JP2006104365A - Coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a coating material made of a thermoplastic resin, which controls a temperature rise by solar radiation in the inside of a material, controls a temperature drop by radiation cooling in the inside and has excellent transparency. <P>SOLUTION: The coating material made of a thermoplastic resin comprises (A) a porphyrin derivative compound having an absorption band in a near infrared ray region at 760-2,000nm and (B) an inorganic compound having an absorption band in an infrared region at 5-25μm and 1.49-1.55 refractive index. A naphthalocyanine or a phthalocyanine compound is used as (A) the porphyrin derivative compound and a hydrotalcite compound, a lithium-aluminum double hydroxide salt compound, a lithium-aluminum-magnesium compound carbonate compound or a lithium-aluminum-magnesium compound silicate compound is suitably used as (B) the inorganic compound. A film, sheet, panel, filament, yarn, nonwoven fabric, woven fabric, hollow molding, etc., may be cited as the coating material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention suppresses the environment under the material and the temperature of the object from rising due to solar radiation, suppresses the temperature from being lowered by nighttime radiation cooling, and condensation occurs in the environment covered with the material. It relates to difficult new coating materials.

  Films, sheets, panels, filaments, yarns, nets, non-woven fabrics, woven fabrics made of thermoplastic resins and coating materials made by combining these are used for stores by making use of their characteristics such as light weight, easy processability, easy workability, and low cost. Used in a wide variety of applications including awnings, window shades, curtains, shutters, tents, dome houses, vehicle seats, field sheets, building construction site seats, facility horticulture houses, agricultural materials, farm pond houses, livestock houses, etc. . If it is not desirable that the temperature inside or below the material and the temperature of the object rise due to sunlight shining from the outside or the top of the material when these materials are used, these materials are colored in dark colors or the light transmittance A method of applying a low material on the surface, pasting it, or adding it to the inside is adopted.

However, in this case, there is a problem that it is difficult to visually recognize an object inside or below from the outside or the top of the material, and there is a problem that workability and safety are impaired because the inside becomes dark. On the other hand, when these materials are used, if it is not desirable that the environment inside or below the material and the temperature of the object decrease due to radiant cooling at night, multiple materials are used, forming bubbles inside the material, heat insulation A method such as pasting the adhesive material is adopted. However, in this case, there are problems that the material is thick, that visibility is lowered, and that the interior is dark. Furthermore, if the internal environment covered with the above materials is not adequately ventilated with the outside, dew will form at night inside the coated material, causing internal items such as windows, floors, equipment, luggage, crops, livestock, etc. The problem of getting wet with water drops often occurred.
JP 2003-195030 A JP-A-6-64664 JP 2000-44883 A

  The present invention suppresses the temperature rise of the environment and objects below and inside the material due to solar radiation, and also suppresses the temperature drop of the environment and objects due to radiation cooling, and visually recognizes the inside of the material. Further, it is an object of the present invention to provide a coating material made of a thermoplastic resin that is less likely to cause condensation at night inside the material.

  The present inventor suppresses the environment and the temperature of the object under the material and the temperature of the object from rising due to solar radiation while ensuring the visibility of the inside of the material, and also suppresses the temperature and the temperature of the object from decreasing due to radiation cooling. In addition, the present invention was completed by earnestly studying to develop a new coating material that hardly causes condensation inside the material.

  That is, the present invention relates to a porphyrin derivative compound (A) having an absorption band in the near infrared region of 760 to 2000 nm and an inorganic compound having an absorption band in the infrared region of 5 to 25 μm and a refractive index of 1.49 to 1.55. It is a covering material made of a thermoplastic resin containing (B).

  As a resin film containing a porphyrin derivative compound, for example, the above-mentioned patent document is disclosed, but patent document 1 relates to a display filter, and patent document 2 relates to an oxygen-absorbing packaging material. There is no mention of solar shading. Patent Document 3 relates to a heat ray blocking organic film, but since the product does not absorb an infrared region of 5 to 25 μm, a temperature decrease due to radiation cooling cannot be suppressed.

  On the other hand, since the porphyrin derivative compound (A) used in the present invention has an absorption band in the near infrared region of 760 to 2000 nm, it absorbs the main part of the solar energy distribution (300 to 3000 nm) excluding the visible light region. It is possible to suppress the environment under the covering material and the temperature of the object from rising. Moreover, since the inorganic compound (B) used in the present invention has an absorption band in the infrared region of 5 to 25 μm, it absorbs radiant energy emitted by air or objects under the coating material and prevents it from escaping to the outside of the material. Therefore, it can suppress that the environment under the said material and the temperature of an object fall.

