JP3307746B2 - Heat ray shielding material composition and heat ray shielding material comprising the composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat ray shielding material composition and, more particularly, to a heat ray shielding material composition which is excellent in transparency, relatively inexpensive and excellent in workability. Heat-shielding agents formed from objects are widely used in so-called glazing materials such as roof materials and wall materials for tennis courts and pools, arcades, ceiling domes, windows of buildings or vehicles, etc. in various forms such as plates, sheets and films. Can be used.

[0002]

2. Description of the Related Art In recent years, in fields such as window materials for various buildings and vehicles, heat rays are shielded while sufficiently taking in visible light.
The demand for a heat ray shielding material that suppresses a rise in room temperature while maintaining brightness is rapidly increasing, and several types of heat ray shielding materials are currently on the market.

[0003] Among them, a typical example is a heat-reflection film obtained by depositing metal particles on a transparent resin film, which is adhered to a transparent substrate. This is not only very expensive but also generally transparent. Since the adhesiveness between the base material and the reflective film is not good, the reflective film may be peeled off during processing, and has a drawback that it is difficult to apply to a window material having a curved surface due to difficulty in thermal processing. .

[0004] Further, since the heat ray shielding plate has a half-mirror shape, it is pointed out that there are problems such as reflection obstruction and a lack of transparency depending on the angle.

In addition, for example, Japanese Patent Application Laid-Open No.
As seen in Japanese Patent Publication No. 0, etc., a heat ray shielding plate in which particles having heat ray reflectivity are kneaded in a transparent resin has also been proposed.
This is a translucent plate that diffuses transparent light, and is not suitable for windows of buildings and vehicles. Also,
It also has the disadvantage of causing a reflection hindrance similar to that using a reflective film. Furthermore, Japanese Patent Publication No. 43-253
As seen in JP-A-35-35 and the like, the use of an infrared absorber composed of an organic dye is conceivable. A heat ray shielding plate using this infrared absorber is transparent and has good workability.

[0006] However, as described in JP-B-43-2533, generally, an organic infrared absorbing agent is used.
Decomposition occurs at a temperature exceeding 0 ° C., and there are restrictions on handling such that it can be used substantially only in cast polymerization.

[0007] In order to solve the problem of heat resistance of the infrared absorbent, for example, as disclosed in JP-A-3-161644, an infrared absorbent having a low heat resistance is added to a transparent resin having a low molding temperature. For example, a method has been considered in which a film is formed from a material, and a laminate is formed by heat laminating a transparent resin plate having a high molding temperature. However, this method does not substantially solve the problem of heat resistance of the infrared absorbent. Further, the film containing the infrared absorbent is produced by cast polymerization, and is considerably expensive.

In general, since an organic infrared absorbing agent is very expensive and the molding method is restricted, a heat ray shielding plate made by adding an organic infrared absorbing agent is used as a building material. It is not economical to use for applications.

Conventionally, a colored transparent resin plate for glazing (including a transparent resin plate colored with a dye and a pigment and a heat ray reflective film adhered to a transparent substrate) has a total light transmittance of 10 to 60%. There are many things, especially 20 ~
The mainstream is about 40%.

[0010] Of the radiant energy of sunlight, about 60% of energy is included in the range of visible light (340 nm to 700 nm), and by blocking visible light to some extent, the glare of the direct sunlight of the sun can be reduced. Thus, the effect of shielding the energy of direct sunlight to some extent can be obtained. However, if visible light is shielded more than necessary, the brightness will be reduced, and it is considered that a light having a total light transmittance of about 20 to 40% is most suitable.

In preparing the heat ray shielding plate, if the total light transmittance is to be adjusted by the addition amount of the infrared absorbing agent, it is necessary to add a considerably large amount of the infrared absorbing agent.

[0012]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, that is, the object is to provide a heat shield excellent in transparency, excellent in heat ray shielding performance, relatively inexpensive, and excellent in workability and heat resistance. It also provides a material composition.

