JPH06256564A - Resin composition and molding composed of the same - Google Patents

Abstract

PURPOSE:To obtain the subject composition, capable of transmitting only rays of light within a prescribed wavelength region and useful as a filter, etc., having optical band pass filter function by blending a transparent optical resin with a near infrared ray absorber and an organic pigment. CONSTITUTION:This resin composition is obtained by blending (A) 100 pts.wt. transparent optical resin such as an acrylic or a polycarbonate resin with (B) preferably 10<-4> to 1 pt.wt. near infrared ray absorber such as a cyanine-based near infrared ray absorber, e.g. a compound of formula I or II and (C) an organic pigment such as a diarylide-based pigment, e.g. Pigment Red 38. A dispersing agent is preferably used so as to uniformly disperse the organic pigment. Furthermore, the composition capable of transmitting rays of light, e.g. at 550-600nm wavelength is obtained by combining the component (B) capable of absorbing rays of light at >=600nm wavelength with the component (C) capable of absorbing rays of light at <=550nm wavelength.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which transmits only light rays of a certain wavelength range and a filter comprising the same.

[0002]

2. Description of the Related Art In recent years, computers, facsimiles,
In the field of optical communication and the like, light rays in the visible to near-infrared region having a specific wavelength of 600 nm or more are used.
When receiving light rays of these specific wavelengths, an optical bandpass filter that transmits light rays only in the vicinity of the used wavelength is used in order to improve the S / N ratio.

Conventionally, such an optical bandpass filter has been manufactured by laminating 10 or more layers of a dielectric substance having a predetermined thickness on a glass substrate by a vacuum deposition method or a sputtering method. However, such a manufacturing method has a problem that the process is complicated and the efficiency is low.

Further, for the purpose of weight reduction and mass production of optical parts, the switch from glass to transparent optical resin is in progress, but generally, there is a large difference in the coefficient of thermal expansion between the optical resin and the dielectric substance. Therefore, when an optical bandpass filter manufactured according to the conventional method is used in an environment with a temperature change except that an optical resin substrate is used instead of a glass substrate, microcracks are generated, or a multilayer film peels from the substrate. There was a problem that it was easy.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have blended a transparent optical resin with a near-infrared absorbing agent and an organic pigment so that the near-infrared absorbing agent absorbs a long wavelength region and an organic pigment in a short wavelength region. It was found that an optical bandpass filter or the like which can be easily used even in an environment where the temperature changes can be obtained by obtaining a resin composition which can be absorbed by the above, and completed the present invention.

[0006]

Thus, according to the present invention, there is provided a resin composition comprising a transparent optical resin and a near-infrared absorber and an organic pigment, and a molded article comprising the resin composition.

(Transparent Optical Resin) The transparent optical resin used in the present invention is not particularly limited and may be a known one.
Examples thereof include acrylic resin, polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, styrene / methyl methacrylate copolymer resin, styrene / butadiene copolymer resin, and thermoplastic norbornene resin.

Various additives may be added to the optical resin as long as the object of the present invention is not impaired. For example, in the case of thermoplastic norbornene-based resin, phenol-based or phosphorus-based antioxidants; phenol-based thermal deterioration inhibitors; benzophenone-based UV stabilizers; amine-based antistatic agents; aliphatic alcohols Lubricants such as esters, partial esters of polyhydric alcohols and partial ethers; and other various additives may be added. Further, other resins, rubbers, fillers and the like can be mixed and used as the optical resin within the range not impairing the object of the present invention.

(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 which is generally blended with a transparent optical resin and used. On the other hand, with respect to a solution in which 0.1 part by weight of the compound is dissolved, the light transmittance of the good solvent as a control is 50% or less, further 30% or less in a part of the near-infrared wavelength region of 600 to 2500 nm. 600
A compound having a light transmittance of 50% or more at a wavelength of less than nm is preferable. Examples of such near-infrared absorbers include cyanine-based near-infrared absorbers such as compounds represented by Structural Formula 1 and compounds represented by Structural Formula 2; pyrylium-based infrared rays such as compounds represented by Structural Formula 3 Absorber; squarylium-based near-infrared absorber such as a compound represented by Structural Formula 4; croconium-based infrared absorber such as a compound represented by Structural Formula 5; azurenium-based near-infrared ray such as a compound represented by Structural Formula 6 Absorbent; compound represented by Structural Formula 7, Structural Formula 8
A phthalocyanine-based near-infrared absorber such as a compound represented by: a dithiol metal complex-based near-infrared absorber such as a compound represented by Structural Formula 9 or a structural formula 10;
A naphthoquinone-based near-infrared absorber such as a compound represented by Structural Formula 11 or a compound represented by Structural Formula 12; Structural Formula 13
An anthraquinone-based near-infrared absorber such as a compound represented by, or a compound represented by Structural Formula 14; an indophenol-based near-infrared absorber such as a compound represented by Structural Formula 15, a compound represented by Structural Formula 16; Examples of the compound represented by Structural Formula 17, azide-based near-infrared absorber such as the compound represented by Structural Formula 18; In addition, commercially available near-infrared absorbers, SIR-103, SIR-114, SIR-12
8, SIR-130, SIR-132, SIR-15
2, SIR-159, SIR-162 (above, manufactured by Mitsui Toatsu Dye), Kayasorb IR-750, Kaya
sorb IRG-002, Kayasor IRG-
003, IR-820B, Kayasorb IRG-
022, Kayasorb IRG-023, Kaya
sorb CY-2, Kayasorb cCY-4,
Kayasorb CY-9 (above, manufactured by Nippon Kayaku) or the like can also be used.

