JP3088161B2 - Near-infrared absorbing styrene resin composition and molded article thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel styrenic resin composition which transmits visible light relatively well and has excellent near-infrared absorbing ability, and a near-infrared absorbing styrenic resin formed into a sheet or film. It relates to a molded article. The near-infrared absorbing material is a functional material that has been actively researched and developed recently, and is a photosensitive material using a semiconductor laser beam having a wavelength in the near-infrared region as a light source, an information recording material such as a recording material for an optical disc. And optical materials such as infrared cut filters and films, and heat ray absorbing glazing materials.

[0002]

2. Description of the Related Art Conventionally, as a near-infrared-absorbing light-transmitting material, as described in US Pat. No. 3,692,688, tungsten hexachloride (WCl ₆ ) and tin chloride (SnCl _2.
2H ₂ O) to methyl methacrylate syrup (monomer)
There is known a material excellent in near-infrared absorbing ability substantially free of haze, which is obtained by dissolving in water and polymerizing. In addition, other near-infrared absorbing materials developed so far include:
JP-B-60-42269 discloses a chromium-cobalt complex salt, JP-B-60-21294 discloses a thiol nickel complex, JP-A-61-1115958 discloses an anthraquinone derivative, and JP-A-61-218551 discloses
A novel squarylium compound having a maximum absorption wavelength in the range of 700 to 800 nm is disclosed.

[0003]

The conventional near-infrared absorbing material has a problem that the organic one is poor in durability and its initial performance deteriorates with changes in environmental conditions and time. On the other hand, although the complex type is durable, there are problems that the compound itself is strongly colored because it absorbs not only in the near-infrared region but also in the visible region, and the application itself is limited. Furthermore, in both systems, an absorption peak was observed at a specific wavelength, and there was almost no absorption ability at a wavelength deviated from the peak. If a recording medium using these materials as a light source, for example, a laser beam having a wavelength in the near infrared region, it is necessary to match the wavelength of the laser beam with the absorption peak of the material. But,
Since the wavelength of the laser beam and the absorption wavelength of the near-infrared absorbing material are limited, only a limited number of combinations of the wavelength of the laser beam and the wavelength at the absorption peak of the near-infrared absorbing material match. I had to become.

In addition, the above-mentioned prior art WCl ₆ and SnCl ₂ .2H ₂ O
Is dissolved in methyl methacrylate syrup, develops a deep blue color and has a property of absorbing near-infrared rays well, but has a problem of fading during long-term storage in a dark place. Such a gradual progress of photochromism and the like was a problem unfavorable in providing industrial products such as optical filters and heat ray absorbing glazing having a certain quality.

[0005]

According to the present invention, there is provided a semiconductor device comprising:
As a result of intensive studies on a near-infrared absorbing material which is uniformly absorbed in the entire near-infrared region, has less coloring, and has excellent durability, a copper compound and a thiourea-based derivative or (and) a thioamide-based derivative are obtained. The present inventors have found that an excellent near-infrared absorbing material of interest can be obtained by incorporating these into a styrene-based resin, and completed the present invention.

That is, according to the present invention, (B) the following general formula (I) (R-X) _n Cu (I) is used for 100 parts by weight of a styrene resin, wherein R is hydrogen, an alkyl group, cycloalkyl group, aryl group, monovalent group selected from the group consisting of aralkyl and heterocyclic residues (each group may have one or more substituents), X is -COO, -SO _{4 , -SO 3, -PO 4, -O} , n is 1
A copper compound represented by the formula:
0.05 to 5 parts by weight of at least one copper compound selected from the group consisting of sodium copper chlorophyllin and copper bisacetylacetonate; (C) the following general formula (II)

[0007]

Embedded image

(R ₁ , R ₂ and R ₃ each represent a monovalent group selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and a 5- or 6-membered heterocyclic residue. And each group may have one or more substituents, and R ₁ and
R ₂ or R ₂ and R ₃ may be linked to form a ring); and a thiourea derivative represented by the following general formula (III):

[0009]

Embedded image

(R _{4 and} R ₅ represent a monovalent group selected from the group consisting of hydrogen, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group and a 5- or 6-membered heterocyclic residue. represents, R ₅ is further also represent an alkoxy group, each group may have one or more substituents, and R ₄
R ₅ may be linked to form a ring). A near-infrared absorbing styrenic resin composition comprising 0.05 to 50 parts by weight of at least one thioamide derivative represented by the following formula: The present invention also relates to a near-infrared absorbing styrenic resin molded article obtained by molding a near-infrared absorbing styrenic resin composition having the above composition into a sheet or film.

