JPH06312487A - Near infrared absorption methacrylate resin laminate and molded form thereof - Google Patents

Abstract

PURPOSE:To obtain a resin laminate which has excellent near infrared absorption capacity and in which instability such as fading, etc., is eliminated by integrally laminating a methacrylate resin film on a methacrylate resin sheet containing a specific ratio of cupric sulfide to methacrylate resin. CONSTITUTION:A methacrylate resin film is integrally laminated on a methacrylate resin sheet containing 0.01-5 wt.pts. of cupric sulfide to 100 pts.wt. of methacrylate resin thereby to form a methacrylate resin laminate having excellent near infrared absorption capacity. Thus, instability such as fading, etc., is eliminated in the laminate and a wavy platelike molded form due to it, and photochromism in which fading occurs when it is left to stand for a long period in a dark place is obviated. Accordingly, the laminate can be applied to an optical filter, an outdoor terrace, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel methacrylic resin laminate having relatively good transmission of visible light and excellent near-infrared absorbing ability and weather resistance formed by corrugated plate or irregular cross-sectional shape. It is an excellent near-infrared absorbing methacrylic resin molding.

[0002]

2. Description of the Related Art Conventionally, as a near-infrared absorbing light-transmitting material, as shown in US Pat. No. 3,692,688, tungsten hexachloride (WCl ₆ ) and tin chloride (SnCl ₂ .2H ₂ O) are used. There is known a material having a substantially haze-free and excellent near-infrared absorbing ability, which is obtained by dissolving it in methyl methacrylate syrup (monomer) and polymerizing it.

Further, in addition to these, as near-infrared absorbing materials which have been developed so far, Japanese Patent Publication No. 60-42269 discloses chromium and cobalt complex salts, Japanese Patent Publication No. 60-21294 discloses thiol-nickel complex, and Japanese Patent Publication No. -115958 discloses an anthraquinone derivative, and JP-A-61-218551 discloses a novel squarylium compound having a maximum absorption wavelength in the region of 700 to 800 nm.

[0004]

Regardless of the outdoor or indoor use, not only flat plates but also corrugated or irregular cross-sectional shapes are often used as translucent plates.
It is expected that the above materials will be applied to such corrugated sheets and those having irregular cross-sectional shapes.

[0005] Conventional near infrared absorbing materials have a problem that organic materials have poor durability and their initial performance deteriorates with changes in environmental conditions and the passage of time.
Although the complex type has durability, it absorbs not only in the near-infrared region but also in the visible region, and many of the compounds themselves are strongly colored, which limits their use. Further, in both systems, an absorption peak was observed at a specific wavelength, and there was almost no absorption ability at a wavelength deviating from the peak. Utilizing these materials,
Considering, for example, a recording body using a laser beam having a wavelength in the near infrared region as a light source, it is necessary to match the absorption peak of the material with the wavelength of the laser. However, since only the laser wavelength and the absorption wavelength of the near-infrared absorbing material can be obtained, the combination of the laser wavelength and the absorption peak of the near-infrared absorbing material must be very limited. There wasn't.

Further, the above-mentioned prior art WCl ₆ and SnCl ₂ .2H ₂ O
A composition obtained by dissolving the above-mentioned in methyl methacrylate syrup develops a deep blue color and has a property of absorbing near-infrared rays well, but it has a problem of fading during long-term storage in a dark place. Such slowly progressing photochromism has been an unfavorable problem in providing industrial products such as optical filters and heat ray absorbing glazings having a certain quality.

[0007]

[Means for Solving the Problems]
As a result of extensive studies on a near-infrared absorbing material that is uniformly absorbed in the entire near-infrared region of 00 nm, has little coloring, and is excellent in weather resistance and durability, a copper compound or a copper compound and a thiourea derivative The present invention has been completed based on the finding that it can be obtained by incorporating a methacrylic resin and / or a thioamide derivative into a methacrylic resin and laminating these.

That is, in the present invention, 0.01 to 5 parts by weight of cupric sulfide or 0.01 to 5 parts by weight of cupric sulfide and 0.001 to 1 part by weight of thiourea derivative and / or thioamide derivative are added to 100 parts by weight of methacrylic resin. The present invention relates to a methacrylic resin laminate excellent in near-infrared absorbing ability, which is obtained by laminating and integrating a methacrylic resin film on a methacrylic resin sheet containing the methacrylic resin film.

Further, the present invention relates to a near-infrared absorbing methacrylic resin laminate molded product obtained by molding the above-mentioned methacrylic resin laminate excellent in near-infrared absorbing ability into a corrugated plate shape or an irregular cross-sectional shape.