[0013]

The heat ray shielding material composition according to the present invention, which can solve the above problems, has the general formula (I)

[0014]

Embedded image

[0015] (wherein, X represents a hydrogen atom independently represents a halogen atom, -SR ¹ or -OR ^2; Y is -NHR
^And R ¹ and R ² each independently represent a phenyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms , and Y represents 4 to 4 in the phthalocyanine skeleton.
And 8 is introduced; R ³ represents an optionally substituted phenyl group or a -C 1-8 alkyl group; a is an integer of 0 to 4, b is 0 to 4 And the sum of a and b is an integer of 1 or more and 4 or less;
M represents a nonmetal, a metal, a metal oxide or a metal halide. The phthalocyanine compound (A) 0.0
005 to 10% by weight, carbon black (B) 0.00
007-3% by weight, and transparent resin (C) 87-9
9.99943% by weight (however, (A), (B), (C)
Is 100% by weight. ) And (A)
/ (B) is a heat ray shielding material composition of 1/1 to 20/1. In addition, according to the present invention, which was able to solve the above problems,
Such a heat ray shielding material composition has a general formula (II)

Embedded image (Where X is independently a fluorine atom, -SR ¹ or
-OR ² and X represents 4 in the phthalocyanine skeleton
R ¹ and R ² are each independently
A phenyl group or a carbon atom which may have a substituent
B represents an integer of 1 to 4;
Yes; M is no metal, metal, metal oxide or metal halogen
Represents a compound. A) a phthalocyanine compound (A)
0.0005 to 10% by weight, carbon black (B)
0.00007 to 3% by weight, and transparent resin (C) 8
7 to 99.99943% by weight (provided that (A), (B),
The total of (C) is 100% by weight. ) And
(A) / (B) is a heat ray shielding material set of 1/1 to 20/1
Adult.

The phthalocyanine compound (A) used in the present invention has excellent heat resistance as compared with other infrared absorbers, and therefore, an acrylic resin, a polycarbonate resin, P
It is possible to mold even with a molding method in which the resin temperature rises to a high temperature of 220 to 350 ° C, such as injection molding and extrusion molding using ET resin, and it is a molded product with good transparency and excellent heat ray shielding performance Can be obtained.

In the general formula (I) of the present invention, examples of the halogen atom include a fluorine atom, a chloro atom and a bromo atom, and among these halogen atoms, a fluorine atom is preferable. Use of a fluorine atom has an effect of improving compatibility with a resin.

Alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n
-Butyl group, isobutyl group, tert-butyl group, linear or branched pentyl group, hexyl group, heptyl group and octyl group. In addition, the number of carbon atoms is 1 to
The 20 alkyl groups include, in addition to the above alkyl groups, a nonyl group, a decyl group, a dodecyl group, an undecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nondecyl group, an eicosyl group, and the like. No.

Examples of the phenyl group having a substituent include a phenyl group substituted by 1 to 3 alkyl groups having 1 to 4 carbon atoms, and a phenyl group substituted by 1 or 2 alkoxy groups having 1 to 4 carbon atoms. Alternatively, a phenyl group substituted with 1 to 5 halogen atoms such as chloro and fluorine may be mentioned.

The central metal (M) is, for example, copper, zinc, cobalt, iron, vanadium, titanium, indium, tin or the like, and the metal halide is, for example, fluoride, chloride, bromide, iodide or the like. That M is non-metal means that M is an atom other than metal, for example, two hydrogen atoms. Preferably, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, chloroindium, and dichlorotin are used as these central metals. In particular, copper, zinc, cobalt, vanadyl, and dichlorotin are preferably used.

In the phthalocyanine compound represented by the general formula (I), -NHR ³ represents a phenylamino group or an alkylamino group which may have a substituent;
It is preferable to introduce 4 to 8 substituents —NHR ³ into the phthalocyanine skeleton. The remaining position may phenylthio group or an alkylthio group optionally having a substituent represented by -SR ^1, -OR ² in which may have a substituent phenyl group or alkyl group represented , A hydrogen atom, and a halogen atom. Among these substituents, a phenylthio group which may have a substituent, an alkylthio group, a phenyloxy group which may have a substituent, an alkyloxy group, and a fluorine atom are preferable.

The phthalocyanine represented by the general formula (II)
In cyanine compounds, X is which may have a substituent represented by -SR ¹ phenylthio group or an alkylthio group, a phenyl group or alkyl optionally having a substituent represented by -OR ² oxy group you and hydrofluoric
4 a substituent selected from hydrogen atom phthalocyanine skeleton
Preferably, 16 are introduced .

The amount of the phthalocyanine compound in the heat ray shielding material composition is 0.0005 to 1 in 100% by weight of the composition.
If the content is less than 0.0005% by weight, the heat ray shielding effect is small, and if the content is more than 10% by weight, it is not possible to achieve a desired reduction in the amount of the phthalocyanine compound added.