  Furthermore, neither the porphyrin derivative compound (A) or the inorganic compound (B) used in the present invention has a main absorption band in the visible light region (380 to 760 nm), and the refractive index of the inorganic compound (B) is Since it is 1.49 to 1.55 and the difference from the refractive index of the thermoplastic resin normally used in the present invention is 0.05 or less, the transparency of the coating material is good and the inner visibility is not hindered. In addition, even when the internal space covered with the coating material of the present invention is not sufficiently ventilated with the outside, the temperature difference between the day and night inside the coating material can be kept small, so that condensation inside the coating material is prevented. Can be suppressed.

  A new covering material that achieves both suppression of temperature increase due to solar radiation provided by the present invention and suppression of temperature decrease due to nighttime radiation cooling, and ensures internal visibility is lightweight, easy to process, easy to work, In addition to low cost, it has the feature that condensation does not easily occur in the coated interior, so it is used for store awnings, window shades, curtains, shutters, tents, dome houses, vehicle seats, field seats, and construction work sites. It is suitable for seats, facility horticulture houses, agricultural materials, aquaculture pond houses, barns, and the like.

The porphyrin derivative compound (A) used in the present invention has an absorption band in the near infrared region of 760 to 2000 nm. Having an absorption band means that an absorption maximum wavelength exists in the same wavelength range. Although content of a porphyrin derivative compound (A) changes with uses of coating | covering material, it is 0.01-1 g / m < ² > normally, Preferably it is 0.03-0.5 g / m < ² >. It is preferable for the content of (A) to be in the above-mentioned range since the temperature rise inside the coating material due to near infrared rays can be prevented and the physical properties of the thermoplastic resin forming the coating material are not impaired.

The porphyrin derivative compound (A) is a tetraazaporphyrin, a phthalocyanine, a naphthalocyanine compound or the like, and a naphthalocyanine compound is particularly preferable.
Examples of phthalocyanine and naphthalocyanine compounds that can be used in the present invention are shown below:

  In Chemical Formula 1 and Chemical Formula 2, R1-R24 each independently represents hydrogen and an alkyl group, cycloalkyl group, or aromatic group which may have a substituent. M represents a divalent metal or two hydrogen atoms, and the metal may be not only a single atom but also an atomic group such as vanadium oxide. Such porphyrin derivative compounds (A) can be used alone or in combination of two or more.

The inorganic compound (B) having an absorption band in the infrared region of 5 to 25 μm and a refractive index of 1.49 to 1.55 used in the present invention has an absorption maximum wavelength in the range of 5 to 25 μm. The refractive index of visible light is in the range of 1.49 to 1.55.
Examples of such a compound (B) include magnesium hydroxide, basic magnesium carbonate, calcium carbonate, calcium silicate, calcium sulfate, talc, kaolin, bentonite, hydrotalcite compound, lithium / aluminum composite hydroxide salt compound, Examples thereof include lithium / aluminum / magnesium composite carbonate compounds and lithium / aluminum / magnesium composite silicate compounds.

  Among these, hydrotalcite compounds, lithium / aluminum composite hydroxide salt compounds, lithium / aluminum / magnesium composite carbonate compounds, and lithium / aluminum / magnesium composite silicate compounds are preferable because of their high infrared absorption ability. Such an inorganic compound (B) can be used individually or in combination of 2 or more types. The average particle size is 0.05 to 10 μm, preferably 0.1 to 5 μm. When the average particle size is smaller than the above range, the handling property may be deteriorated, and when the average particle size is larger than the above range, the transparency of the coating material may be deteriorated. Although content of an inorganic compound (B) changes with uses of a coating material, it is 1-30 wt% normally, Preferably it is about 2-20 wt%. It is preferable for the content to be in the above range since the transparency and mechanical strength of the coating material can be maintained.

  Examples of the thermoplastic resin that can be used in the present invention include polyethylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, polypropylene, propylene-α-olefin copolymer, polymethylpentene, polybutene, polybutadiene, Polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene butadiene resin, ABS resin, AS resin, ionomer resin, AAS resin, acrylic resin, petroleum resin, polylactic acid, polycaprolactone, polybutylene succinate, polyacetal, polyamide , Polycarbonate, modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyethersulfone, polyamideimide, polyphenylene sulfide, polyether Examples include ether ketone, liquid crystal polyester, silicone resin, polytetrafluoroethylene, and ethylene polytetrafluoroethylene copolymer. Among these, polyolefin resin is preferable.

  The porphyrin derivative compound (A) and the inorganic compound (B) may be added in the same thermoplastic resin, or may be added in separate resins, but the resin to which the inorganic compound (B) is added. It is desirable that the refractive index is not greatly deviated from the range of 1.49 to 1.55. Specific examples thereof include polyethylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, polypropylene, propylene-α-olefin copolymer, polyvinyl chloride, polymethyl methacrylate, polyamide and the like.

  In addition, the coating material made of the thermoplastic resin of the present invention may contain a nucleating agent, a weather resistance stabilizer, an ultraviolet absorber, an antioxidant, a flame retardant, a plasticizer, a slip agent, an antiblocking agent, an antistatic agent, and an antifogging as necessary. Agents, antifoggants, antibacterial agents, antifungal agents and the like. Particularly for outdoor use, it is desirable to add a hindered amine weathering stabilizer and an ultraviolet absorber. The hindered amine weathering stabilizer includes the following compounds.