Structural formula 1:

[Chemical 1]

Structural formula 2:

[Chemical 2]

Structural formula 3:

[Chemical 3]

Structural formula 4:

[Chemical 4]

Structural formula 5:

[Chemical 5]

Structural formula 6:

[Chemical 6]

Structural formula 7:

[Chemical 7]

Structural formula 8:

[Chemical 8]

Structural formula 9:

[Chemical 9]

Structural formula 10:

[Chemical 10]

Structural formula 11:

[Chemical 11]

Structural formula 12:

[Chemical 12]

Structural formula 13:

[Chemical 13]

Structural formula 14:

[Chemical 14]

Structural formula 15:

[Chemical 15]

Structural formula 16:

[Chemical 16]

Structural formula 17:

[Chemical 17]

Structural formula 18:

[Chemical 18]

(Organic Pigment) The organic pigment used in the present invention is not particularly limited as long as it is an organic pigment which is generally blended with a transparent optical resin. For solutions in which parts by weight are dissolved, 3
The light transmittance of the good solvent as a control is 50% or less, further 30% in a part of the visible light wavelength region of 00 to 660 nm.
Below, the light transmittance for wavelengths longer than 660 nm is 50.
% Or more of the compound is preferable, and a compound having a small absorption at a target wavelength is selected. Pigment Red 38 and other dialide pigments; Pigment Red 4
8: 2, Pigment Red 53, Pigment Red 5
Azo lake pigments such as 7: 1; Pigment Red 14
4, Pigment Red 166, Pigment Red 22
0, Pigment Red 221, Pigment Red 248
Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208 and other benzimidazolone pigments; Pigment Red 122 and other quinacridone pigments; Pigment Red 149, Pigment Red 178, etc. Pigment Red 179 and other perylene pigments; Pigment Red 177 and other anthraquinone pigments.

(Resin Composition) The resin composition of the present invention comprises a transparent optical resin and a near infrared absorber and an organic pigment. Only the specific wavelength band of interest has high transmittance, so that light of other wavelengths is not substantially transmitted, a near-infrared absorber that absorbs light with a wavelength longer than the specific wavelength range and a wavelength of shorter wavelength than the specific wavelength range. A combination of types and amounts of organic pigments that absorb substances is selected and blended. For example, the width of the transmitted wavelength is 5
When it is 0 nm, the resin composition of the present invention may have a wavelength of 550 nm to 600 depending on the combination of the near infrared absorber and the organic pigment.
660 to 710 from the one that transmits the light of the wavelength of nm
Even those that transmit light with a wavelength of nm are obtained. 55
In order to transmit 0 nm to 600 nm, a near-infrared absorbing agent that absorbs 600 nm or more and an organic pigment that absorbs 550 nm or less may be used in combination.

Depending on the near infrared absorber and the organic pigment used,
Although the amount of compounding varies, usually 100 parts by weight of optical resin is added.
In contrast, near infrared absorber 10^-7~ 100 parts by weight, preferably
Is 10^-6-30 parts by weight, more preferably 10 parts^-Five~ 10 layers
Parts by weight, particularly preferably 10^-Four ~ 1 part by weight, 10 organic pigments
^-Four-20 parts by weight, preferably 5 x 10^-3-10 parts by weight,
More preferably 10^-3To 5 parts by weight, particularly preferably 10
^-2~ 1 part by weight is compounded. If the amount added is too large,
The transparency, glass transition temperature, and heat resistance of the resin will decrease,
If the amount is too small, add a near infrared absorber or organic pigment.
No effect.

Further, it is preferable to use a dispersant so that the organic pigment can be uniformly dispersed. When a dispersant is blended, 1 to 10000 parts by weight, preferably 10 to 1000 parts by weight, more preferably 20 to 200 parts by weight, and particularly preferably 30 to 150 parts by weight are added to 100 parts by weight of the organic pigment. However, the amount of the dispersant in the resin composition is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less. If the blending amount is excessively large, the strength after molding will be insufficient, and the light transmittance in all regions of visible light and near-infrared will be low, and light of the target wavelength will not be transmitted. If the amount is excessively small, it becomes difficult to uniformly disperse the organic pigment, and optical unevenness may occur in the molded product. As dispersants, stearates such as calcium stearate and sodium stearate; polyoxyethylene lauryl ether,
Examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether; alkyl naltalene sulfonates such as sodium alkyl naltalene sulfonate;

The compounding method is not particularly limited as long as the near infrared absorber and the organic pigment are sufficiently dispersed in the thermoplastic norbornene resin. For example, a method of kneading the resin temperature in a molten state with a ribbon blender, a Henschel mixer, a twin-screw kneader, or the like, a method of dissolving and dispersing the resin in an appropriate solvent to disperse the solvent by a coagulation method, a casting method, or a direct drying method. and so on.