The preferred amount varies greatly depending on the shape of the heat ray shielding material. For example, when preparing a heat ray shielding plate having a thickness of 3 mm, the compounding amount is preferably 0.002 to 0.03% by weight, and more preferably 0.004 to 0.03% by weight.
0.02% by weight. When a heat-shielding plate having a thickness of 10 mm is prepared, the amount is preferably 0.0005 to 0.01% by weight, more preferably 0.001 to 0.00%.
6% by weight. When a heat-shielding plate having a thickness of 10 μm is prepared, the amount is preferably 0.5 to 10% by weight, more preferably 1 to 6% by weight.

If the amount of the phthalocyanine compound is indicated irrespective of the thickness of the heat ray shielding material, the amount of the phthalocyanine compound is preferably 0.06 to 1.2 g / m ² , considering the weight in the projected area from above. , More preferably 0.12 to 0.8 g
/ M ² . When the blending amount of the phthalocyanine compound is 0.0
When less than 6 g / m ² , the heat ray shielding effect is small,
If it exceeds 1.2 g / m ² , it is not possible to achieve the desired reduction in the amount of the infrared absorber added. Further, one or more phthalocyanine compounds can be used as a mixture, and when two or more phthalocyanine compounds having different absorption wavelengths are used, the heat ray shielding effect may be improved.

The amount of carbon black in the heat ray shielding material composition is 0.00007 to 3% by weight based on 100% by weight of the composition. More preferably, the amount of carbon black is the same as that of the phthalocyanine compound. It depends greatly on the shape of the material. For example, when preparing a heat ray shielding plate having a thickness of 3 mm, the blending amount is preferably 0.0002 to 0.008% by weight, more preferably 0.001 to 0.008% by weight.
0.004% by weight. When a heat-shielding plate having a thickness of 10 mm is prepared, the compounding amount is preferably 0.00007 to 0.0025% by weight, more preferably 0.000 to 0.0025% by weight.
3 to 0.0013% by weight. When a heat ray shielding film having a thickness of 10 μm is prepared, the amount is preferably 0.07 to 3% by weight, more preferably 0.3 to 1.5% by weight.

The carbon black blended in the heat ray shielding composition has an average particle diameter of 10 to 500 nm. When the particle size of carbon black exceeds 500 nm,
This may cause poor appearance such as aggregation of particles or loss of transparency. Average particle size of carbon black particles is 10n
When the average particle diameter is smaller than m, not only the preparation is difficult but also the handling property is reduced due to the fine powder, the average particle diameter of the carbon black is preferably from 10 to 500 nm, more preferably from 10 to 100 nm. And more preferably 10 to 60 nm.

If the compounding amount of carbon black is indicated irrespective of the thickness of the heat ray shielding material, the compounding amount is preferably 0.01 to 0.3 g / m ² , considering the weight in the projected area from above. , More preferably 0.04 to 0.15 g /
m ² .

The compounding amount of carbon black is 0.3 g / m
^When it exceeds ² , the total light transmittance becomes extremely low, and when it is less than 0.01 g / m ² , the amount of the phthalocyanine compound added cannot be reduced. As carbon black, for example, channel black,
Furnace black, thermal black, acetylene black and the like.

In general, carbon black tends to cause aggregation of particles and is difficult to disperse. Therefore, a method of using a dispersant or dispersing by applying physical force during granulation has been adopted. However, when a dispersant is used, there is a concern that the physical properties may be reduced due to the dispersant, and when kneading and dispersing during granulation, a long-time kneading or carbon black dispersion step is required, It will be a lot of trouble.

However, when a carbon black graft polymer is used as the carbon black, such a problem is solved, and a molded article having a good carbon black dispersion can be produced.

The mixing ratio of the phthalocyanine compound (A) and the carbon black (B) is (A) / (B) in the range of 1/1 to 2
0/1 is preferable, and (A) / (B) is more preferably 3/2 to 10/1. When (A) / (B) is smaller than 1/1, the total light transmittance may be extremely low, and when (A) / (B) is more than 20/1, this is contrary to the purpose of reducing the amount of the phthalocyanine compound added. It will be.

When a heat ray shielding material is molded using a composition in which a phthalocyanine compound and carbon black are blended with a transparent resin, if the color tone is not the intended purpose as a glazing material, a dye is added so as to give an appropriate color tone. Toning can also be performed by adding.

