JP6503203B2 - Method for preventing damage to living tissue by near infrared light - Google Patents

Description

  The present invention relates to the damage to the tissue on the surface of the living body such as the skin, eyeballs and hair of the living body and deep tissue in the deep thereof caused by the near infrared rays including sunlight and artificially created light. The present invention relates to a method for preventing and preventing changes and deterioration of living tissue caused by near-infrared rays, aging, disease deterioration and the like.

Molded articles made of transparent thermoplastic resins such as polycarbonate resins are used for window materials of buildings, houses, automobiles, trains, aircrafts and the like. In these applications, in order to suppress the temperature rise in the room or in the car, it is required to shield near infrared rays from sunlight.
Various proposals have been made for this request. For example, Patent Document 1 proposes a resin composition in which a thermoplastic resin contains an aluminum piece. Patent Document 2 proposes a resin composition in which antimony-doped tin oxide fine particles are contained in a thermoplastic resin.
Further, Patent Document 3 proposes a resin composition in which a hexaboride particle is contained in a polycarbonate resin. Patent Document 4 proposes a resin composition in which a hexaboride particle and a nitride fine particle are contained in a polycarbonate resin.
Further, Patent Document 5 proposes a resin composition in which composite tungsten oxide fine particles are contained in a polycarbonate resin in order to shield near infrared rays and to suppress the temperature rise in a room or a car. These proposals are for preventing the change of indoor environment, such as temperature rise by near-infrared light.
On the other hand, Patent Document 6 proposes a near-infrared shielding agent containing titanium oxide powder or zinc oxide powder in order to prevent damage to a living tissue by near-infrared light. Since this shielding agent contains a large amount of titanium oxide powder and zinc oxide powder, the shielding effect of near infrared rays can be exhibited, but when it is contained in a resin, it is colored white and the transparency of the resin composition can not be secured. Furthermore, although a trial manufacture of glasses aiming at near-infrared shielding is performed in Example 7 of Patent Document 6, in this example, since a material of infrared reflection type is used, it is reflected in a visible light region. There was a problem that a feeling of glaring came out.

Unexamined-Japanese-Patent No. 2003-213846 Unexamined-Japanese-Patent No. 2000-234066 JP, 2005-47179, A WO 2008/075752 pamphlet WO 2010/143732 pamphlet WO 2009/017104 pamphlet

  Therefore, an object of the present invention is to provide a method for preventing damage to a living tissue by near infrared rays while maintaining transparency, and a filter suitable for the method.

  The inventor of the present invention diligently studied a method for preventing damage to a living tissue by near infrared light. As a result, when near infrared rays irradiated to a living tissue are blocked by a filter made of a resin composition in which a thermoplastic resin contains specific composite tungsten oxide particles and / or hexaboride particles, nearness is maintained while maintaining visibility. The inventors have found that the damage to living tissue due to infrared radiation can be significantly reduced, and the present invention has been completed. The method of the present invention does not include medical practice.

That is, the object of the present invention can be achieved by the following invention.
1. A method of blocking near infrared radiation irradiated to a living tissue by a filter to prevent damage to the living tissue by the near infrared radiation,
The filter comprises a layer containing 0.002 to 3 parts by weight of an infrared shielding agent (component A) and 100 parts by weight of a thermoplastic resin (component B),
Here, the A component is a composite tungsten oxide particle (A-1 component) represented by the following formula (i) and / or a hexaboride particle (A-2 component) represented by the following formula (ii),
MxWyOz (i)
(Where M is an alkali metal, x, y, z are numbers satisfying 0.01 ≦ x ≦ 1, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0. )
LaB ₆ (ii)
The method for preventing damage to a living tissue by the near infrared light, wherein the filter satisfies the following formulas (1) to (2).

3.0 × 10 ⁻⁴ ≦ c × d ≦ 2.0 × 10 ⁻³ (1)
(Here, c is the concentration of the A component in the filter (g / cm ³ ), and d is the thickness of the layer containing the A component (mm).)
T _{380 to 780 nm} 45 45% (2)
(Here, T ₃₈₀ to 780 nm is light transmittance at a wavelength of 380 to 780 nm.)
2. The method according to item 1 above, wherein the layer containing the component A further comprises a UV absorber (component C).
3. The method according to claim 1 or 2, wherein the layer containing the component A further comprises a heat stabilizer (component D).
4. The method according to any one of the aforementioned Items 1 to 3, wherein the filter has a surface treatment layer.
5. 5. The method according to any one of the above 1 to 4, wherein the thickness (d) of the layer containing component A of the filter is 0.1 to 20 mm.
6. The method according to any one of the above 1 to 5, wherein the formula (i) is (Cs) x WyOz.
7. 7. The method according to any one of the above 1 to 6, wherein the thermoplastic resin (component B) is a polycarbonate resin or an amorphous polyester.
8. The method according to the preceding paragraph, wherein the living tissue is the epidermis.
9. A filter for blocking near infrared rays irradiated to a living tissue and preventing damage to the living tissue by the near infrared radiation,
And a layer containing 0.002 to 3 parts by weight of an infrared shielding agent (component A) and 100 parts by weight of a thermoplastic resin (component B),
Here, the A component is a composite tungsten oxide particle (A-1 component) represented by the following formula (i) and / or a hexaboride particle (A-2 component) represented by the following formula (ii),
MxWyOz (i)
(Where M is an alkali metal, x, y, z are numbers satisfying 0.01 ≦ x ≦ 1, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0. )
LaB ₆ (ii)
The filter characterized by satisfying the following formulas (1) and (2).

