JPS6331512B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel methacrylic resin material excellent in heat discoloration resistance and solar radiation absorption ability, and a method for producing the same. For more information, see organic compounds containing divalent copper ions and the formula Contains a phosphoric acid derivative shown in and dialkyl peroxide, which has excellent solar radiation absorption ability,
and a methacrylic resin material with improved heat discoloration resistance, as well as organic compounds and formulas containing divalent copper ions. By polymerizing a polymerizable unsaturated monomer mainly composed of methyl methacrylate in the presence of a phosphoric acid derivative and dialkyl peroxide shown in The present invention relates to a method for producing a methacrylic resin material with improved discoloration. Methacrylic resin materials have excellent transparency and weather resistance, so they have been used for so-called glazing applications such as windows, ceiling windows, doors, and domes of buildings and vehicles. Due to the high transmittance, there is a problem in that the internal temperature rises significantly when exposed to direct sunlight, for example. In order to suppress the rise in internal temperature, measures are taken such as installing sunshades on the inside of windows or cooling the room, but when sunshades are installed, the interior becomes darker, If visibility to the outside becomes poor, the excellent transparency of the methacrylic resin material becomes useless, and cooling the room is inherently undesirable from the point of view of energy conservation. Due to the above-mentioned circumstances, attempts have been made to modify the methacrylic resin material itself to effectively reduce the solar radiation transmittance while suppressing the decrease in the visible light transmittance as much as possible. Hereinafter, in the present invention, a low solar radiation transmittance in spite of a high visible light transmittance will be referred to as an excellent solar radiation absorbing ability. The spectral distribution of solar radiant energy and the spectral sensitivity of vision have been described in various publications, e.g.
JIS R 3208 "Heat ray absorbing plate glass" shows the spectral distribution of solar radiant energy and the spectral sensitivity of vision. According to the spectral distribution of solar radiant energy according to JIS R 3208, 80% of solar radiant energy comes from light in the wavelength range of 400 to 1100 nm (nanometers).
The above is occupied. Also, from the spectral sensitivity of vision specified in JIS R 3208, the visible light transmittance is
It can be seen that it is essentially determined by light rays in the wavelength range of 500 to 650 nm. Light rays in the wavelength range of 1100 nm or more are strongly absorbed to some extent by polymethyl methacrylate;
Furthermore, considering that light in the wavelength range of 400 nm or less can be substantially absorbed by appropriately adding a commercially available ultraviolet absorber to the methacrylic resin material, it is possible to suppress the decrease in visible light transmittance. However, in order to effectively reduce solar radiation transmittance, we believe that adding a substance that selectively and strongly absorbs light in the wavelength ranges of 400 to 500 nm and 650 to 1100 nm into the methacrylic resin material is considered a good method. It will be done. For example, in order to absorb light in the wavelength range of 400 to 500 nm, there is a method in which a commercially available yellow dye is added to the resin material to selectively absorb it. When the resin material is yellow or contains other coloring substances, it is inevitable that the resin material will be colored in the color combined with the coloring substance. Therefore, only when it is not inappropriate to color the resin material yellow or yellowish, by appropriately adding yellow dye to the resin material, resins with low transmittance for light in the wavelength range of 400 to 500 nm can be produced. Although obtaining the material is a preferable method, unless it is used in conjunction with a method of reducing the transmittance of light in the wavelength range of 650 to 1100 nm, it is not possible to impart solar radiation absorption ability to a practically sufficient level. Also, in order to absorb light in the wavelength range of 650 to 1100 nm, there is a method of adding commercially available blue or green dyes, but although the visible light transmittance is greatly reduced, the solar radiation transmittance is reduced. is small, and therefore cannot provide sufficient solar radiation absorption ability. As a result of research into a method for selectively and strongly absorbing light in the wavelength range of 650 to 1100 nm, the present inventor found that an organic compound containing a specific amount of divalent copper ions and one or more divalent copper ions in one molecule was found in methacrylic resin. P-O-H
It was discovered that a method of containing both compounds having a bond of 650 to 1,100 nm can selectively and strongly absorb light in the wavelength range of 650 to 1100 nm, and that a methacrylic resin material with excellent solar radiation absorption ability can be obtained. (Patent application No. 1983-49240)
