JP3163813B2 - Near-infrared absorbing resin composition and molded article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic norbornene-based resin composition to which a near-infrared ray absorbing agent is added, and a molded article comprising the resin composition and having a near-infrared ray absorbing ability which does not decrease even under high temperature and high humidity conditions.

[0002]

2. Description of the Related Art In recent years, near infrared rays have been used, such as an infrared cut filter that cuts off infrared rays for the purpose of heat insulation and heat insulation, and an optical character reader that uses near infrared rays as reading light in fields such as computers and facsimile machines. Technology is improving and the scope of application is expanding. Accordingly, the importance of optical components that absorb near-infrared light having a wavelength of 600 to 2500 nm has been increasing.

Conventionally, such optical parts have been manufactured by applying a near-infrared absorbing agent to the surface of glass.
Conversion to lightweight materials that are easy to mold has progressed, and optical components formed by molding a resin composition in which a near-infrared absorbing agent is blended with a transparent resin such as polycarbonate or polymethyl methacrylate have come to be used.

However, conventional near-infrared absorbing optical parts made of a transparent resin have difficulty in long-term reliability, and when used under severe conditions such as high temperature and high humidity for a long period of time, the absorption wavelength region often increases. There was a problem of change.

[0005]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies with the aim of developing a resin composition having a stable near-infrared absorbing ability. As a result, when a thermoplastic norbornene-based resin is used as a transparent resin, it has been used for a long time. The inventors have found that the absorption wavelength region does not change, and have completed the present invention.

[0006]

According to the present invention, there is provided a thermoplastic norbornene-based resin composition comprising a thermoplastic norbornene-based resin and a near-infrared absorbing agent, and a molded article comprising such a resin composition. Is provided.

(Thermoplastic norbornene resin) The thermoplastic norbornene resin used in the present invention is disclosed in
882, JP-A-3-122137, JP-A-4-63
807 and the like. Specific examples thereof include a ring-opening polymer of a norbornene-based monomer, a hydrogenated product thereof, an addition-type polymer of a norbornene-based monomer, and a resin of a norbornene-based monomer and an olefin. Addition type polymers, modified products of these polymers, and the like are included.

[0008] Norbornene monomers are also disclosed in the above publications, JP-A-2-227424 and JP-A-2-276842.
No. A known monomer, etc., for example, norbornene, its alkyl, alkylidene, aromatic-substituted-induced body,
For example, 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5 - Phenyl-2-norbornene, 5-phenyl-5-methyl-2-
Norbornene; multimers of dicyclopentadiene, induction of similar to that described above, for example, cyclopentadiene,
2,3-dihydrodicyclopentadiene, 1,4: 5
8-Dimethano-1,2,3,4,4a, 5,8,8a-
2,3-cyclopentadienonaphthalene, 6-ethyl-
1,4: 5,8-dimethano-1,4,4a, 5,6
7,8,8a-octahydronaphthalene, 1,4: 5
10: 6,9-trimethano-1,2,3,4,4a,
5,5a, 6,9,9a, 10,10a- dodecahydro-2,3 cyclopentadienide Roh anthracene; adducts of cyclopentadiene and tetrahydroindene, etc., the induction of similar to that described above, for example, 1, 4-methano-1,
4,4a, 4b, 5,8,8a, 9a-octahydrofluorene, 5,8-methano-1,2,3,4,4a,
5,8,8a-octahydro-2,3-cyclopentadienonaphthalene; and the like.

The polymerization of the norbornene-based monomer may be carried out by a known method, and if necessary, may be carried out by copolymerization with another copolymerizable monomer or by hydrogenation to form a thermoplastic saturated norbornene-based polymer. It can be an additive. Further, a polymer or a polymer hydrogenated product is disclosed in JP-A-3-95.
By methods known in the such as 235 No., scan styrene hydrocarbons, may be modified with <br/> an organosilicon compound having an olefinically unsaturated binding. In order to obtain a product having good moisture resistance and chemical resistance, a thermoplastic norbornene resin containing no polar group is preferable.

The molecular weight is determined by GP using cyclohexane as a solvent.
The number average molecular weight measured by C (gel permeation chromatography) analysis is suitably from 100,000 to 200,000. In addition, when hydrogen is added, the hydrogenation rate is 90% or more, preferably 95% or more, and more preferably 99% or more, in order to improve light deterioration resistance and weather resistance deterioration.

The thermoplastic saturated norbornene resin used in the present invention may optionally contain a phenol-based or phosphorus-based antioxidant; a phenol-based thermal degradation inhibitor; a benzophenone-based ultraviolet stabilizer; an amine-based , A lubricant such as an ester of an aliphatic alcohol, a partial ester or a partial ether of a polyhydric alcohol, and the like. In addition, other resins, rubbers, fillers, and the like can be mixed and used as long as the object of the present invention is not impaired.

