispersed particle size is 100 nm or less, the scattered light is preferably extremely small. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle size is small. If the dispersed particle size is 1 nm or more, industrial production is easy.

(2) Silane compound (in this specification, the symbol “(B)” may be added)
The silane compound (B) according to the present invention has a three-dimensional siloxane bond as a main skeleton, and as shown in the following formula (1), a part of molecular ends are blocked with a silanol group (Si—OH), It is preferably a high molecular weight product having a group and / or a phenyl group as an organic substituent.

  That is, in the silane compound (B), a part of silicon atoms constituting the three-dimensional siloxane bond has an OH group, and a part of silicon atoms constituting the outermost part of the silane compound also has an OH group. The silane compound molecule is preferably a molecule having an OH group directed outward.

  Since the silane compound (B) has a silanol group (Si—OH) in the structure, it is acidic (or basic) to promote hydrolysis and polycondensation reactions unlike metal alkoxides such as alkoxysilane. No catalyst or water is required. Because of the feature that the addition of water is unnecessary, the surface decomposition of the composite tungsten oxide due to the presence of water does not occur in the surface coating treatment step described later. As a result, the obtained composite tungsten oxide fine particles (A) can maintain the same heat ray shielding function as the composite tungsten oxide fine particles not subjected to the surface coating treatment.

  The molecular weight of the silane compound (B) according to the present invention is preferably 100 to 100,000, more preferably 500 to 10,000. When the molecular weight is 100 or more, the expected effect of water resistance and chemical stability can be obtained in the obtained composite tungsten oxide fine particles (A). On the other hand, when the molecular weight is 100,000 or less, the viscosity of the silane compound (B) does not become too high, and the dispersibility of the composite tungsten oxide fine particles (A) can be avoided.

The silane compound (B) is generally obtained by using four types of chlorosilanes as raw materials and hydrolyzing them.
Moreover, it is also possible to use a commercial item as a silane compound (B), TSR127B (made by Momentive Performance Materials Japan / nonvolatile component 50%), TSR145 (made by Momentive Performance Materials Japan) Etc. are mentioned as preferable examples.

  The addition amount of the silane compound (B) to the composite tungsten oxide (A) is preferably 0.1 to 10.0 parts by weight with respect to 1 part by weight of the composite tungsten oxide (A). When the added amount is 0.1 parts by weight or more, the surface of the composite tungsten oxide fine particles (A) can be sufficiently covered, and the weather resistance of the composite tungsten oxide fine particles (A) is improved. On the other hand, when the added amount is 10 parts by weight or less, the dispersibility of the composite tungsten oxide fine particles is not hindered.

(3) Anti-agglomeration agent (in this specification, the symbol “(C)” may be added)
The anti-aggregation agent (C) according to the present invention is compatible with a polycarbonate resin (in the present specification, a symbol “(D)” may be added), and has surface-coated composite tungsten oxide fine particles. It is a polymer compound having a functional group for adsorbing to the surface of (A).

  Examples of the aggregation inhibitor (C) according to the present invention include a polymer compound containing at least one functional group selected from a hydroxyl group, a glycidyl group, a carboxyl group, or an amino group as a functional group.

  Commercially available products may be used as the anti-aggregation agent (C), and preferred examples include UF-5022 (manufactured by Toa Gosei), UG-4030 (manufactured by Toa Gosei), Jonkrill 611 (manufactured by BASF), and the like. As mentioned. The above UF-5022 and UG-4030 are obtained by continuously polymerizing a composition containing an acrylic monomer as a main component at a high temperature.

  Since the aggregation inhibitor (C) is compatible with the polycarbonate resin (D), the surface-coated composite tungsten oxide fine particles (A) hardly form aggregates in the masterbatch according to the present invention. Therefore, the dispersibility is sufficient, which is preferable. Further, when the aggregation inhibitor (C) has a functional group having an adsorption effect on the surface of the surface-coated composite tungsten fine particles (A), the surface-coated composite tungsten oxide fine particles in the polycarbonate resin (D). It is preferable because the aggregate (A) is difficult to form, the dispersibility is sufficient, and the haze (cloudiness) of the heat ray-shielding molded article is lowered and the design is improved.