issue). However, the methacrylic resin material with excellent solar radiation absorption ability obtained by the above method has a problem in that it tends to discolor when heated. In other words, when trying to obtain a desired shape by heat molding, discoloration is often observed, and the advantage of being easily heat moldable, which is one of the excellent characteristics of methacrylic resin materials, is lost. was. This discoloration caused by heating near the molding temperature of resin materials is mainly caused by yellowing, and the higher the heating temperature and the longer the heating time, the more pronounced the yellowing becomes. When a material is heat-molded, uneven discoloration occurs in the resin material during molding due to non-uniform temperature of the resin material, reducing commercial value. The present inventor has discovered that the above organic compound containing a specific amount of divalent copper ions and one or more P-O-
As a result of continuing intensive studies on a method for reducing heat discoloration of methacrylic resin materials that are endowed with excellent solar radiation absorption ability by containing both compounds having H bonds, we found that dialkyl peroxide was incorporated into the resin materials. The present invention was completed based on the discovery that the degree of heat discoloration of the resin material can be significantly reduced by allowing the resin materials to coexist. That is, the gist of the present invention is that, for 100 parts by weight of a methacrylic resin selected from polymethyl methacrylate or a methacrylic polymer containing 50% by weight or more of methyl methacrylate units,
The organic compound (A) containing divalent copper ions is 0.01 to 5 parts by weight in terms of the weight of copper ions, the dialkyl peroxide (B) is 0.01 to 5 parts by weight, and the following formula (In the formula, R ¹ is selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group, an aralkyl group, an alkenyl group, an acryloyloxyalkyl group, and a methacroyloxyalkyl group,
n is 1 or 2. ) to the organic compound (A) containing the divalent copper ion (1).
A methacrylic resin material with improved thermal discoloration resistance, containing an amount of 0.1 to 10 moles per mole, and a polymerizable unsaturated monomer containing methyl methacrylate alone or 50% by weight or more of methyl methacrylate. 0.01 to 5 parts by weight of the organic compound (A) containing divalent copper ions in terms of the weight of copper ions and the following: formula (In the formula, R ¹ is selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group, an aralkyl group, an alkenyl group, an acryloyloxyalkyl group, and a methacryloyloxyalkyl group, and n is 1 or The phosphoric acid derivative (C) represented by 2) is an organic compound containing the divalent copper ion.
(A) in an amount of 0.1 to 10 moles per mole, and a composition formed by coexisting dialkyl peroxide (B) in the presence of a radical polymerization initiator,
Methacrylic resin 100 made of a polymer of the polymerizable raw material from which the dialkyl peroxide (B) was obtained
A method for producing a methacrylic resin material having heat discoloration resistance and excellent solar radiation absorbing ability, characterized by containing 0.01 to 5 parts by weight per part by weight. Although the methacrylic resin material having excellent solar radiation absorption ability according to the present invention can be obtained by any method, it is preferable to obtain it by bulk polymerization, preferably mold polymerization, of the above-described composition. The polymerizable raw material used in the production of the resin material of the present invention is methyl methacrylate alone, a polymerizable unsaturated monomer mixture containing 50% by weight or more of methyl methacrylate, or a partial polymer thereof. Examples of polymerizable unsaturated monomers that can be copolymerized with methyl methacrylate include (meth)acrylic acid (meaning acrylic acid or methacrylic acid, hereinafter the same), methyl acrylate, ethyl (meth)acrylate, ( Butyl meth)acrylate, stearyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolethanetri (Meth)acrylic acid and alcohol represented by (meth)acrylate, trimethylolbropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, allyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate esters, (meth)acrylamide and its derivatives,
Specific examples include styrene, its derivatives, and vinyl acetate. In the present invention, when using a polymerizable unsaturated monomer mixture containing 50% by weight or more of methyl methacrylate as a polymerizable raw material, methyl methacrylate is 50% by weight or more, preferably 60% by weight or more, and further 80% by weight. It is more preferable to include the above. Methyl methacrylate 85-100% by weight and methyl acrylate within this range,
Ethyl acrylate, butyl acrylate, (meth)
Particularly preferred is one selected from acrylic acid, 2-hydroxyethyl (meth)acrylate, or a mixture thereof in an amount of 0 to 15% by weight. When using methyl methacrylate or a partial polymer of a polymerizable unsaturated monomer mixture containing 50% by weight or more of methyl methacrylate as a polymerizable raw material, the method for obtaining the partial polymer is as follows. A preferred example is a method in which bulk prepolymerization is carried out at the boiling point of methyl methacrylate or a mixture thereof with other unsaturated monomers to obtain a partial polymer with a polymerization rate of 5 to 35%. Preferred specific examples of the organic compound (A) containing divalent copper ions used in the present invention include formic acid, acetic acid, propionic acid, valeric acid, hexanoic acid, octylic acid, decanoic acid, lauric acid, stearic acid, and oleic acid. Examples include salts of divalent copper ions with carboxylic acids such as 2-ethylhexanoic acid, naphthenic acid, and benzoic acid, and complex salts of acetylacetone or acetoacetic acid with divalent copper ions. In the present invention, the organic compound (A) containing these divalent copper ions contains polymethyl methacrylate or 50 methyl methacrylate units in the resin material.