The styrenic resin used in the present invention comprises at least one monomer selected from the group consisting of a styrenic monomer and another vinyl monomer copolymerizable with the styrenic monomer. And, if necessary, those obtained by the presence of a rubber-like substance. Among them, first, styrene-based monomers include styrene, α-methylstyrene, and a hydrogen atom of a benzene nucleus. It is a generic term for styrene derivatives substituted with a halogen atom or an alkyl group having 1 to 2 carbon atoms. Typical examples of such a styrene monomer include styrene, o-chlorostyrene, p-methylstyrene, 2,4-dimethylstyrene, t-butylstyrene, and the like.

[0012] Typical examples of the other copolymerizable vinyl monomers include acrylonitrile-based monomers such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-ethylhexylbutyl (meth) acrylate, or β-hydroxy (meth) acrylate (Meth) acrylic acid such as ethyl, and various ester acids thereof; or vinyl ketones including vinyl acetate, vinyl chloride, vinylidene chloride, vinylpyrrolidone, (meth) acrylamide, maleic anhydride, itaconic anhydride, or maleimide Or vinyl ethers.

Further, typical examples of the rubbery substance include polybutadiene rubber, styrene / butadiene / styrene block copolymer rubber, ethylene / propylene terpolymer rubber, butadiene / acrylonitrile copolymer rubber, butyl rubber, and acrylic rubber. Rubber, styrene / isobutylene / butadiene copolymer rubber, or isoprene /
There are rubbers obtained using conjugated 1,3-diene-based monomers such as isoprene or chloroprene, including acrylate-based copolymer rubbers, and these are used alone or in combination of two or more. Can be These styrene resins may be those produced by any polymerization method such as emulsification, bulk suspension or continuous bulk.

Further, the above-mentioned general formula (I) used in the present invention
Examples of the copper compound represented by are as follows, but the invention is not limited thereto. Copper stearate, copper panaminate, copper oleate, copper behenate, copper laurate, copper caprate, copper caproate,
Copper valerate, copper isobutyrate, copper butyrate, copper propionate, copper acetate, copper formate, copper hydroxide, copper benzoate, copper orthotoluate, copper metatoluate, copper paratoluate, copper p-tert-butylbenzoate, orthochlor Copper benzoate, copper dichlorobenzoate, copper trichlorobenzoate, copper p-bromobenzoate, copper p-iodobenzoate, copper o-benzoylbenzoate, copper p-nitrobenzoate, copper anthranilate, p
-Copper aminobenzoate, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper pimerate, copper suberate, copper azelate, copper sebacate, copper phthalate, monoester phthalate Copper, copper naphthenate, copper naphthalene carboxylate, copper tartrate, copper diphenylamine-2-carboxylate, copper 4-cyclohexylbutyrate, copper diethyldithiocarbamate, copper gluconate, copper diethoxy,
Copper i-propoxy, copper octylate, copper alkylbenzenesulfonate, copper p-toluenesulfonate, copper naphthalenesulfonate, copper naphthylaminesulfonate, copper n-dodecylbenzenesulfonate, copper dodecyl sulfate, 2,5-dimethylbenzenesulfone Copper acid, 2-carbomethoxy-5-
Copper methylbenzene sulfonate, α-naphthyl copper phosphate,
Copper di-2-ethylhexyl phosphate, copper isodecyl phosphate.

Examples of the thiourea derivative represented by the general formula (II) used in the present invention include the following, but are not limited thereto. 1-ethyl-3-phenylthiourea, 1,3-diphenylthiourea, 1,3-diethylthiourea, 1-ethyl-3-p-chlorophenylthiourea, 1-ethyl-3
-(2-hydroxyethyl) thiourea, 1- (2-thiazolyl) -3-phenylthiourea, 1,3-distearylthiourea, 1,3-divehenylthiourea, 1-ethylthiourea, 1-p-bromophenyl- 3-phenylthiourea, 1- (2-thiophenyl) -3-phenylthiourea, 1,3-bis (2-hydroxyethyl) thiourea, 1-p-aminophenyl-3-phenylthiourea, 1-p-nitrophenyl- 3-phenylthiourea, 1-p-hydroxyphenyl-3-phenylthiourea, 1,3-di-m-chlorophenylthiourea, ethylenethiourea, thiourea, 1-methyl-3-p-
Hydroxyphenylthiourea, 1-phenylthiourea, 1-m-nitrophenylthiourea, 1-p-nitrophenylthiourea, 1-p-aminophenylthiourea, 1,3-dimethylthiourea, 1,3-dicyclohexylthiourea, 1-phenyl -3-p-chlorophenylthiourea, 1-phenyl-3-p-methoxyphenylthiourea, 1,1-diphenylthiourea, 1,1-dibenzyl-3-phenethylthiourea, 1-phenyl-
3- (2-hydroxyethyl) thiourea.

