JPH09263658A - Near infrared-absorbing resin composition and its application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a near infrared-absorbing resin composition, useful as a heat-absorbing covering material for agriculture, excellent in durability and easily producible at a low cost by using some kind of naphthalocyanine compound. SOLUTION: This resin composition is obtained by compounding a base resin with at least one kind of naphthalocyanine of the formula (A<1> to A<24> are each independently H or a halogen; M is a pair of H atoms, a divalent metallic atom or a substituted trivalent or tetravalent metallic atom, or an oxygen-bonded trivalent or tetravalent metallic atom). Further, the M is preferably a pair of H atoms, Cu, Pd, Pb, AlCl, InCl, TiO or VO. The base resin is preferably polyvinyl chloride, polyvinyl acetate, polyethylene or a vinyl acetate-ethylene copolymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a near infrared ray absorbing resin composition, a near infrared ray absorbing filter obtained by using the same, a near infrared ray absorbing ink, a near infrared ray absorbing paint, a heat ray absorbing coating material for agriculture, and a heat ray absorbing window. Regarding glass. The near infrared absorbing resin composition can be used as a near infrared absorbing printing ink readable by a near infrared detector. A near infrared absorption filter can also be produced by coating plastic or glass as a paint, or by directly forming a film or plate with a resin composition. Further, as a heat ray absorbing coating material for agriculture, it is possible to suppress the temperature rise in the house during the summer. Further, by combining with a window glass of a building, a car, an electric train, a ship, an aircraft, etc., it is possible to block heat rays from the outside and suppress an increase in temperature inside and inside the vehicle. In addition, as a film for selective use of light quality by cutting a specific wavelength region, it can be used as a film for controlling plant growth, infrared cutting of a semiconductor light receiving element, and eyeglasses that protect human eyes from light rays containing harmful infrared rays. . Among the above, the near-infrared absorption filter for the purpose of intercepting heat rays is a field of interest because it contributes to energy saving.

[0002]

2. Description of the Related Art A heat ray reflection filter is known in which a metal oxide such as indium oxide or tin oxide and a metal such as gold or silver are alternately laminated on a PET film or glass for the purpose of blocking heat rays. However, it has a drawback that the product cost is high due to the complicated manufacturing process. Compared with those inorganic type heat ray reflection filters, the near-infrared absorption filter using the near-infrared absorption dye has a wide application field and a large market need because it is easy to manufacture. However, due to the problems of cost and durability (especially stability against light) of dyes, the current situation is that they have not spread.

As an organic dye that absorbs near infrared rays, a cyanine dye has been well known. However, since cyanine dyes have extremely low light fastness, there are many restrictions when using them. Further, compounds of the aminium salt type described in JP-A-3-161644, or JP-B-54-25060 and JP-A-50-
The metal complex compounds described in 51549 and the like are insufficient in heat resistance and light resistance. In addition, Japanese Patent Laid-Open No. 3-115362,
The anthraquinone compounds described in JP-A-62-903 have heat resistance, but they are insufficient in light resistance. As a near-infrared absorbing dye having high durability, Japanese Patent Publication No. 59-
1311, JP-A-60-209583, Japanese Patent Publication No. 2-51
55, JP-A-61-152685, JP-A-61-223.
The phthalocyanines described in 056 and Japanese Patent Laid-Open No. 3-62878 have complicated manufacturing processes, and even if the dye itself has high durability, it can be used for agricultural and agricultural purposes such as those actually used for agricultural purposes. In a soft resin containing a large amount of a plasticizer such as polyethylene, there is a drawback that the dye bleeds out. JP-A-61-215663, JP-A-63-159
The soluble type naphthalocyanine described in 386 also has a problem of bleeding. Further, phthalocyanine pigments such as phthalocyanine green and phthalocyanine blue have been conventionally used as a stable dye in a soft resin, but they have a drawback that they absorb a large amount in the visible region and do not sufficiently transmit the light necessary for growing a crop. . Further, in JP-A-61-151193, a naphthalocyanine pigment is introduced, but it is not described as a resin composition.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a near-infrared absorbing resin composition which has a low cost, a high durability and a high durability. Further, it is intended to provide a near-infrared absorbing filter, a near-infrared absorbing printing ink, a near-infrared absorbing paint, an agricultural heat ray absorbing coating material, and a heat ray absorbing window glass using the same. In particular, it is an object to provide a material capable of blocking heat rays from the sun during the daytime in summer and releasing radiant heat at night, as a heat ray absorbing coating material for agriculture which is a soft resin.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the inventors of the present invention simply produced a desired near-infrared absorbing resin composition by using a certain kind of naphthalocyanine compound. They have found that they can do so and have completed the present invention. That is, the present invention, in the base resin,
The present invention relates to a near-infrared absorbing resin composition containing at least one naphthalocyanine compound represented by the general formula (1) (formula 2). The present invention also relates to a near-infrared absorbing filter, a near-infrared absorbing printing ink, a near-infrared absorbing paint, a heat ray absorbing coating material for agriculture, and a heat ray absorbing window glass obtained by using the resin composition.