0.01 to 5 parts by weight, calculated as divalent copper ion, is added to 100 parts by weight of a methacrylic resin selected from methacrylic polymers containing at least % by weight. If the added amount of the organic compound containing divalent copper ions does not reach 0.01 part by weight in terms of the weight of divalent copper ions, the solar radiation absorption ability of the resin material is insufficient, and on the other hand, if the amount exceeds 5 parts by weight. In this case, the physical properties such as mechanical strength of the resin material are significantly deteriorated, which is undesirable. It is more preferable to add 0.025 to 0.5 part by weight in terms of the weight of divalent copper ions within the above-mentioned range of addition amount of the organic compound containing divalent copper ions. Formula used in the present invention Examples of phosphoric acid derivatives represented by include ethyl phosphate (mono-ethyl phosphate,
), di-ethyl phosphate, butyl phosphate, di-butyl phosphate, hexyl phosphate, di-hexyl phosphate, heptyl phosphate, di-heptyl phosphate, octyl phosphate ate, di-octyl fluorophosphate, lauryl fluorophosphate, di-lauryl fluorophosphate, stearyl fluorophosphate, di-stearylphophosphate,
2-Ethylhexyl phosphate, bis(2-
ethylhexyl) phosphate, oleyl phosphate, di-oleyl phosphate, phenyl phosphate, di-phenyl phosphate, (nonylphenyl) phosphate, bis(nonylphenyl) phosphate, 2-chloroethyl phosphate, bis (2-chloroethyl) phosphate, 2,3-dichloropropyl phosphate, bis(2,3-dichloropropyl) phosphate, or γ-methacryloyloxypropyl phosphate, bis(γ-methacryloyloxypropyl) phosphate, etc. are preferred. This can be given as a specific example. In the present invention, these phosphoric acid derivatives (C)
is added in an amount of 0.1 to 10 moles per mole of the organic compound containing divalent copper ions. If it is less than 0.1 mol, the improvement in solar radiation absorption capacity is insufficient;
If the amount exceeds 10 moles, the mechanical strength of the resulting resin material will drop significantly, which is undesirable. 0.1 above
As the amount of the phosphoric acid derivative added increases within the range of ~10 moles, the degree of improvement in solar radiation absorption ability increases, but at the same time, as the amount added increases, the mechanical strength of the resin material decreases, etc. Therefore, the amount of the phosphoric acid derivative to be added may be selected by appropriately determining the balance between the degree of improvement in the solar radiation absorption ability of the resin material and other physical properties. The dialkyl peroxide (B) used in the present invention is added for the purpose of improving heat discoloration resistance, and preferred specific examples include the following. The numbers in parentheses are listed in the "Nippon Oil Organic Peroxide Catalog" and "The Chemistry and Industrial Use of Organic Peroxides (Chemical Manufacturers)," and the half-life of decomposition in the solvents listed is 10. Indicates temperature and time. Namely, tertiary butyl peroxide (124℃: benzene), tertiarybutylcumyl peroxide (120℃: benzene), dicumyl peroxide (117℃: benzene, 115℃: toluene), α, α′-
Bis(tertiarybutylperoxy) p-diisopropylbenzene (120℃: benzene), 2,5-
Dimethyl-2,5-di(tertiarybutylperoxy)hexane (154℃: benzene, 117℃: toluene), 2,5-dimethyl-2,5-di(tertiarybutylperoxy)hexane-3 (135 ℃: benzene, 127℃: toluene). In the present invention, the dialkyl peroxide is based on 100 parts by weight of a methacrylic resin selected from polymethyl methacrylate or a methacrylic polymer containing 50% by weight or more of methyl methacrylate units.