Examples of the thioamide derivative represented by the general formula (III) used in the present invention include the following, but are not limited thereto. N-methylthiobenzamide, N-phenylthiobenzamide, N-ethylthioethylamide, N-ethylthio-p-chlorobenzamide, N-propylthiobenzamide, N-ethylthiostearylamide, N-1- (2
-Thiazolyl) thiobenzamide, N-stearylthiostearylamide, N-behenylthiobehenylamide,
Thioacetamide, N-phenyl-thio-p-bromobenzamide, N-1- (2-thiophenyl) thiobenzamide, N-behenylthioacetamide, Np-aminophenylthiobenzamide, Np-nitrophenyl Thiobenzamide, Np-hydroxyphenylthiobenzamide, Nm-chlorophenylthiobenzamide, thionicotinamide, thioacetanilide, O-
Ethyl-N-phenyl (thiocarbamate), thiobenzamide, thio-m-nitrobenzamide, thio-p-
Nitrobenzanid, thio-p-aminobenzamide,
N-methylthioacetamide, N-cyclohexylbenzamide, N-chlorophenylthiobenzamide, N-
p-methoxyphenylthiobenzamide, N-stearylthiobenzamide.

The amounts of the copper compound and the thiourea derivative and / or thioamide derivative used in the present invention can be changed by setting the transmittance in the visible and near-infrared regions. The copper compound is added in an amount of 0.05 to 5 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the styrene resin.
~ 2.5 parts by weight. The addition amount of the thiourea derivative is 0.05 to 50 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the styrene resin. The amount of the thioamide derivative is 0.05 to 50 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the styrene resin.
Further, even with the same content, when the resin material obtained in the present invention is, for example, a plate, the transmittance varies depending on the thickness of the resin material. You need to decide.

In the present invention, when the addition amounts of the copper compound and the thiourea derivative or (and) thioamide derivative are each less than 0.05 part by weight with respect to 100 parts by weight of the styrene resin, the improvement of the near-infrared absorbing ability is sufficient. On the other hand, when the addition amount of the copper compound exceeds 5 parts by weight with respect to 100 parts by weight of the styrene-based resin, no improvement in near-infrared absorption ability is observed,
If the amount of the thiourea derivative or (and) thioamide derivative exceeds 50 parts by weight with respect to 100 parts by weight of the styrene-based resin, no improvement in near-infrared absorbing power is observed and haze occurs in the material. There is fear. In addition to the above components,
If necessary, commonly used additives such as flame retardants, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, coloring agents, inorganic fillers, reinforcing materials such as glass fibers, etc. are compounded. You can also.

The method of mixing the styrene resin, thiourea derivative, thioamide derivative, and copper compound in the present invention does not require any special means or mixing order, and a general-purpose mixing apparatus such as a hot roll, a Banbury mixer or an extruder Can be manufactured more easily. The film or sheet may be manufactured by a usual manufacturing method. It can be manufactured by a T-die method using an extruder, an inflation molding method, a calendar molding method, or a compression molding method. The thickness of the film or sheet is not particularly limited, but is preferably in the range of 0.01 to 10 mm. When the strength of the sheet is further increased or a pattern is to be formed, the sheet may be formed by incorporating a glass fiber net or a stainless steel wire mesh in which glass filament yarns are woven into a lattice of about 5 mm square, for example.

[0020]

As described above, the copper compound of the general formula (I) or chlorophyll copper, sodium copper chlorophyllin, copper bisacetylacetonate and the thiourea derivative of the general formula (II) or the thioamide derivative of the general formula (III) are used. By heating and kneading the contained mixture with the styrene resin by the above mixing method, near infrared rays can be almost uniformly absorbed over the entire range of 800 to 2000 nm. Although the reason is not clear, as is clear from the following Examples and Comparative Examples,
Even if the thiourea derivative, thioamide derivative or copper compound is independently kneaded with the styrene-based resin, it is 800 to 2000
The near-infrared light is not absorbed almost uniformly and intensely over the entire near-infrared region of nm, and it is the same even if styrene-based resin, thiourea derivative, thioamide derivative and copper compound are simply mixed. Then, by heating and kneading a mixture containing a thiourea derivative or a thioamide derivative and a copper compound with a styrene-based resin by the above-described mixing method, some reaction occurs between the thiourea derivative or the thioamide derivative and the copper compound. , Complex
Is presumed to have occurred.