The methacrylic resin in the present invention refers to a polymer or copolymer containing various esters of methacrylic acid as a main component of monomers, and specifically, methyl methacrylate, ethyl methacrylate, methacrylic acid. Homopolymers of various methacrylic acid esters such as butyl, and copolymers of these methacrylic acid esters with various acrylic acid esters, acrylic acid, styrene, α-methylstyrene and the like. As a method for producing these resins, known polymerization methods such as suspension polymerization, emulsion polymerization and solution polymerization can be used. Further, a syrup containing a monomer or a monomer and a partial polymer, which are raw materials for polymerizing these polymers, can also be used.

The cupric sulfide used in the present invention may be in the form of powder produced by a conventional method, and its average particle size is
It is preferably 12 μm or less, more preferably 10 μm or less. Further, it is preferable that substantially no particles of 20 μm or more are present. If the average particle diameter exceeds the above range, not only the appearance of the obtained molded product is deteriorated and parallel light transmittance due to surface irregularities is deteriorated, but also the physical properties of the molded product and the near infrared absorptivity are deteriorated.

Examples of the thiourea derivative represented by the following general formula (I) used in the present invention include the following.

[0013]

[Chemical 3]

(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. Each group may have one or more substituents, and R ₁ and
R ₂ or R ₂ and R ₃ may combine to form a ring), for example, 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-
Distearyl thiourea, 1,3-dibehenyl thiourea, 1-ethyl thiourea, 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 and the like can be mentioned, but the present invention is not limited thereto.

The following can be exemplified as the thioamide derivative represented by the following general formula (II) used in the present invention.

[0016]

[Chemical 4]

(R ₄ and R ₅ are 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, Or R ₅ represents an alkoxy group, each group may have one or more substituents, and R ₄ and R ₅ may combine to form a ring) 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, thionicotinic acid amide, thioacetanilide, o-
Ethyl-N-phenyl (thiocarbamate), thiobenzamide, thio-m-nitrobenzamide, thio-p-
Nitrobenzamide, thio-p-aminobenzamide,
N-methylthioacetamide, N-cyclohexylbenzamide, N-chlorophenylthiobenzamide, N-
Examples thereof include p-methoxyphenylthiobenzamide, N-stearylthiobenzamide and the like, but are not limited thereto.

The amount of cupric sulfide, thiourea derivative and thioamide derivative used in the present invention can be varied depending on the setting of the transmittance in the visible and near infrared regions. The amount of cupric sulfide added is 0.01 to 5 parts by weight, preferably 0.02 to 3 parts by weight, based on 100 parts by weight of the methacrylic resin sheet.

When the thiourea derivative and the thioamide derivative are added, the addition amount is 0.001 to 1 part by weight, preferably 0.002 to 0.5 part by weight, based on 100 parts by weight of the methacrylic resin sheet.

Further, even if the content is the same, the transmittance changes depending on the sheet thickness, so that the content can be finally determined so that the transmittance at the set sheet thickness can be obtained.

In the present invention, a methacrylic resin sheet 1
When the amount of cupric sulfide added is less than 0.01 parts by weight with respect to 00 parts by weight, the near-infrared absorbing ability is not sufficiently improved.

On the other hand, when the amount of cupric sulfide added is 5 parts by weight, or the amount of thiourea derivative or thioamide derivative added is more than 1 part by weight per 100 parts by weight of the methacrylic resin sheet, near infrared absorption is observed. No improvement in Noh is seen,
Haze may occur in the material.

In addition to the above components, in order to improve the dispersion of cupric sulfide, if necessary, for example, sorbitan fatty acid ester such as sorbitan monostearate and glycerin fatty acid ester such as glycerin monostearate. It is also effective to use the dispersant of the present invention added to the composition of the present invention, and suitable additives such as flame retardants, heat stabilizers, antioxidants, light stabilizers, UV absorbers,
Lubricants, colorants, inorganic fillers, reinforcing materials such as glass fibers and the like can also be added.

The methacrylic resin, cupric sulfide or cupric sulfide and thiourea derivative and / or
Alternatively, as a method for mixing the thioamide derivative, a conventional mixing device, for example, without requiring any special means or order,
It can be easily manufactured by a hot roll, Banbury mixer or extruder.

The methacrylic resin sheet itself may be manufactured by a conventional manufacturing method. For example, it can be produced by a T-die method using an extruder, an inflation molding method, a calender molding method, a compression molding method, and a profile extrusion molding method.

In the plastics laminate of the present invention, a methacrylic resin film is laminated on at least one surface of the cupric sulfide-containing methacrylic resin sheet. Then, when this laminate is formed into a corrugated plate, it can be obtained by subjecting to pressure forming (for example, die extrusion, forming roll, etc.), vacuum forming, hot plate forming and the like. The stacking at this time is
It can be carried out by a known method such as so-called wet lamination, dry lamination, extrusion lamination and hot pressing. Further, a co-extrusion method in which a plurality of extruders are used for each resin layer and a single die simultaneously performs composite extrusion can also be applied. Here, the thickness of the methacrylic resin sheet is suitably in the range of 0.01 to 10 mm, preferably 0.05 to 5 mm. On the other hand, the thickness of the methacrylic resin film is 0.01
It is suitable to be within the range of ~ 0.2mm, 0.03 ~ 0.08mm
It is preferably within the range.