3.0 × 10 ⁻⁴ ≦ c × d ≦ 2.0 × 10 ⁻³ (1)
(Here, c is the concentration of the A component in the filter (g / cm ³ ), and d is the thickness of the layer containing the A component (mm).)
T _{380 to 780 nm} 45 45% (2)
(Here, T ₃₈₀ to 780 nm is light transmittance at a wavelength of 380 to 780 nm.)

  According to the method of the present invention, it is possible to significantly reduce the damage to the living tissue due to the near infrared while maintaining the transparency of the filter. The filter of the present invention can prevent damage to living tissue while maintaining visibility.

The present invention is a method of blocking near infrared rays irradiated to a living tissue by a filter having a layer containing an infrared shielding agent (component A) and a thermoplastic resin (component B), and preventing damage to the living tissue by the near infrared rays. is there. Hereinafter, the present invention will be described.
<Infrared shielding agent (A component)>
The infrared shielding agent (component A) is a composite tungsten oxide particle (component A-1) represented by the following formula (i) and / or a hexaboride particle (component A-2) represented by the following formula (ii) It is.
MxWyOz (i)
(Where M is an alkali metal, x, y, z are numbers satisfying 0.01 ≦ x ≦ 1, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0. )
LaB ₆ (ii)

(A-1 ingredient)
The component A-1 is a composite tungsten oxide particle represented by the following formula (i).
MxWyOz (i)
In the formula, M is an alkali metal. Examples of alkali metals include Li, Na, K, Rb, Cs and Fr. Among them, Cs is preferable.
x satisfies 0.01 ≦ x ≦ 1, preferably 0.01 ≦ x ≦ 0.7, and more preferably 0.02 ≦ x ≦ 0.5. x / y satisfies 0.001 ≦ x / y ≦ 1, preferably 0.01 ≦ x / y ≦ 0.8, and more preferably 0.02 ≦ x / y ≦ 0.5. z / y satisfies 2.2 ≦ z / y ≦ 3.0, preferably 2.5 ≦ z / y ≦ 3.0, and more preferably 2.7 ≦ z / y ≦ 3.0.

  The composite tungsten oxide particles (component A-1) can be obtained by heat-treating a tungsten compound as a starting material in an inert gas atmosphere or a reducing gas atmosphere. The composite tungsten oxide fine particles obtained through the heat treatment have sufficient near infrared ray shielding power and have preferable properties as infrared ray shielding fine particles.

The starting material of the composite tungsten oxide fine particles represented by the general formula MxWyOz is a tungsten compound containing the element M in the form of an elemental single substance or a compound. Specifically, tungsten trioxide powder, tungsten dioxide powder, hydrate of tungsten oxide, tungsten hexachloride powder, ammonium tungstate powder, tungsten hexachloride containing element M in the form of elemental single substance or compound Hydrate powder of tungsten oxide obtained by dissolving in alcohol and then drying, tungsten hexachloride is dissolved in alcohol and then precipitated by adding water, and tungsten oxide obtained by drying it It is preferable that it is at least one selected from the group consisting of a hydrate powder, a tungsten compound powder obtained by drying an aqueous solution of ammonium tungstate, and a metal tungsten powder. It is more preferable to use an aqueous solution of ammonium tungstate or a solution of tungsten hexachloride from the viewpoint that each element can be easily mixed uniformly when the starting material is a solution. These raw materials can be heat-treated in an inert gas atmosphere or a reducing gas atmosphere to obtain the composite tungsten oxide fine particles described above.
Here, in order to produce a tungsten compound which is a starting material in which each component is uniformly mixed at the molecular level, it is preferable to mix each material in a solution, and the tungsten compound containing the element M is water, an organic solvent, etc. It is preferable that it is soluble in a solvent. For example, tungstate, chloride, nitrate, sulfate, oxalate, oxide, carbonate, hydroxide and the like containing the element M can be mentioned, but it is not limited to them, but it becomes a solution It is preferable if it is a thing.

The raw material for producing the composite tungsten oxide fine particles described above will be described in detail again below.
Tungsten trioxide powder, tungsten dioxide powder, hydrate of tungsten oxide, tungsten hexachloride powder, ammonium tungstate powder, starting materials for obtaining composite tungsten oxide fine particles represented by the general formula MxWyOz Hydrated powder of tungsten oxide obtained by dissolving tungsten chloride in alcohol and then drying, or dissolving tungsten hexachloride in alcohol and then adding water to precipitate, which is obtained by drying Powder of tungsten oxide, tungsten compound powder obtained by drying an aqueous solution of ammonium tungstate, and powder of any one or more kinds selected from metallic tungsten powder, a single substance or a compound containing the element M The powder which mixed with the powder of can be used.
Furthermore, when the tungsten compound which is the starting material for obtaining the composite tungsten oxide fine particles is a solution or a dispersion, each element can be easily uniformly mixed.
From this point of view, the starting material of the fine particles of the composite tungsten oxide is a powder obtained by mixing an alcohol solution of tungsten hexachloride or an aqueous solution of ammonium tungstate with a solution of the compound containing the element M and drying it. More preferable.

Similarly, the starting material of the fine particles of the complex tungsten oxide is a dispersion liquid in which tungsten hexachloride is dissolved in alcohol and then water is added to form a precipitate, and a simple substance or a compound containing the above M element It is also preferable that it is a powder or a powder which is mixed with a solution of the compound containing the element M and then dried.
Examples of the compound containing an M element include tungstates, chlorides, nitrates, sulfates, oxalates, oxides, carbonates, hydroxides and the like of M elements, but are limited thereto. It is sufficient if it is in the form of a solution. Furthermore, when the composite tungsten oxide fine particles are industrially produced, if a tungsten oxide hydrate powder or tungsten trioxide and a carbonate or hydroxide of an M element are used, the heat treatment etc. can be performed. It is a preferable production method without the generation of harmful gases and the like.