[0021]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition, all the addition rates in an Example show a weight part.

The transmission spectrum of the obtained resin material was measured with a spectrophotometer (type 323, manufactured by Hitachi, Ltd.). Judgment of near infrared absorption is 900, 1000, 1100,
◎, the average of the absorption value of each wavelength of 1500 nm is 80% or more.
○ indicates 60% or more, Δ indicates 30% or more, and × indicates 30% or less.

The stability to near-infrared absorptivity of heat, humidity and light was measured by the following method.

Heat resistance / moisture resistance: near infrared absorbing sheet
After leaving for 480 hours in an oven at 80 ° C and 100% RH,
Near-infrared absorption was measured again with a spectrophotometer (1000 nm). The storage stability was evaluated based on the result calculated by the following equation.

[0025]

(Equation 1)

Lightfastness: After irradiating the near-infrared absorbing sheet with a UV (ultraviolet) tester (super-accelerated lightfastness tester manufactured by Dainippon Plastics Co., Ltd.) for 200 hours, the near-infrared absorbing property was measured again by a spectrophotometer ( (1000 nm). The storage stability was evaluated based on the result calculated by the following equation.

[0027]

(Equation 2)

The thermal stability was measured by using an injection molding machine at a set temperature of 230 ° C. after a residence time of 20 minutes, and the color change of the obtained sample was measured with a color difference meter manufactured by Nippon Denshoku Co., Ltd. Then, the color difference (ΔE) was obtained by the Lab method and determined as follows. ：: Excellent 良好: Good △: No burn (large yellow change) ×: Burns Examples 1 to 23 Combination of 2 parts by weight of thiourea compound and 0.2 part by weight of copper compound shown in Tables 1 and 2 with polystyrene resin The mixture was added to 100 parts by weight, mixed with a tumbler mixer for 20 minutes, kneaded at 220 ° C. with a 40 mmφ extrusion molding machine, and formed into pellets. Then, the pellets are dried, and the thickness of the pellet is adjusted to 3 using an injection molding machine.
A green transparent resin plate having no haze of mm was produced. The transmission spectra of these obtained plates were measured. Table 5
The results are shown in Table 1, but the absorption in the near infrared region was excellent.

Examples 24 to 33 The thiourea compound and the copper compound were added to 100 parts by weight of a polystyrene resin in the combinations and amounts shown in Table 2 and mixed for 20 minutes with a tumbler mixer.
After kneading at 220 ° C., the mixture was formed into pellets. Next, the pellets were dried, and a 3 mm-thick, haze-free green transparent resin plate was prepared using an injection molding machine. The transmission spectra of these obtained plates were measured. Table 6 shows the results.
Excellent absorption in the near infrared region.

Examples 34 to 37 2 parts by weight of the thioamide compound and 0.2 parts by weight of the copper compound in the combination shown in Table 2 were added to 100 parts by weight of a polystyrene resin, mixed for 20 minutes with a tumbler mixer, and extruded with a 40 mmφ extruder. After kneading at 220 ° C., the mixture was formed into pellets. Next, the pellets were dried, and a 3 mm-thick, haze-free green transparent resin plate was prepared using an injection molding machine. The transmission spectra of these obtained plates were measured. Table 6 shows the results. The results were excellent in near-infrared absorption.

[0031]

[Table 1]

[0032]

[Table 2]

Examples 38 to 41 2 parts by weight of the thiourea compound and 0.2 parts by weight of the copper compound shown in Table 3 were added to 100 parts by weight of a styrene resin.
The mixture was mixed by a tumbler mixer for 20 minutes, kneaded at 220 ° C. by a 40 mmφ extruder, and formed into pellets. Then, the pellets were dried, and a 3 mm-thick, haze-free green transparent resin plate was prepared using an injection molding machine. The transmission spectra of these obtained plates were measured. Table 6 shows the results. The results were excellent in near-infrared absorption.

