WO2013146497A1 - Material used for buildings or transportation devices - Google Patents

Abstract

The purpose of the present invention is to provide a material used for buildings or transportation devices that has excellent transparency to visible light and near-infrared absorbency and that comprises a composition including polycarbonate. This material used for buildings or transportation devices comprises a composition including polycarbonate and copper alkylphosphonates, wherein: in 100 mol% of said copper alkylphosphonates, a copper alkylphosphonate represented by general formula (1) (in general formula (1), R¹ is an alkyl group having a carbon number of from 4 to 6) constitutes 70-100 mol%, and a copper alkylphosphonate represented by general formula (2) (in general formula (2), R² is an alkyl group having a carbon number of 2, 3, or from 7 to 40) constitutes 0-30 mol%; and said composition substantially does not include phosphoric monoesters and phosphoric diesters.

Description

Materials used for construction or transportation equipment

The present invention relates to materials used for construction or transportation equipment.

Polycarbonate has excellent physical properties such as transparency, impact resistance, heat resistance, and flame resistance, and is widely used as engineering plastic. Specific uses of polycarbonate include optical applications such as lenses, housings for electronic devices such as personal computers, window materials for transportation equipment such as automobiles, ships and airplanes, and window materials for construction.

By the way, the sun rays include ultraviolet rays, infrared rays and the like in addition to visible rays. Among infrared rays, infrared rays having a wavelength close to visible light are called near infrared rays. Near-infrared rays are also called heat rays and are one of the causes of temperature rise in transportation equipment and buildings.

For this reason, when polycarbonate is used as a window material, it is desired to impart near infrared absorption. In general, when a near-infrared absorptivity is imparted to a resin, a near-infrared absorber is added to the resin.

Inorganic near infrared absorbers such as phthalocyanine near infrared absorbers and hexaboride are known. However, when these polycarbonate resins containing phthalocyanine-based near-infrared absorbers or inorganic near-infrared absorbers are exposed to high temperatures and high humidity for accelerated evaluation under outdoor exposure conditions, phthalocyanine-based near-infrared absorbers When it contains, the molecular weight of the polycarbonate decreases, and when it contains an inorganic near infrared absorber, the haze tends to increase.

Also, antimony-containing tin oxide (ATO) and tin-containing indium oxide (ITO) are known as materials having near infrared absorptivity. These fine particles have low solar radiation shielding power per unit mass and need to be used in a large amount in order to impart sufficient near-infrared absorptivity. It has been difficult to achieve both near infrared absorptivity and visible light transmittance.

In addition, a method for improving near-infrared absorptivity as a whole molded article by providing a resin layer containing a near-infrared absorber on a base material made of polycarbonate instead of adding a near-infrared absorber to polycarbonate. There is. However, there is a problem in that the cost for the resin layer containing the near-infrared absorber and the base material is required to be increased and the cost is increased.

For example, phosphonic acid compounds such as ethylphosphonic acid and vinylphosphonic acid, or phosphinic acid compounds such as dimethylphosphinic acid and diphenylphosphinic acid, and metal ions such as copper ions and rare earth metal ions are contained in the solvent or resin. There is known an optical material characterized by comprising (see, for example, Patent Document 1). Patent Document 1 discloses that the optical material has absorption characteristics or light emission characteristics of light having a specific wavelength, and further, thermal decomposition is less likely to occur than in the prior art.

An optical material comprising at least one compound selected from a phosphonic acid monoester compound, a phosphinic acid compound, a phosphoric acid diester compound, and a phosphoric acid monoester compound, a phosphonic acid compound, and a metal ion such as a copper ion. Materials are known (see, for example, Patent Document 2).

Patent Document 2 discloses that the optical material is excellent in compatibility with a resin, and a resin optical member having sufficient optical characteristics can be obtained by using the optical material.
However, for a composition containing a polycarbonate and a near-infrared absorber that can be suitably used for a window material or the like, the transparency in visible light and the excellent near-infrared absorptivity are compatible at an extremely high level. Has not yet been achieved.

Japanese Patent Laid-Open No. 2002-6101 JP 2002-69305 A

This invention is made in view of the said prior art, and provides the material used for the building or transport apparatus which consists of a composition containing a polycarbonate which is excellent in transparency in visible light and near-infrared absorptivity. With the goal.