It is added in an amount of 0.01 to 5 parts by weight. If it is less than 0.01 part by weight, the effect of reducing the degree of heat discoloration will not be sufficiently recognized, while if it exceeds 5 parts by weight, the weather resistance, mechanical strength, heat distortion temperature, etc. of the obtained resin material will decrease. Undesirable. It is more preferable to add 0.05 to 1 part by weight within the above range. In addition, in the present invention, methyl methacrylate, a polymerizable unsaturated monomer mixture containing 50% by weight or more of methyl methacrylate, or a partial polymer thereof together with an organic compound containing divalent copper ions and a phosphoric acid derivative, A dialkyl peroxide is added and polymerized in the presence of a radical polymerization initiator. The amount of dialkyl peroxide that should be added in advance to the above polymerizable unsaturated monomer when carrying out the method of adding 0.01 to 5 parts by weight to 100 parts by weight of the obtained methacrylic resin is: In consideration of decomposition due to temperature history during polymerization, the amount must be greater than the amount contained in the obtained resin material. The fraction of dialkyl peroxide that decomposes depending on the temperature history during polymerization varies depending on the thermal decomposition characteristics of dialkyl peroxide and the polymerization temperature, but generally the half-life of dialkyl peroxide during polymerization is 10 hours. Since the decomposition rate does not reach 50% because it is not heated for more than 10 hours at a temperature higher than 100%, the decomposition rate is usually within the range of 0 to 20%.
Therefore, the dialkyl peroxide should be added in advance to the polymerizable unsaturated monomer or its partial polymer in an amount of 1 to 2 times the amount to be contained in the obtained resin material, and usually 1 to 1.25 times the amount to be contained in the obtained resin material. Bye. In carrying out the present invention, when using an organic compound containing divalent copper ions, a phosphoric acid derivative is used as a cosolvent, or (meth)acrylic acid or 2-hydroxyethyl (meth)acrylate is used. In this case, they and a phosphoric acid derivative are used as co-solvents, and are dissolved in an unsaturated monomer containing methyl methacrylate as a main component or a partial polymer thereof. However, depending on the type and amount of the organic compound containing divalent copper ions, the solubility may be insufficient, so in this case,
In order to improve the solubility of divalent copper ions, carboxylic acids such as acetic acid, propionic acid, hexanoic acid, octylic acid, decanoic acid, lauric acid, and 2-ethylhexanoic acid, or octyl alcohol, lauryl alcohol, and ethylene glycol are used. , diethylene glycol, tetraethylene glycol, etc., preferably based on 100 parts by weight of methyl methacrylate, a polymerizable unsaturated monomer mixture containing methyl methacrylate as a main component, or a partial polymer thereof. is preferably added in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less. In addition to the components described above, various additives used in the production of ordinary methacrylic resin materials may be added when carrying out the present invention.