[0034]

[Table 3]

Example 42 The combination of Example 1 was mixed with a tumbler mixer for 20 minutes, and formed into a sheet having a thickness of 1 mm by a T-die molding method at 220 ° C. using a 40 mmφ extruder. The temperature of the cooling roll is
95 ° C. The heat shielding effect of the obtained near-infrared absorbing sheet was measured using the apparatus shown in FIG. 1 is a 60 W incandescent lamp, 2 is a measurement sample, and 3 is a precision thermometer. The result was as shown in FIG. The heat-shielding effect of the near-infrared absorbing sheet is indicated by A in the figure, and the heat-shielding effect of the ordinary polystyrene resin containing no near-infrared absorbing agent shown in FIG.
It can be seen from the comparison with that that the heat shielding ability in the near infrared region is excellent. The transmission spectrum of the obtained transparent resin sheet is shown by A in FIG. 3, and as can be seen from a comparison with the transmission spectrum B of a normal polystyrene resin sheet containing no near-infrared absorbing agent shown in FIG. The resin sheet transmits light in the visible range relatively well, but has excellent near-infrared absorption capacity not found in ordinary polystyrene resin sheets.

Comparative Examples 1 to 9 Each of the thiourea compound, the thioamide compound and the copper compound shown in Table 4 was independently added to 100 parts by weight of a polystyrene resin and mixed with a tumbler mixer for 20 minutes.
After kneading at 220 ° C. by an extruder, the mixture was formed into pellets.
Next, the pellets were dried, and a 3 mm-thick, haze-free green transparent resin plate was prepared using an injection molding machine. The transmission spectra of these obtained plates were measured, and Table 6 was obtained.
The results are shown in Table 2, but all of them had a near infrared absorption of 30% or less.

[0037]

[Table 4]

[0038]

[Table 5]

[0039]

[Table 6]

According to Tables 5 and 6, it is clear that a styrene resin sheet obtained by kneading a thiourea compound or a thioamide compound and a copper compound becomes a strong near-infrared absorbing sheet. The near-infrared absorptivity hardly decreases due to heating, humidification, or exposure, indicating that the near-infrared absorptivity is high with respect to changes in environmental conditions of handling and storage.
The styrene resin sheet kneaded with a thiourea compound, a thioamide compound or a copper compound alone did not substantially exhibit near-infrared absorption.

[0041]

The resin material formed by heating and kneading the near-infrared absorbing styrenic resin composition of the present invention and forming it into a sheet or film has no instability such as fading and fades when left in a dark place for a long period of time. It shows no near-infrared absorptivity, and is industrially useful as an optical filter, a heat ray absorbing glazing material and the like. In addition, the obtained near-infrared absorbing sheet is 800 to 2000
It has strong absorption over the entire near infrared region of nm. By utilizing these properties, it can be used as an optical material such as a near infrared cut filter, a recording material, a heat ray shielding material, a heat storage material, a near infrared detection sensor, and the like. Since the composition of the present invention contains a metal and has little coloring, a molded article such as a sheet or film containing the metal has an excellent appearance.

[Brief description of the drawings]

FIG. 1 is a schematic view of an apparatus for measuring a heat shielding effect of a near-infrared absorbing sheet.

FIG. 2 is a diagram showing a measurement result of a heat shielding effect.

FIG. 3 is a diagram showing a transmission spectrum.

Claims (2)

(57) [Claims] (A) 100 parts by weight of a styrene resin, (B) a compound represented by the following general formula (I): (R-X) _n Cu (I) wherein R is hydrogen, an alkyl group, a cycloalkyl group , aryl group, monovalent groups the aralkyl group and the heterocyclic residue (each group is may also have one or more substituents) selected from the group consisting of, X is -COO, -SO _4, -SO _3, -PO _4, -O, n is 1
A copper compound represented by the formula:
0.05 to 5 parts by weight of at least one copper compound selected from the group consisting of sodium copper chlorophyllin and copper bisacetylacetonate; (C) the following general formula (II): (R ₁ , R ₂ , and R ₃ each represent a monovalent group selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a 5- or 6-membered heterocyclic residue; May have one or more substituents, and R ₁ and R ₂ or R ₂
R ₃ may be linked to form a ring); and a thiourea derivative represented by the following general formula (III): (R _{4 and} R ₅ are hydrogen, an alkyl group, an alkenyl group,
R ₅ represents a monovalent group selected from the group consisting of a cycloalkyl group, an aryl group, an aralkyl group and a 5- or 6-membered heterocyclic residue; R ₅ further represents an alkoxy group; _May have a substituent, and R ₄ and R ₅ may be linked to each other to form a ring) at least one selected from thioamide derivatives represented by the formula: A characteristic near-infrared absorbing styrene resin composition. 2. A near-infrared absorbing styrenic resin formed article formed by molding the near-infrared absorbing styrenic resin composition according to claim 1 into a sheet or film.