When the thickness of the methacrylic resin sheet deviates from the above range, the strength of the laminate or the corrugated sheet is lowered and the economy is not preferable, which is not preferable. Further, if the thickness of the methacrylic resin film is too thin, the processability during lamination becomes poor, and if it is too thick, the impact resistance decreases, which is not preferable.

The methacrylic resin film may contain dyes and pigments, ultraviolet absorbers and stabilizers. By providing a layer of methacrylic resin, to improve the smoothness or weather resistance of the near-infrared absorbing methacrylic resin sheet,
The color tone of the methacrylic resin sheet can be adjusted.

On the other hand, the corrugation is performed by imparting continuous irregularities such as a semicircular section, a rectangular shape, a trapezoidal shape, and a triangular section to the above laminated body. The pitch of these corrugations is usually 20 to 150 mm, and the depth thereof is usually 5 to 100 mm. The modified cross-sectional shape may be a tube shape such as a circle or a triangle, a hollow shape partitioned by ribs at predetermined intervals, or an open shape such as an L shape, a U shape, or a semicircular shape.

When the strength of the sheet is further increased or a pattern is formed, for example, a glass fiber net in which glass filament yarns are woven or woven in a lattice shape of about 5 mm square or a stainless steel wire net is contained and molded. May be.

The plastics laminate of the present invention may be used in combination of two or more. For example, two laminated corrugated sheets or laminated sheets are integrally formed by ribs at predetermined intervals (hollow shape). It is particularly useful as a composite sheet that requires strength and heat insulation properties, and is one preferred embodiment of the present invention.

As described above, according to the present invention, the average particle size is 12
By heating and kneading cupric sulfide of less than μm or cupric sulfide and thiourea derivative and / or thioamide derivative into a transparent resin by heating and kneading, near-infrared rays can be absorbed almost uniformly over the entire range of 800 to 2000 nm. A methacrylic resin laminate excellent in near-infrared absorbing ability can be obtained.

[0033]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, the addition ratios in the examples are all parts by weight.

The transmission spectrum of the obtained resin material was measured with a spectrophotometer (manufactured by Hitachi, Ltd .: Model 323). Near infrared absorption capacity is 900, 1000, 1100, 1500
The average value of the absorption value at each wavelength of nm is shown.

The stability of the near-infrared absorbing ability against heat, humidity and light was measured by the following method. Heat resistance and humidity resistance of the near-infrared absorbing sheet should be 48 in an oven at 80 ° C and 100% RH.
After leaving it for 0 hour, the near infrared absorption property was measured again with a spectrophotometer (10
00 nm). The storability was evaluated by the result calculated by the following formula.

[0036]

[Equation 1]

The light resistance was measured by irradiating the near-infrared absorbing sheet with a UV tester (a super accelerated light resistance tester manufactured by Dainippon Plastics Co., Ltd.) for 200 hours, and then measuring the near-infrared absorbing property again with a spectrophotometer (1000 nm). It was measured at. The storability was evaluated by the result calculated by the following formula.

[0038]

[Equation 2]

The thermal stability was determined by placing the laminate in a gear oven at a set temperature of 230 ° C. for 20 minutes, measuring the color tone change of the obtained sample with a color difference meter manufactured by Nippon Denshoku Co., Ltd., and using the Lab method. The color difference (ΔE) was calculated and determined as follows. ⊚: Excellent ◯: Good Δ: No burn (large yellow change) X: Burn is present The stability of the methacrylic resin against light was measured by the following method. After irradiating the near infrared ray absorbing sheet with a UV tester (a super accelerated light resistance tester manufactured by Dainippon Plastics Co., Ltd.) for 200 hours, a change in color tone and a change in tensile strength were measured. The retention rate of tensile strength was calculated by the following formula.

[0040]

[Equation 3]

Examples 1 to 14 The combination shown in Table 1 and cupric sulfide having an average particle size of 8 μm in parts by weight were added to 100 parts by weight of methacrylic resin, mixed with a tumbler mixer for 20 minutes, and then mixed with a 40 mmφ extruder.
After kneading at 230 ℃, make a sheet with a thickness of 0.7mm, and immediately after extrusion.
A 0.05 mm thick methacrylic resin film was extruded and laminated to a 0.75 mm thick laminate. The temperature of the cooling roll used for lamination was 80 ° C. Obtained sheet pitch 32
mm and a valley depth of 9 mm were formed by a corrugating machine. The transmission spectra of the obtained laminated sheets were measured and are shown in Table 3.
The results in the range of 800 to 2000 nm are shown, and the absorption in the near infrared region was excellent. This resin sheet relatively well transmits light in the visible range, but was excellent in the near-infrared absorption capacity, which is not found in ordinary methacrylic resin sheets.