  The addition amount of the anti-aggregation agent (C) is preferably 1.0 to 50 parts by weight, more preferably 2 to 20 parts by weight with respect to 1 part by weight of the composite tungsten oxide (A). . If the addition amount is 1.0 part by weight or more, the composite tungsten oxide fine particles (A) hardly form an aggregate in the dispersion, and the dispersibility becomes sufficient. Moreover, if the said addition amount is 50 weight part or less, the fall of the mechanical strength of a heat ray shielding molded object and the deterioration of the weather resistance at the time of using outdoors can be avoided.

(4) Polycarbonate resin (D)
The polycarbonate resin (D) used in the present invention is not particularly limited as long as it is a polycarbonate resin used in this field. However, an aromatic polycarbonate can be mentioned as a particularly preferable polycarbonate resin (D).
Furthermore, examples of the aromatic polycarbonate include divalent phenolic compounds represented by 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. A polycarbonate synthesized by using one or more and a carbonate precursor represented by phosgene or diphenyl carbonate can be given.

The method for synthesizing the polycarbonate resin (D) used in the present invention may be a known method such as interfacial polymerization, melt polymerization, or solid phase polymerization.
Examples of the divalent phenol compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2bis. (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2, 2bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, Bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane; 1 Bis (hydroxyaryl) cycloalkanes such as 1-bis (4-hydroxyphenyl) cyclopentane and 1,1- (4-hydroxyphenyl) cyclohexane; 4,4′-dihydroxydiphenyl ether, bis (4-hydroxy-3- Dihydroxy aryl ethers such as methylphenyl) ether; dihydroxydiaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide and bis (4-hydroxy-3-methylphenyl) sulfide; 4,4′-dihydroxydiphenyl sulfoxide, bis ( Dihydroxydiaryl sulfoxides such as 4-hydroxy-3-methylphenyl) sulfoxide; dihydroxydia such as 4,4′-dihydroxydiphenylsulfone, bis (4-hydroxy-3-methylphenyl) sulfone Rusuruhon like; 4,4-biphenol and the like. In addition, for example, resorcin, and 3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-cumylresorcin, 2,3, Substituted resorcin such as 4,6-tetrafluororesorcin, 2,3,4,6-tetrabromoresorcin; catechol; hydroquinone, 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3 -T-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butylhydroquinone, 2,3,5 6-tetrafluorohydroquinone, 2, 3, Substituted hydroquinone, such as 1,6-tetrabromohydroquinone, and 2,2,2 ′, 2′-tetrahydro-3,3,3 ′, 3′-tetramethyl-1,1′-spirobis (1H-indene)- 7,7 ′ diol and the like can also be used. These divalent phenol compounds may be used alone or in combination of two or more.

  There is no particular limitation on the carbonate precursor represented by phosgene or diphenyl carbonate, which is reacted with the above-mentioned divalent phenolic compound. For example, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, di Examples thereof include, but are not limited to, naphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Preferably, diphenyl carbonate is used. These carbonate precursors may also be used alone or in combination of two or more.

  When producing the polycarbonate resin (D), a dicarboxylic acid or a dicarboxylic acid ester may be contained as an acid component. Examples of dicarboxylic acids and dicarboxylic acid esters include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl terephthalate and diphenyl isophthalate; succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid Aliphatic dicarboxylic acids such as acid, decanedioic acid, dodecanedioic acid, diphenyl sebacate, diphenyl decanedioate, diphenyl dodecanedioate; cyclopropanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid 1,2′-cyclopentanedicarboxylic acid, 1,3-cyclopentanecarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid diphe 1,2-cyclobutanedicarboxylic acid diphenyl, 1,3-cyclobutanedicarboxylic acid diphenyl, 1,2-cyclopentanedicarboxylic acid diphenyl, 1,3-cyclopentanedicarboxylic acid diphenyl, 1,2-cyclohexanedicarboxylic acid diphenyl, 1 And alicyclic dicarboxylic acids such as diphenyl 4-cyclohexanedicarboxylate. These dicarboxylic acids or dicarboxylic acid esters may be used alone or in combination of two or more. The dicarboxylic acid or dicarboxylic acid ester is contained in the carbonate precursor in an amount of preferably 50 mol% or less, more preferably 30 mol% or less.