Here, as heat treatment conditions in the inert atmosphere of composite tungsten oxide fine particles, 650 ° C. or higher is preferable. The starting material heat-treated at 650 ° C. or higher has sufficient near-infrared shielding power and is efficient as infrared shielding particles. It is preferable to use an inert gas such as Ar or N ₂ as the inert gas. Further, as heat treatment conditions in a reducing atmosphere, first, the starting material is heat treated in a reducing gas atmosphere at 100 ° C. or more and 850 ° C. or less, and then heat treated in an inert gas atmosphere at a temperature of 650 ° C. or more and 1200 ° C. or less It is good to do. The reducing gas at this time is not particularly limited, but H ₂ is preferable. When H 2 is used as the reducing gas, the composition of the reducing atmosphere is preferably 0.1% or more by volume ratio of H ₂ , more preferably 2% or more. If the volume ratio of H ₂ is 0.1% or more, the reduction can be efficiently promoted.
It is preferable from the viewpoint of improving the weather resistance that the surface of the infrared shielding material fine particles obtained in the above-mentioned process is coated with an oxide containing one or more metals of Si, Ti, Zr and Al. . Although the coating method is not particularly limited, it is possible to coat the surface of the infrared shielding material particles by adding the alkoxide of the above metal to a solution in which the infrared shielding material particles are dispersed.

  The composite tungsten oxide fine particles are preferably coated with a dispersant. Examples of the dispersant include polycarbonate, polysulfone, polyacrylonitrile, polyarylate, polyethylene, polyvinyl chloride, polyvinylidene chloride, fluorine resin, polyvinyl butyral, polyvinyl alcohol, polystyrene, silicone resin, derivatives thereof, etc. As a result, the dispersibility when added to the resin is improved, and further, there is an effect of preventing the deterioration of mechanical properties. In addition, as a coating method with a dispersing agent, the composite tungsten oxide fine particles and the dispersing agent are dissolved in a solvent such as toluene and stirred to prepare a dispersion, and then the solvent is removed by a process such as vacuum drying to obtain a composite tungsten oxide fine particle. The coating method etc. are mentioned.

The particle diameter of the component A-1 is preferably 1 nm to 800 nm, more preferably 1 nm to 600 nm, and still more preferably 1 nm to 300 nm. When the particle diameter is smaller than 1 nm, the aggregation effect is increased to easily cause poor dispersibility. When the particle diameter is larger than 800 nm, defects such as high haze of the transparent resin molded product may occur.
Further, as a method of adding the component A-1 to the component B, a method of directly adding the component A-1 to the component B or a method of adding it after diluting it with 1 to 100 times the component A can be mentioned.
The content of the component A-1 is preferably 0.0001 to 5 parts by weight, preferably 0.001 to 4 parts by weight, and more preferably 0.002 to 3 parts by weight with respect to 100 parts by weight of the component B. If the content of the component A is less than 0.0001 parts by weight, the shielding ability of infrared rays can not be sufficiently exhibited, and furthermore, discoloration of the thermoplastic resin (component B) is visually recognized by the tint peculiar to the composite tungsten oxide oxide fine particles. The effect of reducing the light loss is reduced, and when it is more than 1 part by weight, the visible light transmittance becomes very small.

(A-2 ingredient)
A-2 component is a hexaboride particle represented by Formula (ii).
LaB ₆ (ii)
2 nm-100 nm are preferable, and, as for the particle size of hexaboride particle (A-2 component), 5-90 nm is especially preferable. The component A-2 is preferably coated hexaboride fine particles having a coating layer on the surface thereof. As metal borides used as the raw material of hexaboride particles, for example, Sumitomo Metal Mining Co., Ltd. product KHDS-06 etc. are marketed and are easily available.
The covering layer preferably comprises a metal oxide. The covering layer preferably contains an oxide of at least one metal selected from the group consisting of Si (silicon), Ti (titanium), Al (aluminum) and Zr (zirconium). The ratio of the coating layer to the hexaboride is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 10 parts by weight, relative to 1 part by weight of the hexaboride particles, in terms of metal contained in the coating layer. It is.
The cover layer more preferably contains an oxide of Si (silicon). The ratio of the oxide of silicon to the hexaboride is generally in the range of 0.01 to 100 parts by weight, more preferably 0. 1 to 100 parts by weight relative to 1 part by weight of the hexaboride particles in terms of silicon contained in the silicate compound. It is in the range of 1 to 10 parts by weight. If the ratio of the silicate compound is less than 0.01 parts by weight, it is difficult to form a secondary coating film, and conversely, if it exceeds 100 parts by weight, aggregation between particles occurs. The thickness of the coating film is preferably 1 to 100 nm, more preferably 5 to 90 nm, and still more preferably 10 to 80 nm.
The coating layer is formed by dispersing the hexaboride particles in a solvent, adding and mixing a surface treatment agent containing a metal oxide to the solvent, and causing a chemical reaction to coat or physically coat the layer. can do.

As surface treatment agents, silazane-based treatment agents, chlorosilane-based treatment agents, inorganic-based treatment agents having an alkoxy group in the molecular structure, and organic systems having an amino group-containing alkoxysilane at the molecular terminal or side chain which can be expected to improve water repellency. A processing agent and the organic type processing agent which has an alkoxy group in the molecular terminal or a side chain etc. are mentioned. Examples of the solvent to be used include water, an organic solvent such as alcohol, or a mixture of water and an organic solvent.
The covering layer is preferably composed of a pre-coating film with a surface modifier formed on the surface of the hexaboride particles and a coating film based on an oxide of Si formed thereon. That is, it is preferable to previously form a pre-coated film on the surface of the hexaboride particles with a surface modifying agent such as a silane coupling agent, and then to form a coated film containing an oxide of Si as a main component.