Comparative Examples 1 to 4 Addition to methacrylic resin in the same manner as in Examples 1 to 14 with the combination and conditions of the combinations shown in Table 2, sheeting to 0.7 mm thickness, and immediately after extrusion, 0.05 mm thickness of methacrylic resin. The film was extruded and laminated to a 0.75 mm thickness.
The transmission spectra of these obtained sheets were measured, and Table 3 shows the results at 800 to 2000 nm.
It had a near infrared absorption capacity of not more than%.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

Example 15 The laminate obtained in Example 2 was irradiated with a UV tester (manufactured by Dainippon Plastics Co., Ltd. super accelerated light resistance tester) for 200 hours. Almost no yellowing was observed. The retention rate of tensile strength is
It was 92%. It can be seen that the methacrylic resin film has a high ultraviolet blocking effect.

Comparative Example 5 The sheet obtained without laminating the methacrylic resin film in Example 2 was irradiated with light by a UV tester (super accelerated light resistance tester manufactured by Dainippon Plastics Co., Ltd.) for 200 hours. The methacrylic resin, which is the sheet, turned considerably yellow. The retention of tensile strength was 35%, which shows that the methacrylic resin was considerably deteriorated by ultraviolet rays.

According to Table 3, it is clear that the methacrylic resin sheet kneaded with cupric sulfide forms a strong near infrared absorbing resin laminate. Further, it can be seen that this near-infrared absorptivity is hardly deteriorated by heating, humidification or exposure, and is highly stable against changes in environmental conditions of handling and storage. A sheet of methacrylic resin obtained by kneading metal copper alone, or kneading an addition amount of cupric sulfide other than the above, a thiourea compound or a thioamide compound,
Substantially no near infrared absorption.

[0049]

INDUSTRIAL APPLICABILITY As described above, the near-infrared absorbing methacrylic resin laminate and the corrugated plate-shaped molded product of the present invention do not have instability such as fading, and are photochromic in that they fade when left in a dark place for a long period of time. It also shows excellent near-infrared absorption capacity, and has strong absorption over the entire near-infrared region of 800 to 2000 nm. Industrial products such as optical filters, heat-absorbing glazing materials, outdoor terraces, balconies, carports, arcades, garages, windshields and daylight roofs, daylight side walls, skylights, etc. by utilizing these properties. Is useful in providing. Further, since it also has a heat retaining effect, it can be used to prevent heat radiation from a heated room. Although the product of the present invention contains a metal, it is less colored, so that the molded product of the laminate containing the product has an excellent appearance.

Claims (4)

[Claims] 1. Near-infrared absorption, characterized in that a methacrylic resin film is laminated and integrated on a methacrylic resin sheet containing 0.01 to 5 parts by weight of cupric sulfide with respect to 100 parts by weight of methacrylic resin. A methacrylic resin laminate with excellent performance. 2. Further, at least one thiourea derivative selected from the compounds represented by the following general formula (I):
A methacrylic resin film is laminated integrally on a methacrylic sheet containing 0.001 to 1 part by weight and / or 0.001 to 1 part by weight of at least one thioamide derivative selected from the compounds represented by the following general formula (II). The methacrylic resin laminate excellent in near-infrared absorbing ability according to claim 1, wherein the methacrylic resin laminate is excellent. [Chemical 1] (R ₁ , R ₂ and R ₃ are hydrogen, an alkyl group, a cycloalkyl group,
Represents a monovalent group selected from the group consisting of an aryl group, an aralkyl group and a 5- or 6-membered heterocyclic residue, each group being 1
May have one or more substituents, R ₁ and R ₂ or R ₂
R ₃ may combine to form a ring) (R ₄ and R ₅ are hydrogen, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a monovalent group selected from the group consisting of a 5- or 6-membered heterocyclic residue, or R ₅ Represents an alkoxy group, each group may have one or more substituents, and R ₄ and R ₅ may combine to form a ring) 3. A methacrylic resin laminate excellent in near-infrared absorptivity according to claim 1 or 2, wherein the cupric sulfide has an average particle size of 12 μm or less and substantially no particles of 20 μm or more. . 4. A near-infrared absorbing methacrylic resin obtained by molding the methacrylic resin laminate having excellent near-infrared absorbing ability according to any one of claims 1 to 3 into a corrugated plate-like or irregular cross-sectional shape. Laminated body.