The present inventors have intensively studied to solve the above problems. In the research, in order to improve the dispersibility of the near-infrared absorber, the present inventors have found that the presence of dispersants such as phosphoric monoesters and phosphoric diesters that have been used in the past can be used for molding polycarbonate. It has been found that it causes coloring under high temperature conditions.

Further, as a result of further studies by the present inventors, the composition containing the specific alkylphosphonic acid copper salt and the polycarbonate exhibits sufficient near-infrared absorptivity even when the dispersant is not used. It was found that the film was excellent in transparency even when thermoformed, and the present invention was completed.

That is, the material used for the building or transportation equipment of the present invention contains polycarbonate and an alkylphosphonic acid copper salt, and the alkylphosphonic acid copper represented by the following general formula (1) in 100 mol% of the alkylphosphonic acid copper salt. A composition containing 70 to 100 mol% of a salt, 0 to 30 mol% of an alkylphosphonic acid copper salt represented by the following general formula (2), and substantially free of phosphoric monoester and phosphoric diester Become.

(In the general formula (1), R ¹ is an alkyl group having 4 to 6 carbon atoms.)

(In the general formula (2), R ² is an alkyl group having 2, 3 or 7 to 40 carbon atoms.)
In the general formula (2), R ² is preferably an alkyl group having 2, 3 or 7 to 10 carbon atoms.

In the general formula (1), at least a part of R ¹ is preferably an n-butyl group.
It is preferable melt volume rate of the polycarbonate is 1 ~ 100cm ³ / 10min.

The composition preferably contains 0.0005 to 50 parts by mass of the alkylphosphonic acid copper salt with respect to 100 parts by mass of the polycarbonate.
It is preferable that the composition further contains a bluing agent.

It is preferable that the material is a window material.

The material used for the building or transportation equipment of the present invention is composed of a composition containing polycarbonate, and is excellent in transparency in visible light and near infrared absorption.
For this reason, the material used for the construction or transportation equipment of the present invention can be suitably used as a window material.

Next, the present invention will be specifically described.
The material used for the construction or transportation equipment of the present invention comprises a composition containing polycarbonate and alkylphosphonic acid copper salt and substantially free of phosphoric acid monoester and phosphoric acid diester.
In the present specification, “materials used for construction or transportation equipment” is also simply referred to as “materials”.

[Polycarbonate]
There is no limitation in particular as a polycarbonate used for this invention. As the polycarbonate, any polycarbonate conventionally used in construction and transportation equipment can be suitably used.

As the polycarbonate, a polymer obtained by reacting a dihydric phenol compound with a compound that forms a carbonate bond by reacting with a dihydric phenol compound such as phosgene or diphenyl carbonate is usually used. As the dihydric phenol compound, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A) or the like can be used.

There is no limitation in particular as a manufacturing method of a polycarbonate, It can manufacture by a conventionally well-known manufacturing method.
The polycarbonate used in the present invention, it is preferable that the melt volume rate (MVR) is 1 ~ 100cm ³ / 10min, more preferably 2 ~ 80cm ³ / 10min, to be ³ ~ 70cm ³ / 10min Particularly preferred. In the present invention, the MVR of polycarbonate is a value measured at 300 ° C. and a load of 1.2 kgf in accordance with ISO 1133.

The polycarbonate may be a commercially available product, for example, Panlite L-1250Y (manufactured by Teijin Chemicals Ltd., MVR8cm ³ / 10min), Iupilon H-4000 (manufactured by Mitsubishi Engineering-Plastics, MVR60cm ³ / 10min), Iupilon S- 1000 (manufactured by Mitsubishi engineering-plastics, MVR7.1cm ³ / 10min) and the like can be used.

[Alkylphosphonic acid copper salt]
In the present invention, an alkylphosphonic acid copper salt is used. The alkylphosphonic acid copper salt used in the present invention may be a kind of alkylphosphonic acid copper salt or two or more kinds of alkylphosphonic acid copper salts. In addition, as the alkylphosphonic acid copper salt used in the present invention, the alkylphosphonic acid copper salt represented by the following general formula (1) is 70 to 100 mol% in 100 mol% of the alkylphosphonic acid copper salt, The alkylphosphonic acid copper salt represented by the following general formula (2) is 0 to 30 mol%.