In the present invention, the average particle diameter of the coated hexaboride particles (A-2 component) is preferably 2 to 100 nm, more preferably 5 to 90 nm, and still more preferably 10 to 80 nm. When the average particle size is larger than 100 nm, the absorption characteristics of near infrared rays close to the visible light range will be degraded. That is, the profile has a maximum value at a wavelength of 400 to 700 nm, a minimum value at a wavelength of 700 to 800 nm, and a profile in which the difference between the maximum value and the minimum value is 15 points or more in percentage The result is a grayish film with monotonously decreased transmittance. The average particle diameter is obtained by calculating the area of individual primary particles by image analysis of an image obtained by electron microscope observation, determining the diameter of a circle having the area, and weight averaging the diameters. It is calculated. Such calculation is calculated by determining the converted diameter of 500 or more particles.
The reduced diameter of the individual coated hexaboride particles (A-2 component) is preferably 380 nm or less, more preferably 150 nm or less. Furthermore, the reduced diameter of the individual coated hexaboride particles is preferably within the range of 50% of the average particle diameter before and after the average diameter and more preferably within the range of 30% of the average particle diameter before and after .
The content of the hexaboride particles (component A-2) is preferably 0.0001 to 3 parts by weight, more preferably 0.001 to 2 parts by weight, per 100 parts by weight of the thermoplastic resin (component B). More preferably, it is 0.001 to 1 part by weight.

<Thermoplastic resin (B component)>
As a thermoplastic resin, for example, acrylic resin, polystyrene resin, hydrogenated polystyrene resin, AS resin, vinyl chloride resin, MS resin, polycarbonate resin, transparent polypropylene resin, transparent ABS resin, amorphous polyarylate resin, polysulfone, polyether Sulfone, poly-4-methylpentene-1, transparent fluorocarbon resin, transparent phenoxy resin, amorphous polyolefin resin, transparent nylon resin, polyethylene terephthalate resin, amorphous polyester, etc. can be mentioned, among which polycarbonate resin, Transparent ABS resin and amorphous polyester are particularly preferred.
The polycarbonate resin used in the present invention is obtained by reacting dihydric phenol with a carbonate precursor. As an example of the reaction method, an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, a ring opening polymerization method of a cyclic carbonate compound, and the like can be mentioned.

  Representative examples of dihydric phenols used herein are hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) ) Propane (generally called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 '-(p-phenylenediisopropylidene) diphenol, 4,4'-(m-phenylenediisopropyl) Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5 -Dibromo-4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) And the like. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes, among which bisphenol A is particularly preferred in terms of impact resistance.

As the carbonate precursor, carbonyl halide, diester of carbonic acid or haloformate, etc. are used, and specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, etc. may be mentioned.
When the polycarbonate resin is produced by the interfacial polymerization method of the dihydric phenol and the carbonate precursor, the catalyst, the terminal stopper, the antioxidant for preventing the oxidation of the dihydric phenol, etc. You may use it. The polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, and a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid And a copolymerized polycarbonate resin copolymerized with a difunctional alcohol (including an alicyclic group), and a polyester carbonate resin copolymerized together with such a difunctional carboxylic acid and a difunctional alcohol. Moreover, the mixture which mixed 2 or more types of obtained polycarbonate resin may be sufficient.
As trifunctional or higher polyfunctional aromatic compounds, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane and the like It can be used.

Such amount is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, particularly preferably 0. It is 01 to 0.8 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction, and the amount of such branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0. It is preferably 9 mol%, particularly preferably 0.01 to 0.8 mol%. In addition, about this ratio, it is possible to calculate by 1 H-NMR measurement.
The aliphatic difunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Aliphatic difunctional carboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, linear saturated aliphatic dicarboxylic acids such as icosanedioic acid, and cyclohexanedicarboxylic acid Aliphatic dicarboxylic acids such as are preferably mentioned. An alicyclic diol is more preferable as the difunctional alcohol, and examples thereof include cyclohexane dimethanol, cyclohexane diol, and tricyclodecane dimethanol.
It is also possible to use polycarbonate-polyorganosiloxane copolymers, which are copolymerized with polyorganosiloxane units.

The reaction by the interfacial polymerization method is usually a reaction between dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and pyridine.
As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.
Further, a catalyst such as tertiary amine or quaternary ammonium salt can be used to accelerate the reaction, and as a molecular weight modifier, for example, monofunctional phenol such as phenol, p-tert-butylphenol, p-cumylphenol and the like It is preferred to use a class. Furthermore, examples of monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol. Monofunctional phenols having these relatively long-chain alkyl groups are effective when it is required to improve flowability and hydrolysis resistance.
Preferably, the reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is usually 10 or more.

The reaction by the melting method is usually a transesterification reaction of dihydric phenol and diester of carbonic acid, and dihydric phenol and diester of carbonic acid are mixed in the presence of an inert gas and reacted at usually 120 to 350 ° C. under reduced pressure. The degree of pressure reduction is changed stepwise and finally the generated phenol is removed out of the system at 133 Pa or less. The reaction time is usually about 1 to 4 hours.
Examples of the carbonic diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate, and the like, with preference given to diphenyl carbonate.

A polymerization catalyst can be used to accelerate the polymerization rate, and examples of the polymerization catalyst include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide and potassium hydroxide, hydroxides of boron and aluminum, Alkali metal salt, alkaline earth metal salt, quaternary ammonium salt, alkoxide of alkali metal or alkaline earth metal, organic acid salt of alkali metal or alkaline earth metal, zinc compound, boron compound, silicon compound, germanium compound, Examples of the catalyst include organic tin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds and zirconium compounds, which are generally used for esterification reaction and transesterification reaction. The catalyst may be used alone or in combination of two or more. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalents, per 1 mol of the raw material dihydric phenol. It is chosen in the range.
In addition, in the polymerization reaction, for example, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonyl phenyl phenyl carbonate, and 2-ethoxycarbonyl phenyl phenyl carbonate in the polymerization reaction, in order to reduce phenolic terminal groups, in the late stage or after completion of the dehydrogenation reaction. Compounds can be added.