  In producing the polycarbonate resin (D), a polyfunctional compound having three or more functional groups in one molecule can be used. As these polyfunctional compounds, compounds having a phenolic hydroxyl group or carboxyl are preferred, and compounds containing three phenolic hydroxyl groups are particularly preferred.

  It is also possible to use commercially available polycarbonate resin, such as polycarbonate resin pellets (manufactured by Bayer), polycarbonate resin pellets (manufactured by Mitsubishi Engineering Plastics), polycarbonate resin pellets (manufactured by Teijin Chemicals), and polycarbonate resin pellets (Idemitsu Kosan). Product) and the like.

2. Production Process of Dispersion of Composite Tungsten Oxide Fine Particles (A) First, the composite tungsten oxide fine particles (A) and an organic solvent are mixed, dispersed, and slurried. Thereafter, it is preferable to crush the composite tungsten oxide fine particles (A). Thereby, a dispersion liquid in which the composite tungsten oxide fine particles (A) are sufficiently dispersed in the organic solvent is obtained. As a method applied to the pulverization treatment, a wet pulverization method using a medium stirring mill such as an ultrasonic homogenizer or a ball mill (bead mill) is preferable.

Here, as the organic solvent, toluene, xylene, methyl isobutyl ketone and butyl acetate are preferable, and methyl isobutyl ketone is more preferable.
Moreover, it is preferable that the density | concentration range of the composite tungsten oxide fine particle contained in the slurry manufactured is 5-40 wt%, More preferably, it is 10-30 wt%. If the concentration of the composite tungsten oxide fine particles is 5 wt% or more, a large amount of organic solvent is not required for the composite tungsten oxide fine particles, thereby reducing manufacturing costs and improving mass productivity. Moreover, if it is 40 wt% or less, the cohesion force of microparticles | fine-particles will be suppressed and sufficient dispersion stability of microparticles | fine-particles can be maintained in an organic solvent.

3. Surface coating step of the composite tungsten oxide fine particles (A) The dispersion having the composite tungsten oxide fine particles (A) dispersed in an organic solvent has a siloxane bond, and at least one silicon atom is a silanol group. The silane compound (B) having (Si—OH) is added and mixed. And after the said addition mixing, a polymerization catalyst is added and the surface is covered with the polycondensation product of the silane compound (B) by subjecting the silanol group (Si—OH) contained in the silane compound (B) to a polycondensation reaction. A dispersion of the surface-coated composite tungsten oxide fine particles (A) thus obtained is obtained.

Here, an aluminum chelate can be applied as the polymerization catalyst. Commercially available products may be used as the polymerization catalyst, and preferred examples include ALCH (manufactured by Kawaken Fine Chemical Co., Ltd.), ALCH-TR (manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd.), and the like. It is done.
A silane compound (B) having a siloxane bond and at least one silicon atom having a silanol group (Si—OH) in a dispersion in which the composite tungsten oxide fine particles (A) are dispersed in an organic solvent. ) Is added and mixed, and then a polymerization catalyst is added and the mixture is stirred for a predetermined temperature and time, whereby the silanol group (Si—OH) contained in the silane compound (B) can be subjected to a condensation polymerization reaction.