(In the general formula (1), R ¹ is an alkyl group having 4 to 6 carbon atoms.)

(In the general formula (2), R ² is an alkyl group having 2, 3 or 7 to 40 carbon atoms.)
As the alkylphosphonic acid copper salt used in the present invention, at least the alkylphosphonic acid copper salt represented by the above general formula (1) is used, and the alkylphosphonic acid copper salt represented by the above general formula (2), You may use together. The alkylphosphonic acid copper salt represented by the general formula (1) may be used alone or in combination of two or more, and the alkylphosphonic copper represented by the general formula (2). As the salt, one kind may be used alone, or two or more kinds may be used.

As the alkylphosphonic acid copper salt represented by the general formula (2), R ² is preferably an alkyl group having 2, 3 or 7 to 10 carbon atoms from the viewpoint of the transparency of the material of the present invention. More preferably, R ² has ^{2, 3,} 7 or 8 carbon atoms.

The alkylphosphonic copper salt represented by the general formula (1), in view of the material transparency of the present invention, it is preferable that at least a portion of R ¹ is an n- butyl group, R ¹ is n More preferably, it is a -butyl group.

In addition, as the alkylphosphonic acid copper salt used in the present invention, the alkylphosphonic acid copper salt represented by the general formula (1) is 70 to 100 mol% in 100 mol% of the alkylphosphonic acid copper salt, The alkylphosphonic acid copper salt represented by the general formula (2) is 0 to 30 mol%, but from the viewpoint of transparency of the material of the present invention, the alkylphosphonic acid copper salt represented by the general formula (1) The alkylphosphonic acid copper salt represented by the general formula (2) is preferably 0 to 20 mol%, and the alkylphosphonic acid copper salt represented by the general formula (1). Is more preferably 90 to 100 mol%, and the alkylphosphonic acid copper salt represented by the general formula (2) is more preferably 0 to 10 mol%, and the alkylphosphonic acid copper represented by the general formula (1). Salt 00 It is mol%, i.e., it is particularly preferred alkylphosphonic copper salt used in the present invention is an alkyl phosphonic acid copper salt represented by the general formula (1).

Although there is no limitation in particular as a manufacturing method of the alkylphosphonic acid copper salt used for this invention, For example, it can manufacture with the following method.
As a method for producing an alkylphosphonic acid copper salt, for example, in a solvent, an alkylphosphonic acid compound represented by the following general formula (3) and a copper salt are mixed to obtain a reaction mixture (hereinafter also referred to as a reaction step). ), Removing the solvent from the reaction mixture by solvent removal means such as filtration to obtain the alkylphosphonic acid copper salt represented by the general formula (1) as a solid content (hereinafter also referred to as solvent removal step). The method which has is mentioned. In addition, although the alkylphosphonic acid copper salt obtained by this method is the alkylphosphonic acid copper salt represented by the general formula (1), the alkylphosphonic acid compound represented by the general formula (3) is represented by the following general formula ( By replacing with the alkylphosphonic acid compound represented by 4), the alkylphosphonic acid copper salt represented by the general formula (2) can be obtained.

(In the general formula (3), R ¹ is an alkyl group having 4 to 6 carbon atoms.)

(In the general formula (4), R ² is an alkyl group having 2, 3 or 7 to 40 carbon atoms.)
R ¹ in the general formula (3) is the same as R ¹ in the general formula (1), R ² in the general formula (4) is the same as R ² in the general formula (2).

The alkylphosphonic acid compound represented by the general formula (3) may be used alone or in combination of two or more. As the alkylphosphonic acid compound represented by the general formula (4), One kind may be used alone, or two or more kinds may be used.

Further, the alkylphosphonic acid compound represented by the above general formula (3) may be replaced with the alkali metal salt of the phosphonic acid compound to produce an alkylphosphonic acid copper salt represented by the above general formula (1). The alkylphosphonic acid copper salt represented by the general formula (2) may be produced by replacing the alkylphosphonic acid compound represented by the general formula (4) with the alkali metal salt of the phosphonic acid compound. Examples of the alkali metal include sodium and potassium.