The transparent resin of the present invention is not particularly limited as long as it is substantially transparent and does not significantly absorb or scatter. Specific examples thereof include polycarbonate resin and methyl resin. Acrylic resin such as methacrylate, polyvinyl resin such as polystyrene / polyvinyl chloride / polyvinylidene chloride, polyolefin resin such as polyethylene / polypropylene, polybutyral resin
Examples thereof include vinyl acetate-based resins such as polyvinyl acetate, polyester-based resins, polyamide resins, and the like. If it is substantially transparent, not only the above-described one kind of resin but also a blend of two or more kinds of resins may be used. Can be used. In addition, the above-mentioned resin can be inserted into transparent glass and used.

Of these transparent resins, polycarbonate resins, (meth) acrylic resins, PET resins, polyethylene resins, polystyrene resins or polyvinyl chlorides are preferred in consideration of practical applications, and particularly polycarbonate resins, methacrylic resins. Resins or PET resins are preferred.

The polycarbonate resin is produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. The following are typical examples of dihydric phenols.

2,2-bis (4-hydroxyphenyl)
Propane [bisphenol A], 1,1-bis (4-
Hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-
(Hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-
Methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone and the like. A preferred dihydric phenol is bis (4
-Hydroxyphenyl) alkane, particularly preferably bisphenol.

The acrylic resin is methyl methacrylate alone, a polymerizable unsaturated monomer mixture containing 50% or more of methyl methacrylate, or a copolymer thereof. Examples of the polymerizable unsaturated monomer copolymerizable with methyl methacrylate include methyl acrylate, ethyl (meth) acrylate (meaning methyl methacrylate or methyl methacrylate; the same applies hereinafter), butyl (meth) acrylate, Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, (meth)
Ethoxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate Glycidyl (meth) acrylate, (meth)
Tribromophenyl acrylate, tetrahydroxyfurfuryl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolethanedi (meth) Examples include acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate.

In practicing the present invention, various additives used in producing ordinary transparent resin materials may be added. Examples of the additive include a colorant, a polymerization regulator, an antioxidant, an ultraviolet absorber, a flame retardant, a plasticizer, a rubber for improving impact resistance, and a release agent.

Examples of the method for molding the heat ray shielding material composition of the present invention include extrusion molding, injection molding, cast polymerization, press molding, calender molding and cast film forming method. Further, it is also possible to prepare a film using the heat ray shielding material composition of the present invention, and heat press or heat laminate the film on a transparent resin plate to produce a heat ray shielding plate.

Further, a heat ray shielding plate can be obtained by printing or coating an acrylic resin ink or a paint prepared using the heat ray shielding material composition of the present invention on a transparent resin plate.

Most of the general infrared absorbers have low heat resistance, and can be used substantially only in cast polymerization. (The molding temperature is less than 200 ° C.)
Since the phthalocyanine compound used in the present invention has good heat resistance, the heat ray shielding material composition of the present invention can be molded at a molding temperature of 220 to 350 ° C., which is impossible when a normal infrared absorber is used. is there. If molding is possible at a molding temperature of 220 to 350 ° C., a large amount of injection molding, extrusion molding or the like can be performed using a transparent and high-strength general-purpose thermoplastic resin such as an acrylic resin, a polycarbonate resin, or a polyester resin. The productivity can be improved by using a molding method suitable for production. Of course, it is needless to say that molding is possible even if the molding temperature is lower than 220 ° C.

There is no particular limitation on the shape of the heat shielding material.
In addition to the most common flat and film shapes, various shapes such as a corrugated plate shape, a spherical shape, and a dome shape are included. Also,
As long as there is no problem in appearance, the concentration distribution of the phthalocyanine compound and carbon black may be uneven.

[0044]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples.

In the following examples, the total light transmittance was measured by using "NDH-300A" manufactured by Nippon Denshoku Co., Ltd.
It was measured based on ISK7105, and the solar transmittance was measured by using “UV-3100PC” manufactured by Shimadzu Corporation.
It was measured based on ISR3106. In the examples, parts and% indicate parts by weight and% by weight unless otherwise specified.