4). Production process of powder of surface-coated composite tungsten oxide fine particles (A) After adding anti-aggregation agent (C) to the dispersion of surface-coated composite tungsten oxide fine particles (A) and mixing the mixture, By volatilizing the organic solvent, a powdery body of surface-coated composite tungsten oxide fine particles (A) whose surface is coated with a condensation polymer of the silane compound (B) is obtained.

5. Manufacturing process of surface-coated composite tungsten oxide fine particle-dispersed polycarbonate resin master batch The master batch according to the present invention is a surface-coated composite tungsten oxide whose surface is coated with a polycondensation product of the silane compound (B) obtained in the manufacturing process. It is produced by melt-kneading a powdered product fine particle (A) with a polycarbonate resin (D).
The produced master batch according to the present invention is, for example, kneaded with a vent type uniaxial or biaxial extruder and processed into a pellet form. This pellet-like masterbatch can be obtained by the most common method of cutting melt-extruded strands. Accordingly, examples of the shape include a cylindrical shape and a prismatic shape. It is also possible to adopt a so-called hot cut method in which the molten extrudate is directly cut. In such a case, it is common to take a shape close to a sphere.

6). Molded product obtained using masterbatch The molded product according to the present invention is obtained by diluting the masterbatch according to the present invention with a polycarbonate resin (D) or a different kind of thermoplastic resin compatible with the polycarbonate resin. A molded product obtained by melt-kneading and then forming into a predetermined shape.
As the molding method, injection molding, extrusion molding, compression molding, rotational molding, or the like can be used. In particular, injection molding and extrusion molding are preferable because they can be efficiently molded into a desired shape. For example, as a method for obtaining a plate-shaped (sheet-shaped) or film-shaped molded body by extrusion molding, a method is adopted in which a molten acrylic resin extruded using an extruder such as a T-die is drawn while being cooled by a cooling roll. .

  The molding temperature used in the molding method varies depending on the composition of the polycarbonate resin molding material to be used, but is set to a temperature higher by 50 to 150 ° C. than the melting point of the resin or the glass transition temperature so as to obtain sufficient fluidity. Specifically, the temperature is 200 ° C. or higher, preferably 240 ° C. to 330 ° C. When the molding temperature is 200 ° C. or higher, the viscosity specific to the polymer can be lowered, and the surface-coated composite tungsten oxide fine particles can be uniformly dispersed in the polycarbonate resin, which is preferable. If the molding temperature is 350 ° C. or lower, it is preferable that the polycarbonate resin can be prevented from being decomposed and deteriorated.

7). Laminated body The laminated body which concerns on this invention is a laminated body by which the molded object which concerns on the said invention is laminated | stacked on transparent molded objects other than polycarbonate resin (D). The laminate itself can be used for window materials, arcades, ceiling domes, carports and the like used for openings of building roofing materials, wall materials, automobiles, trains, airplanes and the like.

  The molded body according to the present invention can be used as a structural material by forming a transparent laminated body that is laminated and integrated on a transparent molded body such as inorganic glass, resin glass, or resin film by an arbitrary method. Specifically, for example, a transparent laminate having a heat ray shielding function and a scattering prevention function is obtained by laminating and integrating a molded body according to the present invention, which has been previously formed into a film shape, onto an inorganic glass by a thermal lamination method. I can do it.

Furthermore, a heat ray shielding transparent laminate is obtained by co-extrusion, press molding, injection molding, etc., simultaneously with the molding of the molded body according to the present invention, and by laminating and integrating with other transparent molded bodies. Is also possible.
The heat ray shielding transparent laminated body demonstrated above can be used as a more useful structural material by complementing a fault, mutually exhibiting the advantage which both molded objects have effectively.

EXAMPLES Hereinafter, although this invention is demonstrated in detail, referring an Example, this invention is not restrict | limited at all by the following example.
Regarding the optical property evaluation of the molded product obtained in this example, haze (in the present specification, a symbol “(H)” may be added) (unit:%) is a haze meter (Murakami Color Research Laboratory). Measured according to JIS K 7136. Further, the visible light transmittance (in the present specification, a symbol “(T)” may be added) (unit:%) and the solar transmittance ST (unit:%) are spectrophotometers U-4000 ( (Manufactured by Hitachi, Ltd.).