[0006]

Embedded image [In the formula, A ^{1 to} A ²⁴ each independently represent a hydrogen atom or a halogen atom, and M is two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxy metal. Represents]

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The near-infrared absorbing resin composition of the present invention is a resin composition containing a naphthalocyanine compound represented by the general formula (1) in a base resin. In the naphthalocyanine compound represented by the general formula (1) used in the present invention, examples of the halogen atom represented by A ^{1 to} A ²⁴ are fluorine, chlorine, bromine or iodine, which are mixed. May be.

Examples of the divalent metal atom represented by M include Cu (II), Zn (II), Fe (II) and Co (I
I), Ni (II), Ru (II), Rh (II), Pd (I
I), Pt (II), Mn (II), Mg (II), Ti (I
I), Be (II), Ca (II), Ba (II), Cd (I
I), Hg (II), Pb (II), Sn (II) and the like. Examples of mono-substituted trivalent metal atoms include AlC
l, AlBr, AlF, AlI, GaCl, GaF, G
aI, GaBr, InCl, InBr, InI, In
F, TlCl, TlBr, TlI, TlF, FeCl,
_{RuCl, Al-C 6 H 5} , Al-C 6 H 4 (C
_{H 3), In-C 6} H 5, In-C 6 H 4 (CH 3),
_{In-C 6 H 5, Mn} (OH), Mn (OC 6 H 5),
Mn [OSi (CH _{3) 3],} and the like.

An example of a disubstituted tetravalent metal atom is Cr.
Cl ₂ , SiCl ₂ , SiBr ₂ , SiF ₂ , Si
I ₂ , ZrCl ₂ , GeCl ₂ , GeBr ₂ , Ge
I ₂ , GeF ₂ , SnCl ₂ , SnBr ₂ , SnF ₂ ,
TiCl ₂ , TiBr ₂ , TiF ₂ , Si (OH) ₂ ,
Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , S
n (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , SnR
₂ , GeR ₂ [R represents an alkyl group, a phenyl group, a naphthyl group, and a derivative thereof], Si (OR ′) ₂ , S
n (OR ') ₂ , Ge (OR') ₂ , Ti (O
R ′) ₂ , Cr (OR ′) ₂ [R ′ represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkylalkoxysilyl group and derivatives thereof], Sn
(SR ") ₂ , Ge (SR") ₂ (R "is an alkyl group,
A phenyl group, a naphthyl group, and derivatives thereof] and the like. Examples of oxymetal include VO and Mn
O, TiO, etc. are mentioned. Among these, more preferable M is two hydrogen atoms, Cu, Pd, Pb and A.
1Cl, InCl, TiO or VO, more preferably VO. The resin composition of the present invention can be obtained by heating and kneading the powder or pellet of the base resin and the naphthalocyanine compound to uniformly disperse the dye. If necessary, existing UV absorbers, plasticizers,
You may add additives, such as a light stabilizer. The kneading temperature varies depending on the resin used, but is usually 100 to 300 ° C. The content of naphthalocyanine varies depending on the intended absorption in the near infrared region, but is usually 0.001 to 30%.

The base resin is not particularly limited as long as it is a resin that can disperse naphthalocyanine well, but a resin having as high transparency as possible is preferable. Specific examples include polyethylene, polystyrene, polyacrylic acid, polyacrylic acid ester, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride and other vinyl compounds and addition compounds of vinyl compounds, polymethacrylic acid, polymethacrylic acid ester. , Vinylidene chloride, polyvinylidene fluoride, polyvinylidene cyanide, vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene cyanide / vinyl acetate copolymer, and other vinyl compounds or fluorine Copolymers of system compounds, compounds containing fluorine such as polytrifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, nylon 6, nylon 6
Polyamides such as 6 and the like, polyesters such as polyimide, polyurethane, polypeptide and polyethylene terephthalate, polycarbonates, polyoxymethylene, polyethers such as polyethylene oxide and polypropylene oxide, epoxy resins, polyvinyl alcohol, polyvinyl butyral and the like can be mentioned. In particular, it is a soft resin that has good compatibility with the naphthalocyanine compound used in the present application and can be dispersed well, and examples thereof include polyvinyl chloride, polyvinyl acetate, polyethylene, and a vinyl acetate / ethylene copolymer.