As the copper salt, a copper salt capable of supplying divalent copper ions is usually used. The copper salt may be a copper salt other than the alkylphosphonic acid copper salt represented by the general formula (1) and the alkylphosphonic acid copper salt represented by the general formula (2). Examples of the copper salt include copper of organic acids such as anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate, anhydrous copper benzoate, anhydrous ethyl acetoacetate copper, anhydrous pyrophosphate, anhydrous naphthenic acid copper, and anhydrous copper citrate. Salt, hydrate or hydrate of copper salt of organic acid; copper salt of inorganic acid such as copper oxide, copper chloride, copper sulfate, copper nitrate, basic copper carbonate, hydrate of copper salt of inorganic acid Or a hydrate; copper hydroxide is mentioned. In addition, as a copper salt, you may use individually by 1 type, or may use 2 or more types.

As the copper salt, anhydrous copper acetate, copper acetate monohydrate, and copper nitrate are preferably used in terms of solubility and removal of by-products.
In addition, when producing the fine particles composed of the alkylphosphonic acid copper salt represented by the general formula (1) or the fine particles composed of the alkylphosphonic acid copper salt represented by the general formula (2), per 1 mole of the copper salt The alkylphosphonic acid compound represented by the general formula (3) or the alkylphosphonic acid compound represented by the general formula (4) is preferably used in an amount of 0.5 to 1.5 mol, preferably 0.8 to 1.2. It is more preferable to use a mole.

Examples of the solvent include alcohols such as methanol and ethanol, tetrahydrofuran (THF), dimethylformamide (DMF), water, and the like, and methanol, ethanol, THF, and water are preferable from the viewpoint of satisfactory reaction. The reaction step is preferably carried out at room temperature to 60 ° C., more preferably 20 to 40 ° C., preferably for 0.5 to 50 hours, more preferably for 1 to 30 hours.

In the reaction step, the alkylphosphonic acid compound represented by the general formula (3) or the alkylphosphonic acid compound represented by the general formula (4) and the copper salt react with each other. Insoluble fine particles of the alkylphosphonic acid copper salt represented by the general formula (1) or the alkylphosphonic acid copper salt represented by the general formula (2) are formed.

In addition, in the method for producing fine particles comprising the alkylphosphonic acid copper salt, the fine particles comprising the alkylphosphonic acid copper salt are usually obtained by removing at least a part of the solvent from the reaction mixture.

In the solvent removal step, the alkylphosphonic acid copper salt which is a solid content is obtained by removing the solvent from the reaction mixture.
In the solvent removal step, the solvent in the reaction mixture is removed by a method such as filtration of the reaction mixture or removal of the solvent by heating the reaction mixture.

Moreover, in order to dry the solvent contained in the alkylphosphonic acid copper salt after the solvent removing step, a drying step may be appropriately performed.
Conventionally, as a near-infrared absorber used for imparting near-infrared absorptivity to a resin, when using fine particles comprising a copper phosphonate, when producing an alkylphosphonic acid copper salt, a phosphoric acid monoester, Phosphoric acid diester or the like was used as a dispersant. Conventionally, the dispersant has been used in order to improve the dispersibility of the near-infrared absorber in the resin and to exhibit sufficient near-infrared absorptivity. However, when the present inventors use a dispersing agent such as phosphoric acid monoester or phosphoric acid diester, coloring occurs due to decomposition of the dispersing agent itself, or decomposition of the polycarbonate is accelerated by the dispersing agent. Found that there is a case. In order to eliminate these drawbacks, the inventors of the present invention can avoid the use of phosphoric acid monoesters and phosphoric acid diesters in the production of alkylphosphonic acid copper salts. It has been found useful to make it substantially not contained therein.

[Materials used in construction or transportation equipment]
The material used for the building or transportation equipment of the present invention is a composition comprising the polycarbonate and the alkylphosphonic acid copper salt. Moreover, the said composition does not contain phosphoric acid monoester and phosphoric acid diester substantially.