Example 1
200 g of composite tungsten oxide Cs _0.33 WO ₃ having a particle diameter of 1 to 3 μm as composite tungsten oxide fine particles (A) and 1800 g of methyl isobutyl ketone as a solvent were mixed by stirring to prepare a slurry. This slurry was put into a medium stirring mill together with beads, and the slurry was circulated and pulverized and dispersed to obtain a composite tungsten oxide fine particle dispersion (hereinafter, this composite tungsten oxide fine particle dispersion is referred to as “α liquid”). Abbreviated.) The dispersed particle diameter of the composite tungsten oxide fine particles was 90 nm.

  As the silane compound (B), TSR127B (Momentive Performance Materials Japan / nonvolatile component 50%) (hereinafter, the silane compound (B) is abbreviated as “B-1”) is a solvent. A 10% non-volatile component solution was prepared by dissolving in methyl isobutyl ketone (hereinafter, the solution is abbreviated as “β solution”).

  10 g of α solution, 10 g of β solution, and 0.05 g of ALCH (manufactured by Kawaken Fine Chemical Co., Ltd.) as a catalyst were mixed with stirring to prepare a mixed solution. Subsequently, while the mixture was stirred, the mixture was reacted at room temperature for 15 hours and further at 70 ° C. for 3 hours to prepare a surface-coated composite tungsten oxide fine particle (A) dispersion (hereinafter, the solution was (Abbreviated as “γ liquid”).

  UF5022 (manufactured by Toagosei Co., Ltd.) (hereinafter referred to as “Togyo Gosei Co., Ltd.”) is used as an aggregation inhibitor (C) having a compatibility with the polycarbonate resin (D) and having a functional group adsorbed on the surface of the surface coated composite tungsten oxide fine particles (A) The aggregation inhibitor (C) is abbreviated as “C-1”.) Was dissolved in methylxobutyl ketone as a solvent to prepare a 40 mass% solution (hereinafter, the solution is abbreviated as “δ solution”). To do.)

  10 g of the γ solution and 7.5 g of the δ solution were mixed. Then, the methyl isobutyl ketone is volatilized from the obtained mixed liquid, and further pulverized with a raking machine, so that the surface-coated composite tungsten oxide fine particles are uniformly dispersed in the aggregation inhibitor (C-1). A powdery body is obtained. The powdery body contains 1 part by weight of the silane compound (B-1) and 6 parts by weight of the aggregation inhibitor (C-1) with respect to 1 part by weight of the composite tungsten oxide fine particles (A).

  Next, the powdered body in which the surface-coated composite tungsten oxide fine particles are uniformly dispersed in the obtained anti-aggregation agent (C-1) has a composite tungsten oxide fine particle content of 0.5% by weight. Add to the polycarbonate resin pellets (manufactured by Bayer). And after mixing the said powdery body and a polycarbonate resin pellet uniformly, it melt-kneads with a twin-screw extruder (made by Toyo Seiki Seisakusho), cuts the extruded strand of 3 mm in diameter into a pellet form, and surface coating composite A master batch mainly composed of tungsten oxide fine particles and polycarbonate resin was obtained.

  The obtained master batch and polycarbonate resin pellets (manufactured by Bayer) were uniformly mixed so that the content of the composite tungsten oxide fine particles (A) was 0.05% by weight, and then an injection molding machine ( Toyo Seiki Seisakusho) was used to obtain a sheet-like molded body having a size of 10 cm × 5 cm and a thickness of 2.0 mm.

Optical properties of the obtained sheet-like molded product: haze (H), visible light transmittance T (unit:%), and solar radiation transmittance ST (unit:%) were evaluated. The evaluation results are shown in Table 1.
Subsequently, after the obtained sheet-like molded body was kept in an air bath at 120 ° C. for 30 days, again, optical characteristics: haze (H), visible light transmittance T (unit:%), solar transmittance ST (unit) :%). The evaluation results are shown in Table 1.