(Molding) The method for molding the resin composition of the present invention is not particularly limited. Depending on the purpose, injection molding method, blow molding method, injection blow molding method, rotational molding method,
A vacuum molding method, an extrusion molding method, a calender molding method, a solution casting method and the like are possible.

(Molded Product) A molded product made of the resin composition of the present invention is not particularly limited, and examples thereof include optical parts such as lenses, prisms and filters.

[0035]

The present invention will be described in detail below with reference to examples. The absorption region refers to a range in which a solution of 0.1 part by weight of the compound in 100 parts by weight of a good solvent has a light transmittance of 50% or less with the good solvent as a control.

Example 1 Thermoplastic Norbornene Resin (ZEON, ZEON
EX 280, glass transition temperature about 140 ° C, number average molecular weight about 28,000) 100 parts by weight of near-infrared absorber SI
R-128 (Mitsui Toatsu Dye Co., Ltd., absorption wavelength range about 700 to about 1000 nm) 0.02 parts by weight, Pigment Red 149 (Mitsui Toatsu Dye, PS Brillian)
t Red HEY, absorption wavelength region about 400 to about 590
nm) and 0.05 parts by weight of calcium stearate as a dispersant, and using a twin-screw extrusion kneader having a diameter of 35 mm (TEM-35B, manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 220 ° C. It was kneaded and pelletized with a pelletizer.

Using this pellet, a resin temperature of 280
A sheet of 20 × 20 × 1 mm was formed by injection molding at a temperature of 90 ° C., a mold temperature of 90 ° C., and an injection pressure of 600 kg / cm ² to obtain a sheet having an optical bandpass function. The light transmittance of this sheet was measured and found to be 5% at a wavelength of 500 nm and 60%.
30% at 0 nm, 75% at 650 nm, 7 at 700 nm
7%, 50% at 750 nm, 30% at 800 nm, 90
It was 30% at 0 nm.

Example 2 Polycarbonate resin (Taflon IR manufactured by Idemitsu Petrochemical Co., Ltd.
-1700) 100 parts by weight of near-infrared absorber SIR-1
30 (manufactured by Mitsui Toatsu Dyestuff Co., Ltd., absorption wavelength region: about 800)
~ About 1000 nm) 0.02 parts by weight, Pigment Red 178 (manufactured by BASF Japan, Paliogen Re
d K3911HD, absorption wavelength range about 400 to about 600
nm) and 0.05 parts by weight of calcium stearate as a dispersant, and using a twin-screw extrusion kneader having a diameter of 35 mm (TEM-35B, manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 220 ° C. It was kneaded and pelletized with a pelletizer.

Using this pellet, a sheet of 20 × 20 × 1 mm was formed by injection molding in the same manner as in Example 1, and the light transmittance was measured. It was 10% at a wavelength of 500 nm and 60%.
50% at 0 nm, 80% at 650 nm, 8 at 700 nm
1%, 55% at 750 nm, 35% at 800 nm, 90
It was 33% at 0 nm.

Example 3 Acrylic resin (Acrypet VH manufactured by Mitsubishi Rayon) 1
Near infrared absorber Kayasob IRG-
002 (manufactured by Nippon Kayaku Co., Ltd., absorption wavelength range of about 800 to
0.02 parts by weight, Pigment Red 1
77 (manufactured by Nippon Kayaku, Kayaset RED 130,
Absorption wavelength region about 400 to about 600 nm) 0.08 parts by weight, and calcium stearate 0.0 as a dispersant.
2 parts by weight are compounded, and a twin-screw extruder kneader with a diameter of 35 mm (T
EM-35B, manufactured by Toshiba Machine Co., Ltd.)
The mixture was kneaded at 0 ° C. and pelletized with a pelletizer.

The pellets were injection-molded under the same conditions as in Example 1 to obtain a diameter of 20 mm, R1 = 50 mm and R2.
= ∞, a spherical lens was molded, and the light transmittance was measured to be 3% at a wavelength of 500 nm, 20% at 600 nm, and 65%.
70% at 0 nm, 76% at 700 nm, 4 at 750 nm
It was 8%, 28% at 800 nm, and 36% at 900 nm.

[0042]

EFFECTS OF THE INVENTION From the resin composition of the present invention, a resin-based molded product having an optical bandpass filter function can be easily obtained, and the molded product can be used without losing its function even in an environment with temperature change. it can.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Izu Natsume 1-2-1, Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Inside Zeon Corporation R & D Center

Claims (3)

[Claims] 1. A resin composition comprising a transparent optical resin, a near infrared absorber and an organic pigment. 2. A molded article comprising the resin composition according to claim 1. 3. The molded product according to claim 2, wherein the molded product is a filter.