The near-infrared absorbing printing ink or paint of the present invention comprises the above-mentioned near-infrared absorbing resin composition obtained by adding chloroform, methyl ethyl ketone, ethyl acetate, butyl acetate, acetone, toluene, xylene, dibutyl ether, dimethylformamide, ethanol, isopropanol. It is manufactured by dissolving in a solvent such as or a mixed solvent thereof. Further, in order to prepare a practical printing ink or paint, it is possible to add necessary additives depending on each application. Further, any of the printing inks or paints can be produced by adding the composition of the present invention and other necessary additives to a thermosetting or photocuring base resin.

The near infrared ray absorbing filter and the heat ray absorbing coating material for agriculture of the present invention can be obtained by producing a film or plate using the above near infrared ray absorbing resin composition.
Examples of the method for producing the resin film or the resin plate include a melt casting method, a melt extrusion method, and a calender method. In the case of melt extrusion molding, a T-die method, an inflation method or the like is applied. Further, the near-infrared absorption filter and the heat ray absorption coating material for agriculture of the present invention, the near-infrared absorption coating material of the present invention, on a transparent resin film, transparent resin, transparent glass, etc., a bar coder, a blade coater,
It is also manufactured by coating with a spin coater, reverse coater, die coater, spray, or the like. The agricultural heat ray absorbing coating material of the present invention can also be produced by bonding the near infrared ray absorbing filter of the present invention to a transparent resin film, a transparent resin, transparent glass or the like. The agricultural heat ray absorbing coating material of the present invention can be used as it is for the near infrared ray absorbing filter to prepare a pipe house, a tunnel, a glass house, and the like.
It can also be used as an exterior or interior lining for existing agricultural houses. Further, the agricultural heat ray absorbing coating material of the present invention, the film or plate may be used as it is, or by making a thread or by finely cutting the film, knitting, the agricultural heat ray absorbing coating material improved ventilation. You may use as.

By using the near infrared ray absorbing resin composition of the present invention for a window glass, an excellent heat ray absorbing window glass can be obtained. As a method for use in a window glass, for example, the near-infrared absorbing paint described above can be produced by coating the window glass with a bar coater, a blade coater, a spin coater, a reverse coater, a die coater, a spray, or the like. Further, it can be produced by sticking the above-mentioned near-infrared absorption filter to a window glass with an adhesive or an adhesive.

The agricultural vinyl (agricultural vinyl) film and agricultural polyolefin (agricultural PO) film containing the naphthalocyanine compound represented by the general formula (1) used in the present application are
Since the absorption in the far-infrared region is very small, it also has the effect of releasing the heat stored in the house (radiant heat), and is particularly effective in suppressing the temperature rise in the summer, making it an excellent heat ray absorbing coating material for agriculture. It is a thing.

[0015]

EXAMPLES The present invention will be described in more detail below with reference to examples. In addition, a part represents a weight part here. Example 1 Polyvinyl chloride (Nippon Vinyl 4000M3) (100
Parts by weight), dioctyl phthalate (45 parts), tricresyl phosphate (5 parts), bisphenol A type epoxy resin (2 parts), zinc stearate (0.5 parts), barium stearate (0.5 parts). , A surfactant (sorbitan ester, MTN-A-403 manufactured by Marubishi Yuka) (2
Part) and naphthalocyanine represented by the following formula (2) (chemical formula 3) (0.2 part) are added, and the mixture is heated at 110 ° C. with a high-speed mixer.
After stirring and mixing for 5 minutes, the mixture was kneaded on a roll heated to 180 ° C. for 5 minutes, and a calender molding machine was used to form a soft film having a thickness of 0.10 mm. JIS-R-
3106 according to Shimadzu spectrophotometer (UV31
00), the visible light transmittance (Tv) and the heat ray transmittance (Te) of the film were measured, and Tv = 75.6.
%, Te = 63.5%. Further, the film 1
A light resistance test with a carbon arc lamp (63 ° C.) for 000 hours was conducted, but no decrease in absorption rate due to deterioration of the dye was observed. Further, no decrease in the absorption rate due to the decomposition of the pigment was observed after the outdoor spreading for 6 months.

[0016]

Embedded image For comparison, a soft film having a thickness of 0.10 mm was prepared and Tv and Te were measured in the same manner as above except that naphthalocyanine was not added. Tv = 89.8 %, Te = 89.3%. Further, when an agricultural house was produced from each of the above two types of films, the temperature inside the house during the day was 2 to 7 ° C. lower in the naphthalocyanine-containing film, and the heat ray absorbing effect was recognized.