(Near-Infrared Absorber) The near-infrared absorber used in the present invention is not particularly limited as long as it is a near-infrared absorber generally used by being added to a transparent resin.
With respect to a solution in which 0.1 part by weight of the compound is dissolved with respect to 00 parts by weight, the light transmittance with respect to the good solvent is 50% or less in a part of the near-infrared wavelength region of 600 to 2500 nm or in the entire region, and more preferably 30%. % Is preferable. . Examples of such near-infrared absorbers include cyanine-based near-infrared absorbers such as compounds represented by the following structural formula 1 and compounds represented by the following structural formula 2: pyrylium-based infrared rays such as compounds represented by the structural formula 3 Absorbent; Squarylium-based near-infrared absorbent such as compound represented by Structural Formula 4; Structural Formula 5
A croconium-based infrared absorber such as a compound represented by
Azulnium-based near-infrared absorber such as a compound represented by Structural Formula 6; a phthalocyanine-based near-infrared absorber such as a compound represented by Structural Formula 7 and a compound represented by Structural Formula 8; Compounds, dithiol metal complex-based near infrared absorbers such as compounds represented by Structural Formula 10; Structural Formula 11
A naphthoquinone-based near-infrared absorber such as a compound represented by Structural Formula 12; a compound represented by Structural Formula 13 or an anthraquinone-based near infrared absorber such as a compound represented by Structural Formula 14; A compound represented by Formula 15,
Indophenol-based near-infrared absorbers such as compounds represented by Structural Formula 16; compounds represented by Structural Formula 17 and azimuth-based near-infrared absorbers such as compounds represented by Structural Formula 18; In addition, a commercially available near-infrared absorber, SIR-
103, SIR-114, SIR-128, SIR-1
30, SIR-132, SIR-152, SIR-15
9, SIR-162 (Mitsui Toatsu Dye), Kay
asorbIR-750, Kayasorb IRG-
002, Kayasor IRG-003, IR-82
0B, Kayasorb IRG-022, Kayas
orb IRG-023, Kayasorb CY-
2, Kayasorb cCY-4, Kayasorb
CY-9 (all manufactured by Nippon Kayaku) and the like can also be used.

Structural formula 1:

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Structural formula 2:

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Structural formula 3:

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Structural formula 4:

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Structural formula 5:

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Structural formula 6:

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Structural formula 7:

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Structural formula 8:

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Structural formula 9:

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Structural formula 10:

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Structural formula 11:

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Structural formula 12:

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Structural formula 13:

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Structural formula 14:

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Structural formula 15:

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Structural formula 16:

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Structural formula 17:

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Structural formula 18:

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(Thermoplastic norbornene-based resin composition) The thermoplastic norbornene-based resin composition of the present invention comprises a thermoplastic norbornene-based resin composition in an amount of 100 parts by weight of a near-infrared absorbing agent, usually 10 ^{-7 to} 100 parts by weight. , Preferably 10 ^-6
To 30 parts by weight, more preferably 10 ^-5 to 10 parts by weight, particularly preferably 10 ^-4 to 1 part by weight. If the addition amount is excessively large, the transparency of the resin, the glass transition temperature,
If the heat resistance is lowered, and if the heat resistance is excessively low, the effect of blending the near-infrared absorber cannot be obtained.

The method of addition is such that the near-infrared absorbing agent is sufficiently dispersed in the thermoplastic norbornene resin.
There is no particular limitation. For example, there are a method in which the resin temperature is kneaded in a molten state using a mixer, a twin-screw kneader, or the like, a method in which the resin is dissolved and dispersed in an appropriate solvent, and a solvent is removed by a coagulation method, a casting method, or a direct drying method.

(Molding) The method for molding the thermoplastic norbornene resin is not particularly limited. Depending on the purpose, injection molding, blow molding, injection blow molding, rotational molding, vacuum molding, extrusion molding, calendar molding, solution casting, and the like are possible.

(Molded Article) Examples of the molded article having near-infrared absorbing ability according to the present invention include optical character readers used in computers and facsimile machines, optical parts for information processing-related equipment such as laser printers; Films and films for agricultural plant cultivation and cultivation, infrared absorption / protection filters / films such as films for cooling / heating used for window glass and automobile glass; light-receiving sensors such as remote control devices using near infrared rays;

[0035]

The present invention will be described below in detail with reference to Reference Examples, Examples and Comparative Examples.

Example 1 A thermoplastic saturated norbornene resin (ZEO) was used in a twin screw extruder with a diameter of 35 mm (TEM-35B, manufactured by Toshiba Machine Co., Ltd.).
NEX280, manufactured by Nippon Zeon Co., Ltd., glass transition temperature of about 140 ° C., number average molecular weight of about 28,000) 100 parts by weight of a near infrared absorber SIR-128 (manufactured by Mitsui Toatsu Dye Co., Ltd., absorption wavelength range of about 700 to About 1000nm)
Add 0.02 parts by weight, knead at 220 ° C resin temperature,
Pelletized with a pelletizer.

The pellet was injection-molded at a resin temperature of 260 ° C. to form a 1 mm × 100 mm × 60 mm plate.