(1) Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, (2) Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6- Tetramethylpiperidine polycondensate, (3) tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (4) 2,2,6, 6-tetramethyl-4-piperidinylbenzoate, (5) bis- (1,2,6,6-tetramethyl-4-piperidinyl) -2- (3,5-di-t-butyl-4-hydroxy (Benzyl) -2-n-butylmalonate, (6) bis (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, (7) 1,1 ′-(1,2- Ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), (8) (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4 -Butanetetracarboxylate, (9) (mixed 1,2,2,6,6-pentamethyl -4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (10) mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ', β '-Tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (11) mixed { 1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5,5) Undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (12) N, N'-bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butyl-N- (1, 2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, (13) N, N'-bis (2,2,6,6-tetra (Methyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane condensate, (14) [N- (2,2,6,6-tetramethyl] -4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) imino] propionamide, (15) poly {[6-[(1,1,3,3 -Tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [[(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2, 6,6-tetramethyl-4-piperidyl) imino]] (trade name Chimassorb 944), (16) 1,5,8,12-tetrakis [4,6-bis (N-butyl-N-1,2, 2,6,6-pentamethyl-4-piperidylamino) -1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane, (17) bis (2,2,6, 6-tetramethyl-1 (octyloxy) -4-piperidinyl) sebacate and the like.

  These hindered amine weathering stabilizers can be used alone or in combination of two or more. The content of the hindered amine weathering stabilizer is usually 0.05 to 3 wt%, preferably 0.1 to 1 wt%.

In addition, salicylic acid-based UV absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate;
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, Benzophenone ultraviolet absorbers such as 2'-dihydroxy-4,4'-dimethoxybenzophenone and 2-hydroxy-4-methoxy-5-sulfobenzophenone;
2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'- Di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5 '-Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- [5-chloro-benzotriazole- Benzotriazole ultraviolet absorbers such as 2-yl] -4-methyl-6- (t-butyl) phenol;

Cyanoacrylate-based UV absorbers such as 2-ethylhexyl-2-cyano-3,3′-diphenylacrylate and ethyl-2-cyano-3,3′-diphenylacrylate;
2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -s-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) ) -S-triazine, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol and other triazine UV absorbers ;
There are oxanilide UV absorbers such as 2-ethoxy-2'-ethyl oxalic acid bisanilide.
The content of the ultraviolet absorber is usually 0.05 to 3 wt%, preferably 0.1 to 1 wt%.

  The method for producing the thermoplastic resin coating material of the present invention is not particularly limited. A method of molding a thermoplastic resin composition containing a porphyrin derivative compound (A) and an inorganic compound (B) into a film, sheet, panel, filament, yarn, nonwoven fabric, woven fabric, hollow molded body, or the like, an inorganic compound (B There is a method of applying a porphyrin derivative compound (A) to these molded products produced from a thermoplastic resin containing Moreover, (A) and (B) do not need to be contained in the same molded body, and can be formed into a covering material by combining those contained in different resins or different molded bodies. Further, for the purpose of adding another function such as strength improvement, it may be combined with another molded body or material not containing (A) or (B).

When molding a thermoplastic resin containing a porphyrin derivative compound (A) and / or an inorganic compound (B), each component may be directly mixed, or a high concentration of (A) and / or (B ) May be prepared in a thermoplastic resin and mixed with a base resin. A known method such as extrusion molding or inflation molding can be used for molding. The components (A) and (B) and the thermoplastic resin may be mixed and used for molding as they are solid, or may be once melt-kneaded and pelletized for use in molding.

Claims (6)

A porphyrin derivative compound (A) having an absorption band in the near infrared region of 760 to 2000 nm and an inorganic compound (B) having an absorption band in the infrared region of 5 to 25 μm and a refractive index of 1.49 to 1.55 Covering material made of thermoplastic resin. The covering material according to claim 1, wherein the porphyrin derivative is selected from a tetraazaporphyrin compound, a phthalocyanine compound, and a naphthalocyanine compound. The inorganic compound is selected from a hydrotalcite compound, a lithium / aluminum composite hydroxide salt compound, a lithium / aluminum / magnesium composite carbonate compound, and a lithium / aluminum / magnesium composite silicate compound. The covering material according to 1. The coating material according to any one of claims 1 to 3, wherein the coating material made of a thermoplastic resin is a molded body selected from a film, a sheet, a panel, a filament, a yarn, a nonwoven fabric, and a woven fabric. The covering material according to any one of claims 1 to 3, wherein the thermoplastic resin is a polyolefin resin. The covering material according to any one of claims 1 to 3, wherein the covering material is used for a facility horticultural house or an agricultural covering material.