(Example 2)
Example 2 in which 50 g of β solution was added to 10 g of α solution and mixed, and the surface-coated composite tungsten oxide fine particles (A) were uniformly dispersed in the aggregation inhibitor (C) in the same manner as in Example 1. The powdery body which concerns on was obtained. The powdery body contains 5 parts by weight of the silane compound (B-1) and 6 parts by weight of the aggregation inhibitor (C-1) with respect to 1 part by weight of the composite tungsten oxide fine particles (A). .

Next, the obtained powdery body according to Example 2 was used, and a sheet-like molded body according to Example 2 was obtained in the same manner as in Example 1. The optical properties (haze, visible light transmittance T (unit:%), solar transmittance ST (unit:%)) of the obtained sheet-like molded product according to Example 2 were evaluated. The evaluation results are shown in Table 1.
Subsequently, after holding the sheet-like molded product according to Example 2 in a 120 ° C. air bath for 30 days, again, optical characteristics: haze (H), visible light transmittance T (unit:%), solar radiation transmittance. ST (unit:%) was evaluated. The evaluation results are shown in Table 1.

(Example 3)
Example 3 in which 1 g of β solution was added to 10 g of α solution and mixed, and the surface-coated composite tungsten oxide fine particles (A) were uniformly dispersed in the aggregation inhibitor (C) in the same manner as in Example 1. The powdery body which concerns on was obtained. The powdery body contains 0.1 part by weight of the silane compound (B-1) and 6 parts by weight of the aggregation inhibitor (C-1) with respect to 1 part by weight of the composite tungsten oxide fine particles (A). ing.

Next, the obtained powdery body according to Example 3 was used, and a sheet-like molded body according to Example 3 was obtained in the same manner as in Example 1. The optical properties (haze, visible light transmittance T (unit:%), solar transmittance ST (unit:%)) of the obtained sheet-like molded product according to Example 3 were evaluated. The evaluation results are shown in Table 1.
Subsequently, after holding the molded body according to Example 3 in a 120 ° C. air bath for 30 days, the optical characteristics: haze (H), visible light transmittance T (unit:%), solar transmittance ST ( (Unit:%) was evaluated. The evaluation results are shown in Table 1.

Example 4
In 10 g of γ liquid, 1.1 g of σ liquid is added and mixed, and the surface-coated composite tungsten oxide fine particles (A) are uniformly dispersed in the aggregation inhibitor (C) in the same manner as in Example 1. A powdery body according to Example 4 was obtained. The powdery body contains 1 part by weight of the silane compound (B-1) and 0.9 part by weight of the aggregation inhibitor (C-1) with respect to 1 part by weight of the composite tungsten oxide fine particles (A). ing.

Next, the obtained powdery body according to Example 4 was used, and a sheet-like molded body according to Example 4 was obtained in the same manner as in Example 1. The optical properties (haze, visible light transmittance T (unit:%), solar transmittance ST (unit:%)) of the obtained sheet-like molded product according to Example 4 were evaluated. The evaluation results are shown in Table 1.
Subsequently, after holding the molded body according to Example 4 in a 120 ° C. air bath for 30 days, the optical characteristics: haze (H), visible light transmittance T (unit:%), solar transmittance ST ( (Unit:%) was evaluated. The evaluation results are shown in Table 1.

(Example 5)
68.8 g of σ liquid is added to 10 g of γ liquid, and the surface-coated composite tungsten oxide fine particles (A) are uniformly dispersed in the aggregation inhibitor (C) in the same manner as in Example 1. A powdery body according to Example 5 was obtained. The powdery body contains 1 part by weight of the silane compound (B-1) and 55 parts by weight of the aggregation inhibitor (C-1) with respect to 1 part by weight of the composite tungsten oxide fine particles (A).