In the present invention, the fact that the composition is substantially free of phosphoric acid monoester and phosphoric acid diester means that phosphoric acid monoester and phosphoric acid diester are used for the purpose of dispersion and micronization of alkylphosphonic acid copper salt. Do not use it. Specifically, the said composition is normal, and 0.1 mass part or more of phosphoric acid monoester and phosphoric acid diester in total is not contained in 100 mass parts of compositions.

The material used for the building or transportation equipment of the present invention is excellent in visible light transmission, that is, transparency, and near infrared absorption. Moreover, since the material of the present invention can be produced without using phosphoric acid monoesters and phosphoric acid diesters, which have been conventionally used, it can be obtained at a lower cost than in the past.

In particular, according to the present invention, a material having a low HAZE, solar transmittance and YI (Yellow Index), while having a high visible light transmittance and an excellent balance between them can be obtained. HAZE (%) is usually 5.0% or less, preferably 4.0% or less, and particularly preferably 3.5% or less. The visible light transmittance (%) is usually 80% or more, preferably 83% or more, and particularly preferably 85% or more. The solar radiation transmittance (%) is 80% or less, preferably 70% or less, and particularly preferably 65% or less. YI is usually 5.0 or less, preferably 4.5 or less, and particularly preferably 4.0 or less.

A composition comprising the polycarbonate and the alkylphosphonic acid copper salt constituting the material of the present invention is obtained by molding the composition into a material constituting a part of a building or transportation equipment. Preferably, the resulting material contains 0.0001 g to 0.15 g of alkylphosphonic acid copper salt per square centimeter, more preferably 0.0005 to 0.1 g.

The composition may contain components other than the polycarbonate and the alkylphosphonic acid copper salt (hereinafter also referred to as other components).
Examples of the other components include a bluing agent, an ultraviolet absorber, and a release agent. In particular, it is preferable that the composition contains a bluing agent because coloring due to heat at the time of molding the material used in the building or transportation equipment of the present invention can be further suppressed.

In addition, the said other component may be added separately in a composition, and when a commercial item is used as said polycarbonate, the other component may be contained in the polycarbonate. In addition, when a commercial item is used as the polycarbonate, a bluing agent is usually added as an additive.

As the bluing agent, those conventionally used for the purpose of reducing coloring during processing of the polycarbonate can be used.
Examples of the bluing agent include the general name Solvent Violet 13 [CA. No (color index No) 60725], generic name Solvent Violet 31 [CA. No. 68210], generic name Solvent Violet 33, generic name Solvent Blue 94 [CA. No 61500], generic name Solvent Violet 36 [CA. No 68210], generic name Solvent Blue 97 ["Macrolex Violet RR" manufactured by Bayer, Inc.] [CA. No 615290] and the generic name Solvent Blue 45 [CA. No. 61110] is given as a representative example.

In addition, when the composition contains a bluing agent, the bluing agent is preferably contained in the composition in an amount of 0.01 ppm to 1000 ppm, more preferably 0.1 ppm to 100 ppm. Within the above range, it is possible to reduce the coloration of the polycarbonate during processing, and it is preferable because the influence of the visible light absorption of the bluing agent is small.

The ultraviolet absorber is not particularly limited. Examples of the ultraviolet absorber include metal oxide fine particles such as titanium oxide, cerium oxide, zinc oxide, tin oxide, tungsten oxide, zinc sulfide, and cadmium sulfide; 2- (2′-hydroxy-5′-methylphenyl) Benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-3) ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-3'- Dodecyl-5'-methyphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3, -tetramethylbutyl) -6- (2H-benzoto Riazol-2-yl) phenol], 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol and other benzotriazole ultraviolet absorbers; Salicylate ultraviolet absorbers such as rate, pt-butylphenyl salicylate, p-octylphenyl salicylate; benzophenone ultraviolet absorbers; 2- (4,6-diphenyl-1,3,5-triazine- And triazine ultraviolet absorbers such as 2-yl) -5- (hexyl) oxyphenol. Commercially available products may be used as the ultraviolet absorber, for example, Chemisorb 79 (trade name, manufactured by Chemipro Kasei Co., Ltd.), Hostain PR-25 and Hostavin B-CAP XP (trade names, both manufactured by Clariant). Can be mentioned.