The wavelengths of this plate are 800 nm, 850 nm, 9
When the light transmittance at 00 nm was measured,
5.2%, 16.0% and 27.9%.

This plate was heated at 80 ° C. and 90% humidity for 5 days.
After leaving for 00 hours, the wavelength is 800 nm, 850 nm, 9
When the light transmittance at 00 nm was measured,
5.4%, 16.3% and 27.8%.

Example 2 SIR instead of SIR-128 as a near infrared absorber
-159 (Mitsui Toatsu Dye Co., Ltd., absorption wavelength region about 7
A plate was formed in the same manner as in Example 1 except that the thickness was in the range of 0.00 to 1000 nm), and the light transmittance was measured.

The wavelength of the plate before the high temperature and high humidity treatment is 800 nm, 8
The light transmittances at 50 nm and 900 nm are 5.
The light transmittances at wavelengths of 800 nm, 850 nm, and 900 nm of the plate after the high-temperature and high-humidity treatment were 5.3%, 14.0%, and 47.3%, respectively. there were.

Example 3 SIR instead of SIR-128 as a near infrared absorber
-114 (Mitsui Toatsu Dye Co., Ltd., absorption wavelength region about 6
A plate was formed in the same manner as in Example 1 except that the thickness was in the range of from about 0.00 to about 800 nm), and the light transmittance was measured.

The wavelength of the plate before the high temperature and high humidity treatment was 650 nm, 7
The light transmittances of 00 nm and 750 nm are 4
The light transmittances at wavelengths of 650 nm, 700 nm, and 750 nm of the plate after the 5.0%, 9.8%, 29.9%, and high temperature and high humidity treatments are 45.3%, 9.9%, and 29.1, respectively. %Met.

Example 4 SIR instead of SIR-128 as near-infrared absorber
A plate was formed in the same manner as in Example 1 except that -103 (manufactured by Mitsui Toatsu Dye Co., Ltd., having a wide absorption region from 600 nm or less to 1500 nm or more with a maximum around 930 nm) was used, and the light transmittance was measured. did.

The wavelength of the plate before high-temperature and high-humidity treatment is 800 nm, 9
The light transmittances at 00 nm and 1000 nm are 3
The light transmittance at a wavelength of 800 nm, 900 nm, and 1000 nm of the plate after the 3.4%, 28.9%, 23.9%, and high-temperature and high-humidity treatments is 33.6%, 29.1%, and 24.
4%.

Comparative Example 1 A plate was molded in the same manner as in Example 1 except that a thermoplastic saturated norbornene resin (ZEONEX 280) was molded without using a pellet to which a near-infrared absorbing agent was added, and the light transmittance was measured. .

Before the high-temperature and high-humidity treatment, the plate had a wavelength of 600 nm, 7
The light transmittances of 00 nm, 800 nm, and 900 nm are 91.0%, 91.2%, 91.2%, and 91.
1%, wavelength 600nm, 700n of plate after high temperature and high humidity treatment
The light transmittances of m, 800 nm, and 900 nm are 91.0%, 91.1%, 91.1%, and 91.0%, respectively.
Met.

Comparative Example 2 A polycarbonate resin (AD5503, manufactured by Teijin) was used in place of the thermoplastic norbornene resin, except that the resin temperature during kneading was changed to 230 ° C. and the resin temperature during injection molding was changed to 270 ° C. A plate was formed in the same manner as in Example 1, and the light transmittance was measured.

The wavelength of the plate before high-temperature and high-humidity treatment is 800 nm, 8
The light transmittance at 50 nm and 900 nm is 3
The light transmittances of the plates after the 4.8%, 15.2%, 27.1%, high-temperature, high-humidity treatment at wavelengths of 800 nm, 850 nm, and 900 nm are 46.7%, 25.2%, and 15.0, respectively.
%Met.

Comparative Example 3 Polymethyl methacrylate resin (Acrypet VH, manufactured by Mitsubishi Rayon) instead of thermoplastic norbornene resin
Is replaced with SIR128 as a near infrared absorbing agent
Example 1 except that the resin temperature during kneading was changed to 200 ° C. and the resin temperature during injection molding was changed to 230 ° C.
A plate was formed in the same manner as described above, and the light transmittance was measured.

The wavelength of the plate before high-temperature and high-humidity treatment is 800 nm, 8
The light transmittance at 50 nm and 900 nm is 3
The light transmittances at wavelengths of 600 nm, 700 nm, and 800 nm of the plate after 6.1%, 16.4%, 28.5%, and high-temperature and high-humidity treatment are 49.8%, 30.2%, and 15.3, respectively.
%Met.

[0052]

The molded article comprising the resin composition of the present invention
Has a stable infrared absorption ability.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-218558 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 65/00

Claims (2)

(57) [Claims] 1. A thermoplastic norbornene resin composition comprising a thermoplastic norbornene resin containing no polar group and a near infrared absorbing agent. 2. A molded article comprising the resin composition according to claim 1.