  Furthermore, it is preferable to use a deactivator which neutralizes the activity of the catalyst in the melt transesterification method. The amount of such deactivator is preferably in the range of 0.5 to 50 moles with respect to 1 mole of the remaining catalyst. Further, it is used in a proportion of preferably 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, and particularly preferably 0.01 to 100 ppm based on the aromatic polycarbonate after polymerization. Preferred examples of the quenching agent include phosphonium salts such as dodecylbenzenesulfonic acid tetrabutylphosphonium salt, and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate. The details of reaction types other than the above are also well known in written documents and patent publications.

The viscosity average molecular weight of the polycarbonate resin is preferably 14,000 to 100,000, more preferably 20,000 to 30,000, still more preferably 22,000 to 28,000, and 23,000 to 26,000. Most preferred. If the molecular weight is too low beyond the above range, mechanical properties such as impact value become insufficient, and cracking tends to occur. In addition, when the molecular weight is high beyond the above range, injection molding becomes difficult, and a crack failure is likely to occur due to residual stress or the like. Furthermore, in the more preferable range, it is excellent in coexistence with impact resistance and moldability. In addition, the said polycarbonate resin may be obtained by mixing the thing whose viscosity average molecular weight is out of the said range.
The viscosity average molecular weight (M) of the polycarbonate resin is obtained by inserting the specific viscosity (η sp) obtained at 20 ° C. from a solution of 0.7 g of the polycarbonate resin dissolved in 100 ml of methylene chloride into the following equation.
η _sp /c=[η]+0.45×[η] ² c (where [η] is the limiting viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

The following can be mentioned as an aspect of polycarbonate resin. That is, it comprises an aromatic polycarbonate (PC-i) having a viscosity average molecular weight of 70,000 to 300,000, and an aromatic polycarbonate (PC-ii) having a viscosity average molecular weight of 10,000 to 30,000, and the viscosity average molecular weight is Aromatic polycarbonates (hereinafter sometimes referred to as "high molecular weight component-containing aromatic polycarbonates") of 15,000 to 40,000, preferably 20,000 to 30,000 can also be used.
Such high molecular weight component-containing aromatic polycarbonates increase the entropy elasticity of the polymer due to the presence of PC-i, which is more advantageous in injection press molding suitable in the present invention. For example, appearance defects such as hesitation marks can be further reduced, and the condition width of injection press molding can be expanded accordingly. On the other hand, the low molecular weight component of the PC-ii component lowers the overall melt viscosity and promotes relaxation of the resin, allowing for lower strain molding. The same effect is also observed in polycarbonate resins containing a branched component.

<UV absorber: C component>
The B component may contain an ultraviolet absorber (C component). As the component C, a triazine-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and an oxazine-based ultraviolet absorber are preferable. In particular, benzotriazole type is preferable, and it is excellent in the effect of suppressing damage to cells.
The content of the component C is preferably 0.01 to 1 part by weight, more preferably 0.07 to 0.7 parts by weight, and particularly preferably 0.1 to 0.5 parts by weight with respect to 100 parts by weight of the component B. When the content of the component C is less than 0.01 parts by weight, the weatherability of the resin composition is lowered, and when it is more than 1 part by weight, not only molding stability and mechanical properties are reduced but also visible light transmittance Decline in

<Heat stabilizer (component D)>
Component B may contain a heat stabilizer (component D). As a heat stabilizer (component D), a phosphorus stabilizer (component D-1), a hindered phenol stabilizer (component D-2), and a sulfur stabilizer (component D-3) can be mentioned.

(D-1 ingredient: phosphorus system stabilizer)
Phosphorus stabilizers are already widely known as heat stabilizers for aromatic polycarbonates. The phosphorus-based stabilizer enhances its thermal stability to such an extent that the resin composition can withstand extremely severe heat loads. As phosphorus stabilizers, phosphite compounds and phosphonites are mainly mentioned.
Here, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite , Diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (diethylphenyl) ) Phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) Sulfite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, Bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite and the like are exemplified.

  Furthermore, as another phosphite compound, one having a cyclic structure by reacting with a dihydric phenol can be used. For example, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite And 2,2'-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and the like.

  As a phosphonite compound, for example, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-bipheny Di-phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylene diphospho Knight, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, Bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,2, -Di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butyl Phenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphospho Knight, bis (di-tert-butylphenyl) -phenyl-phenyl phosphonite is preferable, tetrakis (2,4-di-tert-butylphenyl) -biphenylene diphosphonite, bis (2,4-di-tert-butyl) More preferred is phenyl) -phenyl-phenyl phosphonite. Such phosphonite compounds can be used in combination with phosphite compounds having an aryl group in which two or more alkyl groups are substituted, which is preferable. The content of the phosphorus-based stabilizer is preferably 0.0001 to 1 parts by weight, more preferably 0.001 to 0.5 parts by weight, and still more preferably 0.007 to 0.1 parts by weight per 100 parts by weight of the component B. 0.01 to 0.07 parts by weight is particularly preferred.