In addition, when the composition contains an ultraviolet absorber, the ultraviolet absorber is preferably contained in an amount of 0.005 to 10 parts by mass, and 0.1 to 1 part by mass with respect to 100 parts by mass of the polycarbonate. More preferably. Within the above range, it is preferable because coloring due to deterioration of the ultraviolet absorber during processing can be suppressed.

As the release agent, fatty acid esters are generally used, and lower fatty acid esters such as stearic acid stearate, higher fatty acid esters such as sebacic acid behenate, and erythritol esters are used. When a release agent is used, it is usually used in an amount of 0.01 to 1 part by mass per 100 parts by mass of the polycarbonate resin.

There is no particular limitation on the method for producing the material used for the building or transportation equipment of the present invention. As a method for producing the material, for example, a dispersion in which the alkylphosphonic acid copper salt is dispersed in a solvent and a solution in which the polycarbonate is dissolved in a solvent are prepared, and the dispersion and the solution are mixed. Then, a method of obtaining a composition containing the polycarbonate and the alkylphosphonic acid copper salt by removing the solvent, melt-kneading the polycarbonate and the alkylphosphonic acid copper salt, Examples thereof include a method for obtaining a composition containing an alkylphosphonic acid copper salt.

The solvent used for producing the material is preferably a low-boiling solvent that can be easily removed, and the low-boiling solvent preferably has a boiling point of 20 to 80 ° C., specifically dichloromethane, methanol, etc. Is preferred.

[Use]
The material used for the building or transportation equipment of the present invention is excellent in visible light transmission, that is, in transparency, and in near-infrared absorption. Although the material of the present invention is used for construction or transportation equipment, since it has the optical characteristics described above, it is particularly preferable to use it as a window material.

That is, the material of the present invention is preferably a building window material and a window material for transportation equipment. Note that transportation equipment includes automobiles, ships, airplanes, helicopters, and the like.
In addition, the material of this invention may manufacture a molded article only from this material, and may manufacture a molded article as a laminated body which has a layer formed from this material.

For example, when the material of the present invention is used as a window material, the window may be formed only from the material. Usually, the window is formed as a laminate having a layer formed of the material of the present invention. .
By using a laminated body, various performances can be imparted to the window in addition to the near infrared absorptivity. For example, by providing a layer formed of the material of the present invention between two sheet glasses, a window having not only excellent near-infrared absorption but also excellent crime prevention can be obtained. Further, by providing a layer containing an ultraviolet absorber, the window can be provided with ultraviolet absorptivity in addition to the near infrared absorptivity.

Moreover, when forming a window as a laminated body which has the layer formed from the material of this invention, you may provide abrasion resistance by providing a hard-coat layer on the outer side of the layer formed from the material of this invention. . In addition, the said outer side means the side which faces outside air, when attached to a building or a transport equipment. The hard coat layer is usually formed from acrylic resin or silica. Further, an ultraviolet absorber may be added to the hard coat layer. By adding an ultraviolet absorber to the hard coat layer, it is possible to effectively prevent coloring of the layer formed from the material of the present invention, and it can be suitably used as a window material.

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
[Synthesis Example 1]
(Method for producing n-butylphosphonic acid copper salt)
Solution A was obtained by dissolving 1.03 g of n-butylphosphonic acid in 20 g of ethanol. 1.49 g of copper acetate monohydrate was dissolved in 50 g of ethanol to obtain a solution B. Solution A was added dropwise to Solution B at room temperature and stirred for 2 hours.
After stirring for 2 hours, the precipitate was filtered and vacuum dried at 60 ° C. for 4 hours to obtain n-butylphosphonic acid copper salt.

[Synthesis Example 2]
(Method for producing ethylphosphonic acid copper salt)
An ethylphosphonic acid copper salt was obtained in the same manner as in Synthesis Example 1 except that 1.03 g of n-butylphosphonic acid was replaced with 0.82 g of ethylphosphonic acid.