Next, the obtained powdery body according to Example 5 was used, and a sheet-like molded body according to Example 5 was obtained in the same manner as in Example 1. The optical properties (haze, visible light transmittance T (unit:%), solar transmittance ST (unit:%)) of the obtained sheet-like molded product according to Example 5 were evaluated. The evaluation results are shown in Table 1.
Subsequently, the molded body according to Example 5 was held in a 120 ° C. air bath for 30 days, and then again optical characteristics: haze (H), visible light transmittance T (unit:%), solar transmittance ST (unit) :%). The evaluation results are shown in Table 1.

(Example 6)
A sheet-like molded body according to Example 6 was obtained in the same manner as in Example 1 except that TSR145 (manufactured by Momentive Performance Materials Japan) was used as the silane compound (B).
The optical properties of the obtained sheet-like molded article according to Example 6 were evaluated for haze (H), visible light transmittance T (unit:%), and solar transmittance ST (unit:%). The evaluation results are shown in Table 1.
Subsequently, after holding the molded body according to Example 6 in a 120 ° C. air bath for 30 days, again, optical characteristics: haze (H), visible light transmittance T (unit:%), solar radiation transmittance ST (unit) :%). The evaluation results are shown in Table 1.

(Example 7)
A sheet-like molded product according to Example 7 was obtained in the same manner as in Example 1 except that BR52 (manufactured by Mitsubishi Rayon Co., Ltd.) was used as the aggregation inhibitor (C). The optical properties: haze (H), visible light transmittance T (unit:%), and solar transmittance ST (unit:%) of the obtained sheet-like molded product according to Example 7 were evaluated. The evaluation results are shown in Table 1.
Subsequently, the molded body according to Example 7 was held in a 120 ° C. air bath for 30 days, and then again optical characteristics: haze (H), visible light transmittance T (unit:%), solar transmittance ST (unit) :%). The evaluation results are shown in Table 1.

(Comparative Example 1)
A sheet according to Comparative Example 1 in the same manner as in Example 1 except that UC-3920 (manufactured by Toagosei Co., Ltd.) that is not compatible with the polycarbonate resin (D) was used as the aggregation inhibitor (C). A molded body was obtained. The optical properties: haze (H), visible light transmittance T (unit:%), and solar radiation transmittance ST (unit:%) of the obtained sheet-like molded article according to Comparative Example 1 were evaluated. The evaluation results are shown in Table 1.
Subsequently, the molded body according to Comparative Example 1 was kept in a 120 ° C. air bath for 30 days, and then again optical characteristics: haze (H), visible light transmittance T (unit:%), solar transmittance ST (unit) :%). The evaluation results are shown in Table 1.

(Comparative Example 2)
A comparison was made in the same manner as in Example 1 except that BR-105 (manufactured by Toagosei Co., Ltd.) having no functional group adsorbing on the surface of the surface-coated composite tungsten oxide fine particles was used as the aggregation inhibitor (C). A sheet-like molded body according to Example 2 was obtained. The optical properties of the sheet-like molded product according to Comparative Example 2 obtained were evaluated for haze (H), visible light transmittance T (unit:%), and solar transmittance ST (unit:%). The evaluation results are shown in Table 1.
Subsequently, after holding the molded body according to Comparative Example 2 in a 120 ° C. air bath for 30 days, again, optical characteristics: haze (H), visible light transmittance T (unit:%), solar radiation transmittance ST (unit) :%). The evaluation results are shown in Table 1.

(Comparative Example 3)
A sheet-like molded body was obtained in the same manner as in Example 1 except that tetraethoxysilane (manufactured by Tama Chemical Co., Ltd.) was used as the silane compound (B). The optical properties (haze, visible light transmittance T (unit:%), solar transmittance ST (unit:%)) of the obtained sheet-like molded product according to Comparative Example 3 were evaluated. The evaluation results are shown in Table 1.
Subsequently, after holding the molded body according to Comparative Example 3 in a 120 ° C. air bath for 30 days, optical properties: haze (H), visible light transmittance T (unit:%), solar radiation transmittance ST (unit:%) ) Was evaluated. The evaluation results are shown in Table 1.