(D-2 ingredient: hindered phenol type stabilizer)
Examples of hindered phenol stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) Propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N , N-Dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'- Methylene bis (4-ethyl-6-tert-butylphenol), 4,4'-methylene bis (2,6- -Tert-Butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis (6-.alpha.-methyl-benzyl-p-cresol) 2,2'-ethylidene -Bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol ), Triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-) Butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) 5-Methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethyl Ethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3-methyl- 6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-di -Thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodiethyle Bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di- tert-Butylanilino) -1,3,5-triazine, N, N′-hexamethylene bis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanate Nuralate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3 ′, 5′-di-tert) -Butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available.
The hindered phenolic stabilizers can be used alone or in combination of two or more. The content of the hindered phenol-based stabilizer is preferably 0.0002 to 0.8 parts by weight, more preferably 0.0005 to 0.45 parts by weight, and 0.002 to 0.25 parts by weight per 100 parts by weight of the AB component. Parts are further preferred, and 0.005 to 0.15 parts by weight are particularly preferred.

(D-3 ingredient: sulfur stabilizer)
As sulfur-based stabilizers, dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate), pentaerythritol tetrakis (3-dodecyl thiopropionate), pentaerythritol tetrakis (3-octadecyl thiopropionate), pentaerythritol tetrakis (3-myristyl thiopropionate), pentaerythritol tetrakis (3-stearyl thiopropionate), etc. It can be mentioned. These may be used alone or in combination of two or more.
The content of the sulfur stabilizer is preferably 0.0001 to 1 parts by weight, more preferably 0.001 to 0.5 parts by weight, and still more preferably 0.007 to 0.1 parts by weight per 100 parts by weight of the component B. 0.01 to 0.07 parts by weight is particularly preferred.

<Production of Resin Composition>
The method for producing the resin composition used in the present invention is not particularly limited. However, it is preferable that the resin composition of this invention is manufactured by melt-kneading each component.
Specific examples of the melt-kneading include a Banbury mixer, a kneading roll, and an extruder. Among them, an extruder is preferable from the viewpoint of kneading efficiency, and a multi-screw extruder such as a twin-screw extruder is more preferable. The more preferable aspect in this twin-screw extruder is as follows. The screw configuration can use a single-row, double-row and triple-row screw screw, and in particular, a double-row screw screw having a wide application range of both the transport ability of molten resin and the shear kneading ability can be preferably used. The ratio (L / D) of screw length (L) to diameter (D) in the twin-screw extruder is preferably 20 to 45, and more preferably 28 to 42. When L / D is large, homogeneous dispersion is easily achieved, but if it is too large, the resin is likely to be decomposed due to thermal degradation. It is necessary for the screw to have one or more kneading zones composed of kneading disc segments (or kneading segments corresponding thereto) for enhancing the kneadability, and it is preferable to have one to three.
Furthermore, as the extruder, one having a vent capable of degassing the water content in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed to efficiently discharge generated water and volatile gases out of the extruder from the vent. It is also possible to remove foreign matter from the resin composition by installing a screen for removing foreign matter mixed in the extruded material in the zone in front of the extruder die. Such screens may include wire mesh, screen changers, sintered metal plates (such as disc filters) and the like.

Furthermore, the method for feeding the B component, C component and other additives (referred to simply as “additives” in the following examples) into the extruder is not particularly limited, but the following methods are typically exemplified. (I) A method of feeding the additive into the extruder independently of the polycarbonate resin. (Ii) A method of pre-mixing the additive and the polycarbonate resin powder using a mixer such as a super mixer, and supplying the resultant to an extruder. (Iii) A method of melt-kneading the additive and the polycarbonate resin in advance to form a master pellet.
One of the above methods (ii) is a method in which all necessary raw materials are premixed and supplied to the extruder. Another method is a method of preparing a master agent compounded with a high concentration of additives, and further pre-mixing the master agent independently or with the remaining polycarbonate resin and the like, and then supplying it to the extruder. As the master agent, any of a powder form and a form obtained by compression granulation of the powder can be selected. Other pre-mixing means include, for example, a Nauta mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer, but a high-speed stirring mixer such as a super mixer is preferable. Yet another method of premixing is, for example, a method of removing the solvent after preparing a solution in which the polycarbonate resin and the additive are uniformly dispersed in the solvent.
The resin extruded from the twin-screw extruder is directly cut and pelletized or, after forming a strand, such strand is cut and pelletized by a pelletizer. Furthermore, when it is necessary to reduce the influence of external dust and the like, it is preferable to clean the atmosphere around the extruder.

<Filter>
The filter can be manufactured by injection molding or extrusion of the pellet manufactured as described above. In such injection molding, injection compression molding, injection press molding, gas assist injection molding, foam molding (including injection of a supercritical fluid), insert molding, as well as ordinary molding methods according to the purpose as appropriate. Molded articles can be obtained using injection molding methods such as in-mold coating molding, insulation mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra high speed injection molding. The advantages of these various molding methods are already widely known. In addition, either cold runner method or hot runner method can be selected.
The filter includes a layer containing an infrared shielding agent (component A) and a thermoplastic resin (component B), and satisfies the following formulas (1) and (2).
3.0 × 10 ⁻⁴ ≦ c × d ≦ 2.0 × 10 ⁻³ (1)
Here, c is the concentration of the A component in the filter (g / cm ³ ), and d is the thickness of the layer containing the A component (mm).
c × d is preferably 3.0 × 10 ⁻⁴ ≦ c × d ≦ 1.7 × 10 ⁻³ , more preferably 3.5 × 10 ⁻⁴ ≦ c × d ≦ 1.5 × 10 ⁻³ I am satisfied.
T _{380 to 780 nm} 45 45% (2)
Here, T ₃₈₀ to 780 nm is a light transmittance at a wavelength of 380 to 780 nm. T _{380 to 780 nm} preferably satisfies T _{380 to 780 nm} ≧ 50%, more preferably T _{380 to 780 nm 6060} %.