[Synthesis Example 3]
(Method for producing copper decylphosphonate)
A copper decylphosphonate was obtained in the same manner as in Synthesis Example 1 except that 1.03 g of n-butylphosphonic acid was replaced with 1.66 g of decylphosphonic acid.
The physical properties (HAZE, visible light transmittance, solar transmittance, yellow index) of the press sheets obtained in the following examples and comparative examples were measured and calculated by the following methods.

(Measurement of HAZE)
The HAZE of the press sheet was measured using a haze meter NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.

(Measurement of visible light transmittance and solar transmittance)
The visible light transmittance and solar transmittance of the press sheet were measured using a spectrophotometer U-4000 manufactured by Hitachi High-Technologies.

(Measurement of yellow index)
The yellow index (YI) of the press sheet is calculated from the following formula using tristimulus values (X, Y, Z values) measured using a spectrophotometer U-4000 (C light source) manufactured by Hitachi High-Technologies. did.
YI = 100 (1.28X-1.06Z) / Y

[Example 1]
(Manufacture of press sheets)
Dispersion C was prepared by adding 0.149 g of copper n-butylphosphonate to 15 g of dichloromethane and stirring for 5 min using a stirrer.

Polycarbonate solution D by dissolving (Teijin Chemicals Ltd., Panlite L-1250Y, melt volume rate ^{(MVR) 8cm 3 / 10min)} 10g was prepared in dichloromethane 50 g.

The dispersion C and the solution D were mixed using a stirrer, and the obtained mixture was spread on a vat and air-dried at room temperature to obtain a sheet-like copper salt-containing resin composition. This sheet-like copper salt-containing resin composition was dried at 120 ° C. for 8 hours to obtain a copper salt-containing resin composition.

The obtained copper salt-containing resin composition was press-molded at a temperature of 260 ° C. and 5 MPa for 5 minutes using a press machine to prepare a press sheet having a thickness of 0.78 mm.
The press sheet made of the resin composition contains 0.00138 g of n-butylphosphonic acid copper salt per square centimeter.

[Comparative Example 1]
A press sheet was prepared in the same manner as in Example 1 except that only the solution D was used without using the solution C.

[Example 2]
Polycarbonate (Teijin Chemicals Ltd., Panlite ^{L-1250Y, MVR8cm 3 / 10min} ) and was replaced by polycarbonate (manufactured by Mitsubishi Engineering-Plastics Iupilon ^{H-4000, MVR60cm 3 / 10min} ) the same manner as in Example 1, a press sheet It was created.

[Comparative Example 2]
Polycarbonate (Teijin Chemicals Ltd., Panlite ^{L-1250Y, MVR8cm 3 / 10min} ) and was replaced by polycarbonate (manufactured by Mitsubishi Engineering-Plastics Iupilon ^{H-4000, MVR60cm 3 / 10min} ) is performed in the same manner as in Comparative Example 1, a press sheet It was created.

[Comparative Example 3]
Dispersion E was prepared by adding 0.149 g of n-butylphosphonic acid copper salt to 15 g of dichloromethane and 0.075 g of Prisurf A219B as a dispersing agent, and stirring for 5 min using a stirrer.

A press sheet was prepared in the same manner as in Example 1 except that the dispersion E was used instead of the dispersion C. Plysurf A219B (Daiichi Kogyo Seiyaku Co., Ltd.) is a mixture of phosphoric acid monoester and phosphoric acid diester.

Example 3
Polycarbonate (Teijin Chemicals Ltd., Panlite ^{L-1250Y, MVR8cm 3 / 10min} ) , and polycarbonate (manufactured by Mitsubishi Engineering-Plastics IUPILON ^{S-1000, MVR7.1cm 3 / 10min} ) was replaced the same manner as in Example 1, A press sheet was created.

[Comparative Example 4]
Polycarbonate (Teijin Chemicals Ltd., Panlite ^{L-1250Y, MVR8cm 3 / 10min} ) , and polycarbonate (manufactured by Mitsubishi Engineering-Plastics IUPILON ^{S-1000, MVR7.1cm 3 / 10min} ) was used in place to perform the same manner as in Comparative Example 1, A press sheet was created.