Specific examples of additives include dyes and pigments used for coloring, antioxidants, stabilizers such as ultraviolet absorbers, flame retardants, plasticizers, and release agents that facilitate the release of resin materials from molds. be able to. Among these additives, it is preferable to add an ultraviolet absorber to the resin material in order to suppress deterioration of the resin material due to ultraviolet rays, such as coloring, crazing, and rough skin. Further, the addition of an ultraviolet absorber is preferable from the viewpoint of improving the solar radiation absorbing ability because it can reduce the solar radiation transmittance without reducing the visible light transmittance of the resin material. The desired performance of the ultraviolet absorber used is that it should sufficiently absorb light in the wavelength range that causes deterioration of the resin plate, and that it should not react with divalent copper ions and be difficult for the methacrylic resin used in the present invention. One example is that it is difficult to form soluble complexes. Specific examples of UV absorbers with such performance include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, and 2-hydroxy-4-decyloxybenzophenone. Non, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4,
4'-dimethoxybenzophenone, 2-hydroxy-4,4'-dibutoxybenzophenone, 2-hydroxy-4,4'-dioctyloxybenzophenone, 2-hydroxy-4-methoxy-4'-chlor 2-hydroxybenzophenone derivatives such as benzophenone, 2-hydroxy-4-methoxy-2′,4′-dichlorobenzophenone, and 2-hydroxy-4-methoxy-2′-carboxybenzophenone; or 2-(2′-hydroxy-3′,5′-dic-syabutylphenyl)benzotriazole, 2-[2′-hydroxy-3′,5′-bis(2″,
2″-dimethylpropyl)phenyl]benzotriazole or benzotriazole derivatives such as halogen-substituted derivatives thereof, phenyl salicylate, p-ethyl phenyl salicylate,
Examples include esters of salicylic acid such as p-tertiarybutylphenyl salicylate. The UV absorber used is based on 100 parts by weight of the polymer whose main component is methyl methacrylate.
It is preferable to add 0.01 to 1 part by weight, and 0.05 to 1 part by weight.
It is more preferable to add 0.5 parts by weight. Furthermore, among the additives in the resin material, the addition of a yellow dye improves the solar radiation absorption ability of the resin material, so it is listed as an example of a preferable additive as long as it is in a quantitative range that does not impede the purpose of the present invention. It will be done. In addition, among the dyes and pigments used to color resin materials, carbon black provides an anti-glare effect to resin materials, and at the same time, it is generally used from 290 nm to
Since it has absorption over the entire wavelength range of solar radiation up to 2140 nm, when carbon black is used in combination with the method of the present invention, a resin material with improved heat discoloration resistance, anti-glare properties, and excellent solar radiation absorption ability can be obtained. can get. Therefore, a method of adding 0.0001 to 0.05 parts by weight of carbon black to 100 parts by weight of methacrylic resin is one of the preferred embodiments of the present invention. Furthermore, a radical polymerization initiator such as an azo compound or an organic peroxide used when producing the methacrylic resin material of the present invention by polymerization is added to 50% of methyl methacrylate or methyl methacrylate.
It is necessary to add 0.0001 to 0.5 parts by weight per 100 parts by weight of polymerizable unsaturated monomers or partial polymers thereof containing % by weight or more, and furthermore 0.001 parts by weight.
It is preferable to add up to 0.5 part by weight. Specific examples of azo compounds used as radical polymerization initiators include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), etc. Specific examples of organic peroxides include tertiary butyl peroxyacetate, tertiary butyl peroxyisobutyrate, and tertiary butyl peroxyisobutyrate. Peroxypivalate, tertiary butyl peroxy-2-ethylhexanoate,
Tertiary butyl peroxylaurate, Tertiary butyl peroxybenzoate, Ditertiary butyl diperoxyphthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, Tertiary butyl peroxymalate Peroxy esters such as acid, tertiary butyl peroxyisopropyl carbonate, lauroyl peroxide, stearoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, p-chloro Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, acetyl peroxide, propionyl peroxide, isobutyryl peroxide, octanoyl peroxide,
Examples include diacyl peroxide such as decanoyl peroxide, acetylcyclohexylsulfonyl peroxide, and the like. The above radical polymerization initiators may be used alone or in combination of two or more. The methacrylic resin material can be obtained by mold polymerization by sealing the periphery of the above composition with a gasket according to a conventional method, and then injecting the composition between two sheets of tempered glass facing each other and heating it. Single-sided mirror-polished 2 moving at the same speed in the direction
Specific polymerization methods include a method in which the composition is continuously injected from upstream of a space sealed by a sheet of endless belt and a gasket, and the composition is continuously polymerized by heating. The polymerization temperature varies depending on the type of radical polymerization initiator used, but is generally 40 to 140°C, and is a two-stage polymerization in which the first stage is 40 to 90°C and the second stage is 90 to 140°C. It is preferred to polymerize at temperature. The thickness of the resin plate obtained by mold polymerization is not particularly limited, but it is preferably within the range of the thickness of commercially available methacrylic resin plates, that is, 1 to 65 mm. The present invention will be explained below based on specific examples. In addition, in the examples, parts represent parts by weight,
In addition, the visible light transmittance and solar radiation transmittance of the resin material were determined by converting them into values for a 5 mm thick resin plate in accordance with the JIS R 3208 "heat ray absorbing plate glass" standard.