Example 2 Polyethylene (V5993 manufactured by Mitsui DuPont) (100
Part) and naphthalocyanine (0.15 part) represented by the following formula (3) (formula 4) were pelletized at 200 ° C. using a twin-screw extruder to prepare a near-infrared absorbing resin composition. . Furthermore, at 200 ° C., a single screw extruder equipped with a T-die melt-extrudes to obtain a thickness of 0.1 mm.
Was formed into a film. Tv and T as in the first embodiment.
When e was measured, Tv = 78.6%, Te = 64.
7%, and the agricultural house made of the film is
The increase in the temperature inside the house was suppressed as compared with the case where naphthalocyanine was not contained. Furthermore, regarding the film, 1
A light resistance test with a carbon arc lamp (63 ° C.) for 000 hours was conducted, but no decrease in absorption rate due to deterioration of the dye was observed.

[0018]

Embedded image

Example 3 Modified polyolefin resin (EVA, Dumilan D-219 manufactured by Takeda) (100 parts) and the following formula (4) (formula 5)
Naphthalocyanine (0.2 parts) represented by
The mixture was kneaded for 20 minutes to prepare a near-infrared absorbing resin composition. The resin composition was dissolved in 1000 parts of toluene to prepare a near infrared absorbing coating. The paint is difficult to see when used as an ink, but it is 780 to 830 nm.
It can be used as a hidden ink that can be detected by the laser and corresponds well to the semiconductor laser of. In addition, a glass having an excellent heat ray absorbing function was obtained by applying it as a paint on a glass plate with a roll coater (Tv = 70.3).
%, Te = 58.9%).

[0020]

Embedded image

Examples 4 to 10 An agricultural film was prepared in the same manner as in Example 1 except that the kind of naphthalocyanine was changed, and Tv and Te were measured. The results are shown in Table-1 (Table 1 and Table 2). Decrease in Te was observed in all cases, confirming the heat ray blocking effect.

[0022]

[Table 1]

[0023]

[Table 2]

Comparative Example 1 A film was produced in exactly the same manner as in Example 1 except that phthalocyanine green was used instead of naphthalocyanine. When Tv and Te were measured in the same manner for the obtained film, Tv = 68.4% and Te = 7
It was 0.0%, the heat ray cut rate was small, and it was insufficient as a heat ray absorbing coating material for agriculture.

[0025]

Industrial Applicability The present invention provides a near-infrared absorbing resin composition having high durability easily, and the obtained near-infrared absorbing resin composition is a near-infrared absorbing filter,
It is extremely valuable in practical use and can be applied to near-infrared absorbing ink, near-infrared absorbing paint, heat ray absorbing coating material for agriculture, heat ray absorbing window glass and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08L 31/04 LHE C08L 31/04 LHE 101/00 101/00 C09B 47/00 C09B 47/00 C09D 5/32 PRB C09D 5/32 PRB 11/00 PSX 11/00 PSX (72) Inventor Matsu ▲ Saki ▼ ▲ Ryimei Mitsui Toatsu Chemical Co., Ltd. 1190 Kasamacho, Sakae-ku, Yokohama-shi, Kanagawa (72) Imon Shuhei 2-1, Tango Dori, Minami-ku, Aichi Prefecture, Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Masataka Iwata 2-1-1, Tango Dori, Minami-ku, Aichi Prefecture Mitsui Toatsu Chemical Co., Ltd. ( 72) Inventor Keisuke Soma, 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (10)

[Claims] 1. A near-infrared absorbing resin composition containing a naphthalocyanine compound represented by the following general formula (1) (formula 1) in a base resin. Embedded image [In the formula, A ^{1 to} A ²⁴ each independently represent a hydrogen atom or a halogen atom, and M is two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxy metal. Represents] 2. M is two hydrogen atoms, Cu, Pd, P
The near infrared absorbing resin composition according to claim 1, which is b, AlCl, InCl, TiO or VO. 3. The near infrared absorbing resin composition according to claim 2, wherein M is VO. 4. The base resin is a soft resin.
The near-infrared absorbing resin composition according to any one of 3 above. 5. The near infrared ray absorbing resin composition according to claim 4, wherein the base resin is polyvinyl chloride, polyvinyl acetate, polyethylene, or a vinyl acetate / ethylene copolymer (EVA). 6. A near infrared ray absorbing printing ink obtained by using the near infrared ray absorbing resin composition according to claim 1. 7. A near infrared absorbing coating material obtained by using the near infrared absorbing resin composition according to claim 1. 8. A near-infrared absorption filter obtained by using the near-infrared absorption resin composition according to claim 1. 9. A heat ray absorbing coating material for agriculture, which is obtained by using the near infrared ray absorbing resin composition according to any one of claims 1 to 5. 10. A heat ray absorbing window glass obtained by using the near infrared ray absorbing resin composition according to claim 1 for a window glass.