[Comparative Example 5]
Dispersion F was prepared by adding 0.149 g of n-butylphosphonic acid copper salt to 15 g of dichloromethane and 0.075 g of PRISURF A219B as a dispersant, and stirring for 5 min using a stirrer.
A press sheet was prepared in the same manner as in Example 3 except that the dispersion F was used in place of the dispersion C.

[Example 4]
A press sheet was prepared in the same manner as in Example 1 except that 0.149 g of copper n-butylphosphonate was replaced with 0.019 g (15 mol%) of ethylphosphonic acid and 0.127 g (85 mol%) of n-butylphosphonic acid. It was created.

[Comparative Example 6]
A press sheet was prepared in the same manner as in Example 1 except that 0.149 g of copper n-butylphosphonate was replaced with 0.065 g (50 mol%) of ethylphosphonic acid and 0.075 g (50 mol%) of n-butylphosphonic acid. It was created.

[Comparative Example 7]
A press sheet was prepared in the same manner as in Example 1 except that 0.149 g of copper n-butylphosphonate was replaced by 0.130 g of copper ethylphosphonate.
In addition, the press sheet | seat which consists of resin compositions contains 0.00112g of ethylphosphonic acid copper salts per square centimeter.

[Comparative Example 8]
A press sheet was prepared in the same manner as in Example 1 except that 0.149 g of copper n-butylphosphonate was replaced with 0.220 g of copper decylphosphonate.
The press sheet made of the resin composition contains 0.00197 g of copper decylphosphonate per square centimeter.

[Comparative Example 9]
0.30 g of copper n-butylphosphonate was finely crushed and mixed with 9.69 g of methyl methacrylate, 10.0 g of cyclohexyl methacrylate and 0.04 g of α-methylstyrene to obtain a preparation solution (monomer solution). To this monomer solution, 0.20 g of t-butylperoxydecanate as a radical initiator is added, put in a test tube, and heated to different temperatures in sequence of 45 ° C. for 16 hours, 60 ° C. for 8 hours, and 100 ° C. for 3 hours. And polymerized to obtain a cylindrical optical material. The obtained copper salt-containing resin composition was press-molded at a temperature of 150 ° C. and 5 MPa for 5 minutes using a press machine to prepare a press sheet having a thickness of 0.78 mm.

Table 1 shows the physical properties of the press sheets obtained in Examples and Comparative Examples.
From Table 1, Examples 1 to 4 containing n-butylphosphonic acid copper salt in an amount of 70 mol% or more of 100 mol% of all alkylphosphonic acid copper salts have small HAZE, solar radiation transmittance and YI, while visible light transmittance. Is expensive. That is, the material of the present invention is excellent in these balances. Further, from Comparative Examples 3 and 5, it is clear that YI increases when Plysurf, which is a mixture of phosphoric acid monoester and phosphoric acid diester, is used.

Claims (7)

1. Including polycarbonate and alkylphosphonic acid copper salt,
   In 100 mol% of the alkylphosphonic acid copper salt, the alkylphosphonic acid copper salt represented by the following general formula (1) is 70 to 100 mol%, and the alkylphosphonic acid copper salt represented by the following general formula (2) is 0 to 30 mol%,
   A material used for construction or transportation equipment comprising a composition substantially free from phosphoric monoester and phosphoric diester.
   

   

   (In the general formula (1), R ¹ is an alkyl group having 4 to 6 carbon atoms.)
   

   

   (In the general formula (2), R ² is an alkyl group having 2, 3 or 7 to 40 carbon atoms.)
2. The material according to claim 1, wherein R ² in the general formula (2) is an alkyl group having 2, 3 or 7 to 10 carbon atoms.
3. The material according to claim 1 or 2, wherein at least a part of R ¹ in the general formula (1) is an n-butyl group.
4. The melt volume rate of the polycarbonate is the 1 ~ 100cm ³ / 10min, material according to any one of claims 1 to 3.
5. The material according to any one of claims 1 to 4, wherein the composition contains 0.0005 to 50 parts by mass of the alkylphosphonic acid copper salt with respect to 100 parts by mass of the polycarbonate.
6. The material according to any one of claims 1 to 5, wherein the composition further comprises a bluing agent.
7. The material according to any one of claims 1 to 6, wherein the material is a window material.