Example 1 60 parts of a polycarbonate resin (Panlite 1285Z manufactured by Teijin Chemicals Limited) and 40 parts of channel black having an average particle diameter of 30 nm were heated and melt-mixed in a kneader, and then pulverized. Polycarbonate resin (Panlite 1285Z manufactured by Teijin Chemicals Limited) 99.
To 99 parts, 0.005 part of the above pulverized product (0.002 part as carbon black) and 0.005 part of infrared absorbent 1 (phthalocyanine compound) were added and mixed by a blender. Create pellets using a pelletizer. 3 using an injection molding machine using the prepared pellets
Molding was performed at a set temperature of 25 ° C. to obtain a resin plate having a thickness of 3 mm. Although the resin temperature rose to 330 ° C., there was no problem with the physical properties of the molded article.

Example 2 60 parts of a polycarbonate resin (Panlite 1285Z manufactured by Teijin Chemicals Limited) and 40 parts of channel black having an average particle size of 30 nm were heated and melt-mixed in a kneader, and then pulverized. Polycarbonate resin (Panlite 1285Z manufactured by Teijin Chemicals Limited) 99.
To 98675 parts, 0.00625 parts of the above pulverized product (0.0025 parts as carbon black) and 0.007 part of infrared absorbent 1 (phthalocyanine compound) were added.
After mixing with a blender, set the temperature to 29 using a T-die.
Extrusion was performed at 0 ° C. to obtain a resin plate having a thickness of 3 mm. Although the resin temperature rose to 300 ° C., there was no problem with the physical properties of the molded article.

Example 3 60 parts of a polycarbonate resin (Panlite 1285Z manufactured by Teijin Chemicals Limited) and 40 parts of channel black having an average particle diameter of 30 nm were heated and melt-mixed in a kneader, and then pulverized. Polycarbonate resin (Panlite 1285Z manufactured by Teijin Chemicals Limited) 99.
To 989 parts, 0.005 part of the above crushed product (0.002 part as carbon black) and 0.006 part of infrared absorber 2 (phthalocyanine compound) were added and mixed by a blender. By extrusion at a set temperature of 290 ° C., a resin plate having a thickness of 3 mm was obtained. Resin temperature is 30
The temperature rose to 0 ° C., but there was no problem in the physical properties of the molded article.

Example 4 A carbon black graft polymer "CX-GLF-21" was added to 99.9855 parts of a methacrylic resin (Sumipex B manufactured by Sumitomo Chemical Co., Ltd.).
(Manufactured by Nippon Shokubai Co., Ltd., carbon content 33.3%, styrene-acrylic polymer component) 0.0045 parts (0.0015 parts as carbon black), 0.01 parts infrared absorbent 3 (phthalocyanine compound) Add
After mixing with a blender, set the temperature to 24 using a T-die.
Extrusion was performed at 0 ° C. to obtain a resin plate having a thickness of 3 mm. Although the resin temperature rose to 250 ° C., there was no problem with the physical properties of the molded article.

Example 5 A carbon black graft polymer "CX-GLF-21" was added to 99.979 parts of a methacrylic resin (Sumipex B manufactured by Sumitomo Chemical Co., Ltd.).
(Manufactured by Nippon Shokubai Co., Ltd., carbon content 33.3%, styrene-acrylic polymer component) 0.003 part (0.001 part as carbon black), infrared absorber 3
(Phthalocyanine compound) was added in an amount of 0.018 parts, and the mixture was mixed in a blender.
The resin was extruded at a temperature of 300 ° C. to obtain a resin plate having a thickness of 3 mm. Although the resin temperature rose to 250 ° C., there was no problem with the physical properties of the molded article.

Infrared absorber 1 (phthalocyanine compound) Substance name: 3,6-octafluoro- (4,5-octakisanilino) oxyvanadium phthalocyanine Infrared absorber 2 (phthalocyanine compound) Substance name: 4,5-octa Kisanilino- (3,6-octakisphenylthio) oxyvanadium phthalocyanine Infrared absorber 3 (phthalocyanine compound) Substance name: 4,5-octakisbutylthio- (3,6-octakisphenylthio) oxyvanadium phthalocyanine <Comparative Example 1> 0.013 parts of an infrared absorbent 1 (phthalocyanine compound) was added to 99.987 parts of a polycarbonate resin (Panlite 1285Z manufactured by Teijin Chemicals Limited) and mixed with a blender. Thereafter, the same operation as in Example 1 was performed to obtain a resin plate having a thickness of 3 mm.

Comparative Example 2 Infrared absorbent 1 (phthalocyanine compound) was added to 99.993 parts of a polycarbonate resin (Panlite 1285Z manufactured by Teijin Chemicals Limited) at a concentration of 0.00.
7 parts were added and mixed with a blender to obtain a composition. Thereafter, the same operation as in Example 2 was performed to obtain a resin plate having a thickness of 3 mm.