In addition, the degree of yellowish color of the resin plate is determined by the formula [] a = 1/tln (T ₀ /T) ... [] (where t is the thickness of the resin plate in cm,
T ₀ is the light transmittance (%) at 450 nm of the colorless transparent methacrylic resin plate = 92.2 (%), T is the light transmittance in % at 450 nm of the resin plate as a sample, and therefore a is the light transmittance of the resin plate at 450 nm. Each represents the absorbance. ) It was expressed as the absorbance at 450 nm. Also, the heat deformation temperature of the resin plate is
It was measured based on the method specified in ASTM D-648. Example 1 Seal the surrounding area with a PVC pipe gasket,
Between two pieces of tempered glass facing each other, 100 parts of methyl methacrylate, 0.2 parts of copper formate (Cu(HCOO) _{2.4H 2} O), 2-ethylhexyl phosphate, bis(2
-Ethylhexyl) phosphate mixture (manufactured by Johoku Kagaku Kogyo, trade name "JP508") 0.2 parts 2-ethylhexanoic acid 1.5 parts 2-hydroxy-4-methoxybenzophenone
0.3 part 2,2'-azobis(isobutyronitrile)
0.07 parts benzoyl peroxide 0.02 parts tertiary butylcumyl peroxide
A composition consisting of 0.3 parts was injected, immersed in a water bath at 65°C for 5 hours, then heated in an air bath at 110°C for 2 hours to complete polymerization, and after cooling, it was peeled off from the tempered glass to form a 3 mm thick sheet. A pale blue-green transparent resin plate was obtained. The visible light transmittance of this resin plate was 75.6%, the solar radiation transmittance was 65.1%, and it had excellent solar radiation absorption ability. In addition, the heat deformation temperature of this resin plate is 98.5
℃, and the absorbance at 450 nm was a=0.098. Furthermore, as a result of analysis by gas chromatography, tertiary butyl cumyl peroxide was found to be 0.277% per 100 parts by weight of polymethyl methacrylate.
Parts by weight were present. When the resin plate obtained in this way was heated for 30 minutes in a hot air circulation oven heated to 140°C, there was almost no change in the appearance of the resin plate due to heating, and the visible light of the resin plate after heating was Transmittance is 75.9%, solar radiation transmittance is 65.5%, absorbance at 450nm a=
0.099, which showed virtually no change and excellent heat discoloration resistance. Comparative Example 1 The same operation as in Example 1 was repeated except that tertiary butyl cumyl peroxide was removed from the composition to be injected, to obtain a pale blue-green transparent resin plate with a thickness of 3 mm. The visible light transmittance of this resin plate was 75.8%, the solar radiation transmittance was 65.3%, and it had excellent solar radiation absorption ability. Also, the heat distortion temperature of this resin plate is 98.8
The absorbance at 450 nm at ℃ was 0.096. When this resin plate was heated for 30 minutes in a hot air circulating oven heated to 140° C. in the same manner as in Example 1, the resin plate became noticeably yellowish. In addition, the absorbance a at 450 nm after heating was 0.561. Example 2 A methyl methacrylate partial polymer (polymer content
6.5%) 98 parts Methyl acrylate 2 parts Copper oleate (Cu(C ₁₈ H ₃₃ O ₂ ) ₂ ) 0.8 parts 2-Chloroethyl phosphate, bis(2-
chloroethyl) phosphate mixture (manufactured by Johoku Kagaku Kogyo Co., Ltd., trade name "JPC502") 0.4 parts 2-(2'-hydroxy-3',5'-ditertyabutylphenyl)benzotriazole 0.1 part Benzoyl peroxide 0.06 parts 2, A composition consisting of 0.5 part of 5-dimethyl-2,5-di(tertiarybutylperoxy)hexane was injected, immersed in a 70°C water bath for 5 hours, and then heated in a 115°C air bath for 2 hours. After completion of polymerization, the resin plate was peeled off from the reinforced glass after cooling to obtain a pale blue transparent resin plate with a thickness of 2 mm. The visible light transmittance of this resin plate is 76.4%,
The solar radiation transmittance was 62.6%, and the solar radiation absorption ability was excellent. In addition, the heat distortion temperature of this resin plate is 93.8℃, and the absorbance at 450nm is a=0.101
It was hot. In addition, as a result of gas chromatography analysis, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane was found to be methyl methacrylate-methyl acrylate per 100 parts by weight.