The filter can be subjected to various surface treatments. The surface treatment referred to here is to form a new layer on the surface layer of a resin molded product such as painting, coating, printing, etc., and a method used for a normal polycarbonate resin can be applied. Specific examples of the surface treatment include various surface treatments such as a hard coat, a water / oil repellent coat, an ultraviolet ray absorbing coat, and an infrared ray absorbing coat. Hard coat is a particularly preferred and required surface treatment. By performing the surface treatment, it is possible to further impart the performance such as the designability and the weather resistance to the performance of the molded article.
The haze value of the filter is preferably less than 10%, more preferably less than 5%, and still more preferably less than 1% when a measurement method in accordance with ISO 14782-1 is used.

<Living tissue>
In the present invention, the biological tissue is not limited to the tissue on the surface of the living body such as the skin, eyeballs and hair of the living organism, and constitutes a living organism including deep tissues such as subcutaneous tissue, fat tissue and muscle. Say everything about the organization.

  Hereinafter, the present invention will be more specifically described by way of examples. The present invention is not limited at all by these examples and the like. In the following, “parts” indicates “parts by weight” and% indicates “% by weight” unless otherwise noted.

(Examples 1 to 11 and Comparative Examples 1 to 5)
The present invention will be more specifically described by way of the following examples.
(1) Preparation of resin composition (1-1) Raw materials used (component A)
A-1: Infrared shielding agent comprising Cs _0.33 WO ₃ about 23% by weight and an organic dispersion resin (YMDS-874 manufactured by Sumitomo Metal Mining Co., Ltd.)
A-2: An infrared shielding agent comprising about 21.5% by weight of LaB ₆ fine particles and a resin binder (KUDS, manufactured by Sumitomo Metal Mining Co., Ltd.)
A-3: About 92% by weight of titanium oxide fine particles (PC-3 manufactured by Ishihara Sangyo Co., Ltd.)

(B component)
B-1: A polycarbonate resin powder having a molecular weight of 24,200 obtained by the following production method: A stirrer with a three-stage six-blade blade and a reflux condenser were attached to a reaction container with a baffle. In this reaction vessel, 45.6 parts of bisphenol A, 2.78 mol% of p-tert-butylphenol relative to bisphenol A, 265 parts of dichloromethane and 200 parts of water are charged, and nitrogen purged to remove oxygen in the reaction vessel Did. At this stage, the content in the reaction vessel was less than 80% of the vessel volume. Next, about 80 parts of an aqueous solution for supplying 0.09 parts of sodium hydrosulfite and 21.8 parts of sodium hydroxide was supplied to the above suspension, and bisphenol A was dissolved at 15 ° C. Under agitation, 23.35 parts of phosgene were fed to the mixture over a period of 30 minutes. Then, 0.016 parts (0.08 mol% with respect to bisphenol A) of triethylamine was added, and it stirred for 60 minutes, and terminated reaction. Thereafter, the reaction mixture was allowed to stand and the organic phase was separated. Methylene chloride is added to a dichloromethane solution of the obtained polycarbonate resin to make a solution having a concentration of 14% by weight, and 0.5% hydroxylated using a centrifugal extractor with a perforated plate (KCC centrifugal extractor manufactured by Kawasaki Engineering Co., Ltd.) The sodium aqueous solution is supplied at a flow rate of 1,000 ml / min and the organic phase is supplied at a flow rate of 1,000 ml / min and treated under the conditions of 3,500 rpm, then the organic phase is acidified with hydrochloric acid and then water washing is repeated to obtain an aqueous phase When the conductivity was almost the same as that of the ion-exchanged water, methylene chloride was evaporated to obtain a polycarbonate resin powder.
B-2: Amorphous polyester resin (manufactured by SK Chemical: J-2003)

(C ingredient)
C-1: Benzotriazole-based ultraviolet light absorber (manufactured by Ciba Specialty Chemicals: Tinuvin 234)
C-2: Triazine-based ultraviolet absorber (Ciba-Specialty Chemicals Co., Ltd .: Tinuvin 1577)
C-3: Triazine-based ultraviolet absorber (manufactured by Ciba Specialty Chemicals: CGX-006)
C-4: Benzotriazole-based ultraviolet absorber (chemisorb 79 manufactured by Chemi-Pur Chemical Co., Ltd.)
C-5: 2- (5 chloro-2H benzotriazol-2-yl) 6- (1,1-dimethylethyl) 4-methyl-phenol 3896-11-5 (manufactured by Chiba Specialty Chemicals: Tinuvin 326)

(D component)
D-1: Phosphorus stabilizer (P-EPQ manufactured by Clariant Japan Co., Ltd.)
D-2: Hindered phenolic stabilizer (Ciba Specialty Chemicals Inc .: Irganox 1076)
(Others)
VP: Fatty acid full ester (Cognis Japan KK: VPG 861)
SA: Fatty acid partial ester (manufactured by Riken Vitamin Co., Ltd .: Rikemar S-100A)

(2) Preparation of Test Sample (2-1) Production of Resin Composition Each component described in Table 1 is weighed and mixed in the ratio described in Table 1 and mixed in a blender, and then a vent type twin screw extruder is used. The mixture was melt-kneaded to obtain pellets of a polycarbonate resin composition. In addition, content of A component is the quantity of the inorganic type infrared shielding material contained in A-1, A-2, and A-3 mentioned by the said using raw material, and shows in parenthesis in A component of Table 1 The The additives to be added to PC were prepared in advance as a pre-mixture with PC, using a concentration of 10 to 100 times the compounding amount as a standard, and then the entire mixing was performed by a blender. The vent type twin-screw extruder manufactured by Japan Steel Works, Ltd .: TEX30α (complete meshing, co-rotation, double thread screw) was used. The kneading zone was of one type in front of the vent port. The extrusion conditions were a discharge amount of 20 kg / h, a screw rotation speed of 150 rpm, and a degree of vacuum of 3 kPa for the vent, and the extrusion temperature was 280 ° C. from the first supply port to the die portion. The production of the above-mentioned resin composition was carried out in an atmosphere where clean air circulated through the HEPA filter was circulated, and it was carried out with great care so as to prevent the entry of foreign matter at the time of operation.