Comparative Example 3 A dye Kayaset Blue A-2R 0.00 was added to the composition of Comparative Example 2 in place of carbon black.
11 parts, Kayaset Red A-2G 0.0014 parts, Kayaset
Green AB 0.0005, Kayaset Yellow AG
0.0003 parts (all dyes were manufactured by Nippon Kayaku Co., Ltd.) were added, and thereafter the same procedure as in Example 2 was performed to obtain a resin plate having a thickness of 3 mm.

Comparative Example 4 To 99.967 parts of a methacrylic resin (SUMIPEX B manufactured by Sumitomo Chemical Co., Ltd.) was added 0.033 part of an infrared absorbent 3 (phthalocyanine compound), and the mixture was mixed with a blender. Thereafter, the same operation as in Example 4 was performed to obtain a resin plate having a thickness of 3 mm.

Comparative Example 5 Methacrylic resin 99.99
Part, infrared absorbent 3 (phthalocyanine compound) 0.0
Except having changed to 1 part, it carried out similarly to the comparative example 4, and obtained the resin plate of 3 mm in thickness.

Comparative Example 6 A dye Kayaset Blue A-2R 0.00 was added to the composition of Comparative Example 5 in place of carbon black.
055 parts, Kayaset Red A-2G 0.0007 parts, Kayas
et Green A-B 0.00025 copy, Kayaset Yellow AG
0.00015 parts (all of the dyes were manufactured by Nippon Kayaku Co., Ltd.) were added, and thereafter the same procedure as in Comparative Example 5 was performed.
A resin plate having a thickness of 3 mm was obtained.

Comparative Example 7 A dye was added to 100 parts of a polycarbonate resin (Panlite 1285Z manufactured by Teijin Chemicals Limited).
Kayaset Red A-2G 0.003 copy, Kayaset Green AB
0.0035 parts (the dye is Nippon Kayaku Co., Ltd.)
And mix with a blender. Thereafter, the same operation as in Example 2 was performed to obtain a resin plate having a thickness of 3 mm.

Comparative Example 8 A polycarbonate resin (Panlite 1285Z manufactured by Teijin Chemicals Ltd.) was extruded at a set temperature of 290 ° C. using a T-die to obtain a resin plate having a thickness of 3 mm.

<Comparative Example 9> 0.019 parts of a polycarbonate resin (Panlite 1285Z manufactured by Teijin Chemicals Limited) was mixed with 0.01 infrared absorbing agent 2 (phthalocyanine compound).
Add 5 parts and mix with a blender. Thereafter, the same operation as in Example 2 was performed to obtain a resin plate having a thickness of 3 mm.

The amounts of the phthalocyanine compounds, carbon blacks and dyes of Examples 1 to 5 and Comparative Examples 1 to 9 and the values of the total light transmittance are shown in Table 1, and the transmittance and wavelength of representative ones among these are shown. Are shown in FIGS.

<Reference> Thermogravimetry of a phthalocyanine compound and a commercially available infrared absorber was performed using TG-DTA-2000 manufactured by Mac Science Corporation. The measured values are shown in Table 2.

-Measurement conditions- Measured under a nitrogen stream. The nitrogen flow rate is 200 ml / min. 1
The temperature was raised to 50 ° C at a rate of 10 ° C / min.
min. The pyrolysis onset temperature is the temperature at the intersection of the weight decay curves.

[0063]

[Table 1]

The larger the value of the total light transmittance is, the larger the amount of visible light transmitted and the brightness is higher. The smaller the value of the solar light transmittance is, the better the performance of shielding the heat rays.

[0065]

[Table 2]

Infrared absorber 4 Substance name: 2,5-cyclohexadiene-1,4-diylidene-bis (N, N-bis (4-dibutylaminophenyl) ammonium) bis (hexafluoroantimonate) Infrared absorber 5 Substance name: N, N-bis (4-dibutylaminophenyl)
-N- (4- (N, N-bis (4-dibutylaminophenyl) amino) phenyl) -aminium hexafluoroantimonate Infrared absorbent 6 Substance name: bis (trichlorobenzene-1,2, dithiol) nickel (2 1) Tetrabutylammonium As is clear from Table 1, the heat ray shielding material using the phthalocyanine compound of the present invention in combination with carbon black is:
It can be seen that compared with the heat ray shielding material using only the phthalocyanine compound, the amount of the phthalocyanine compound used is equal to or less than half and has the same heat ray shielding effect.