(Comparative Example 4)
A sheet-like molded body was obtained in the same manner as in Example 1 except that the silane compound (B) was not added. The optical properties (haze, visible light transmittance T (unit:%), solar transmittance ST (unit:%)) of the obtained sheet-like molded product according to Comparative Example 4 were evaluated. The evaluation results are shown in Table 1.
Subsequently, after holding the molded body according to Comparative Example 4 in a 120 ° C. air bath for 30 days, optical characteristics: haze (H), visible light transmittance T (unit:%), solar radiation transmittance ST (unit:%) ) Was evaluated. The evaluation results are shown in Table 1.

Claims (10)

In an organic solvent, the 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, V , Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0), in which the composite tungsten oxide fine particles are dispersed, the siloxane bond is present, and at least one silicon atom has a silanol group (Si—OH). Adding a silane compound having
Adding a catalyst to the dispersion to which the silane compound is added, and obtaining a dispersion of the surface-coated composite tungsten oxide fine particles coated with the condensation product of the silane compound;
From the hydroxyl group, glycidyl group, carboxyl group, or amino group that is compatible with the polycarbonate resin and adsorbed on the surface of the surface-coated composite tungsten oxide fine particles in the dispersion liquid of the surface-coated composite tungsten oxide fine particles. After adding the aggregation inhibitor having at least one selected functional group, the organic solvent is volatilized from the dispersion liquid of the surface-coated composite tungsten oxide fine particles, and the powder of the surface-coated composite tungsten oxide fine particles is obtained. Obtaining a step;
A step of melt-kneading the powder of the surface-coated composite tungsten oxide fine particles with a polycarbonate resin to obtain a polycarbonate resin master batch in which the surface-coated composite tungsten oxide fine particles are dispersed. A method for producing a composite tungsten oxide fine particle-dispersed polycarbonate resin master batch.   2. The composite tungsten oxide fine particle according to claim 1, wherein the aggregation inhibitor is a polymer compound containing at least one functional group selected from a hydroxyl group, a glycidyl group, a carboxyl group, or an amino group. A method for producing a dispersed polycarbonate resin masterbatch.   3. The composite tungsten oxide according to claim 1, wherein an addition amount of the aggregation inhibitor is 1.0 to 50 parts by weight with respect to 1 part by weight of the composite tungsten oxide. Production method of fine particle dispersed polycarbonate resin masterbatch.   The molecular weight of the said silane compound is 100-100000, The manufacturing method of the composite tungsten oxide fine particle dispersion | distribution polycarbonate resin masterbatch in any one of Claims 1-3 characterized by the above-mentioned.   5. The composite tungsten oxidation according to claim 1, wherein the addition amount of the silane compound is 0.1 to 10.0 parts by weight with respect to 1 part by weight of the composite tungsten oxide. Of manufacturing fine particle-dispersed polycarbonate resin masterbatch.   6. The method for producing a composite tungsten oxide fine particle-dispersed polycarbonate resin master batch according to claim 1, wherein a primary particle size of the composite tungsten oxide fine particles is 1 nm or more and 200 nm or less.   A composite tungsten oxide fine particle-dispersed polycarbonate resin master batch produced by the production method according to claim 1, wherein the surface-coated composite tungsten oxide fine particles are dispersed in a polycarbonate resin.   A molding characterized in that it is obtained by diluting, melting and kneading the master batch according to claim 7 with a polycarbonate resin or a different kind of thermoplastic resin compatible with the polycarbonate resin, and molding the master batch into a predetermined shape. body.   A molded article comprising at least one coating layer selected from a hard coat layer and an antireflection layer on one or both sides of the molded article according to claim 8.   A laminate comprising the molded product according to claim 8 laminated on another transparent molded product.