(2-2) Method of making a filter After drying the obtained pellet at 110 to 120 ° C. for 6 hours with a hot air circulating drier, an injection molding machine (Sumiumi Heavy Industries, Ltd. SG 260 M-HP) is used. A filter having a thickness (2 mm, 5 mm, 20 mm) described in Table 1 was molded under the conditions of a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C.
For the filter with a thickness of 0.1 mm described in Table 1, the obtained pellet is dissolved in methylene chloride to prepare a dope having a solid concentration of 19% by weight, and a glass having a thickness of 0.1 mm from this dope solution It was poured onto a plate, peeled off, and dried to prepare a cast film.

(3) Evaluation item (3-1) T _{380-780 nm} measurement (visible light transmittance measurement)
A 50 mm square test piece was cut out from the filter prepared in (2-2) above. The spectral beam was calculated based on JIS R 3106 using a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 1.
(3-2) HAZE Measurement A 50 mm square test piece was cut out from the filter prepared in (2-2) above. The total light transmittance was measured according to ISO 13468-1 using a haze meter HR-100 manufactured by Murakami Color Research Laboratory.

(3-3) Measurement of Cell Viability Human normal skin fibroblasts were used as target cells. The cells were cultured in 5 × 10 ³ cells / well in a humidified 37 ° C. culture apparatus containing 5% CO ₂ in a commercially available medium in the wells of culture dishes. As a light source, Titan (manufactured by Kutera; trade name, wavelength range 1000 to 1800 nm) used for rejuvenation treatment in plastic surgery and dermatology was used. The irradiation conditions were set to an output intensity of 20 J / cm ² , and a single pulse was used as one shot, and irradiation of a plurality of shots repeated ten times was performed. Note that the intensity of 20 J / cm ² by this treatment device is an output that allows a healthy person to feel a weak feeling of heat even if it is irradiated to the skin, and even if irradiated a plurality of times, the healthy person feels warm to the skin It does not cause redness, burns or secondary events, with an output level that feels Furthermore, the temperature of the bottom of the culture medium in each well is measured at a temperature of 37 ° C. for each shot in order to prevent excessive temperature rise and to eliminate the possibility of cell damage due to accumulated heat based on the excessive temperature. I waited until I got back and took the next shot.
Specifically, the method of measuring the medium temperature of each well is, for each group, the temperature of the medium bottom of the water immediately after the irradiation of each shot with a digital thermometer MC3000-000 (product of Chino Co., Ltd.) equipped with a thermocouple. It is something to measure.

The measurement of cell viability is as follows.
The near infrared irradiation group was measured after 24 hours of culture after irradiation of 10 shots at an intensity of 20 J / cm ² .
A specific method of cell viability measurement is the tetrazolium salt MTT (3- (4,5-di-methylthiazol-2-yl) -2,5-diphenyltetrazolium bromide, by the dehydrogenase in the mitochondria of the cell. With regard to formazan (Formazan), which is produced by reduction of yellow tetrazole) in living cells, the absorbance is measured using a microplate reader.

  As apparent from the above, according to the present invention, when a predetermined inorganic infrared shielding material is used, it can be said that cell viability can be remarkably improved and cell damage can be prevented.

The filter of the present invention is used for a transparent film, a transparent plate, and a transparent molded article having a three-dimensional shape for the purpose of bioprotection. Therefore, window members for vehicles, window members for construction materials, window glass for buildings, houses, and greenhouses, roofs for arcades, glasses lenses, goggles, windshields for motorcycles, covers for display devices, touch panels, game machines (pachinko machines Can be used in a wide range of applications such as machine parts) (chassis etc.).
Therefore, the filter of the present invention is useful for various applications for the purpose of bioprotection, and the industrial effects to be exhibited are remarkable.

Claims (8)

A filter for blocking near infrared rays irradiated to a living tissue and preventing damage to the living tissue by the near infrared radiation,
A layer containing 0.002 to 3 parts by weight of an infrared shielding agent (component A) and 100 parts by weight of a thermoplastic resin (component B),
Here, the A component is a composite tungsten oxide particle (A-1 component) represented by the following formula (i) and / or a hexaboride particle (A-2 component) represented by the following formula (ii),
MxWyOz (i)
(Where M is an alkali metal, x, y, z are numbers satisfying 0.01 ≦ x ≦ 1, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0. )
LaB ₆ (ii)
The filter characterized by satisfying the following formulas (1) and (2).
3.0 × 10 ⁻⁴ ≦ c × d ≦ 2.0 × 10 ⁻³ (1)
(Here, c is the concentration of the A component in the filter (g / cm ³ ), and d is the thickness of the layer containing the A component (mm).)
T _{380 to 780 nm} 45 45% (2)
(Here, T ₃₈₀ to 780 nm is light transmittance at a wavelength of 380 to 780 nm.) The filter according to claim 1, wherein the layer containing the component A further contains a UV absorber (component C). The filter according to claim 1 or 2, wherein the layer containing the component A further contains a heat stabilizer (component D). Filter according to claim 1 having a front surface processing layer. The filter according to any one of claims 1 to 4, wherein the thickness (d) of the layer containing the component A is 0.1 to 20 mm. The filter according to any one of claims 1 to 5, wherein the formula (i) is (Cs) x WyOz. The filter according to any one of claims 1 to 6, wherein the thermoplastic resin (component B) is a polycarbonate resin or an amorphous polyester. The filter according to claim 1, wherein the living tissue is an epidermis.