As compared with the case where the phthalocyanine compound and the dye are used in combination, it can be seen that the total light transmittance is the same, but the solar transmittance is small and the heat ray shielding effect is considerably improved. In Examples 1 to 5, the molding methods are injection molding and extrusion molding, and the resin temperature is considerably high at 250 to 330 ° C. When a commercially available infrared absorbing agent is used, when molded at such a high temperature, the infrared absorbing agent is thermally decomposed and the absorption of infrared light is attenuated, so that it cannot be used as a heat ray shielding material. Table 2 clearly shows that the heat resistance of the phthalocyanine compound of the present invention is superior to that of a commercially available infrared absorber.

It is also apparent that the heat ray shielding effect is superior to that of a resin plate colored with a dye.

2 and 3, when a dye is added to the phthalocyanine compound, only the transmittance of visible light decreases, but when carbon black is added, the transmittance decreases as a whole. You can see that there is. This is probably because carbon black has the ability to absorb not only visible light but also infrared light.

[0070]

By using a specific amount of the phthalocyanine compound and carbon black, it is possible to reduce the use amount of the phthalocyanine compound by half or less, as compared with the case where the phthalocyanine compound is used alone. it can. Further, the heat ray shielding effect is improved as compared with the case where the phthalocyanine compound and the dye are used in combination.

That is, by adding a specific phthalocyanine compound and carbon black to a specific amount of the transparent resin, molding at a high temperature is possible, and the molded product has a good transparency and excellent heat ray shielding effect. Has been able to provide a relatively inexpensive heat ray shielding material composition.

[Brief description of the drawings]

FIG. 1 is a chart showing the relationship between light transmittance and wavelength in Example 1 and Comparative Example 1.

FIG. 2 is a chart showing the relationship between light transmittance and wavelength in Example 2 and Comparative Examples 2 and 3.

FIG. 3 is a chart showing the relationship between light transmittance and wavelength in Example 4 and Comparative Examples 5 and 6.

FIG. 4 is a chart showing the relationship between light transmittance and wavelength in Comparative Examples 7 and 8.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08K 5: 3467 C08K 5: 3467 3:04) 3:04) (72) Inventor Koji Yoshinori 1-chome Kannondai, Tsukuba, Ibaraki Prefecture 25-12 Nippon Shokubai Co., Ltd. Tsukuba Research Laboratories (56) References JP-A-60-226551 (JP, A) JP-A-55-66922 (JP, A) JP-A-49-87792 (JP, A) 53-35835 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 C08J 5/00

Claims (3)

(57) [Claims] 1. A compound of the general formula (I) (Where X is independently a hydrogen atom, a halogen atom,
-SR ¹ or an -OR ^2; Y represents -NHR ^3;
R ¹ and R ² each independently represent a phenyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms , and 4 to 8 Y are introduced into the phthalocyanine skeleton.
It is,; R ³ represents an optionally substituted phenyl group or a -C 1-8 alkyl group; a is 0
B is an integer of 0 to 4, and the sum of a and b is an integer of 1 or more and 4 or less; M is a metal-free,
Represents a metal, metal oxide or metal halide. The phthalocyanine compound (A) represented by 0.0005 to 10
%, Carbon black (B) 0.00007 to 3% by weight, and transparent resin (C) 87 to 99.99943.
% By weight (however, the sum of (A), (B) and (C) is 100
% By weight. ) And (A) / (B) is 1 /
A heat ray shielding material composition of 1 to 20/1. 2. A compound of the general formula ( II ) (Wherein, X independently represents a fluorine atom, —SR ¹ or —OR ² , and X represents 4 to
And 16 are introduced; R ^1, R ² are each independently
A phenyl group which may have a substituent or 1 carbon atom
Represents 20 alkyl groups ; b is an integer of 1-4
M represents a metal-free, metal, metal oxide or metal halide. A) a phthalocyanine compound (A)
0.0005 to 10% by weight, carbon black (B)
0.00007 to 3% by weight, and transparent resin (C) 8
7 to 99.99943% by weight (provided that (A), (B),
The total of (C) is 100% by weight. And (A) / (B) being 1/1 to 20/1. 3. A heat ray shielding material obtained by molding and processing the heat ray shielding material composition according to claim 1.