0.498 parts by weight were present. When the resin plate obtained in this way was heated for 30 minutes in a hot air circulation oven heated to 135°C, there was almost no change in the appearance of the resin plate due to heating, and the visible light of the resin plate after heating was Transmittance is 76.6%, solar radiation transmittance is 62.7%, absorbance at 450nm a=
It was 0.102, and no substantial change was observed. Comparative Example 2 2,5-dimethyl-2,5 from the composition to be injected
The same operation as in Example 2 was repeated except that -di(tert-butylperoxy)hexane was removed to obtain a pale blue transparent resin plate with a thickness of 2 mm. The visible light transmittance of this resin plate was 76.5%, the solar radiation transmittance was 62.8%, and it had excellent solar radiation absorption ability. In addition, the heat deformation temperature of this resin plate is 94.3
The absorbance at 450 nm at ℃ was 0.100. When this resin plate was heated for 30 minutes in a hot air circulating oven heated to 135° C. in the same manner as in Example 1, the resin plate became noticeably yellowish. The absorbance a after heating was 0.492. Examples 3 to 6, Comparative Examples 3 to 5 Continuously from upstream of the mold space formed by sealing with two single-sided mirror-polished endless stainless steel belts and gaskets moving in the same direction at the same speed, The composition shown below is a partially polymerized methyl methacrylate (polymer content
21.5%) 99 parts 2-hydroxyethyl methacrylate 1 part n-octylic acid 2 parts Copper acetate (Cu(CH ₃ COO) _{2.H 2} O) 0.4 parts Butyl phosphate 0.06 parts Di-butyl phosphate 0.54 parts 2-Hydroxy-4-octyloxybenzophenone 0.3 parts 2,2-azobis(2,4-dimethylvaleronitrile) 0.026 parts Benzoyl peroxide 0.025 parts Di-tertiary butyl peroxide
The modified amount shown in Table 1 was injected, passed through a hot water shower zone at 82℃ in 36.7 minutes, passed through a far-infrared heater heating zone and slow cooling zone heated to a maximum temperature of 115℃ in 18.3 minutes, and then Several types of greenish, pale blue transparent resin plates with a thickness of 5 mm were manufactured continuously. These resin plates were quantified by visible light transmittance, solar radiation transmittance, heat distortion temperature, absorbance a at 450 nm, and gas chromatography. The content of jet ash butyl peroxide was as shown in Table 1, and all had excellent solar radiation absorption ability. Next, these resin plates were heated for 1 hour in hot air circulation ovens heated to 120°C and 150°C, respectively, and changes in the appearance of the resin plates and absorbance a at 450 nm were measured. The results are shown in Table 1.

[Table] Example 7 Similar to those used in Examples 3 to 6, the mold space formed by sealing with two mirror-polished endless stainless steel belts and gaskets moving in the same direction and at the same speed. Continuously from upstream, the following composition methyl methacrylate partial polymer (polymer content
20%) 99 parts methacrylic acid 1 part copper acetate (Cu(CH ₃ COO) _{2.H 2} O) 0.2 parts bis(γ-methacryloxypropyl) phosphate 0.35 parts p-tertiarybutylphenyl salicylate
Pour 0.1 part carbon black pigment (Toyo Ink Manufacturing Co., Ltd. trade name "ANC901") 0.0046 parts 2,2'-azobis(2,4-dimethylvaleronitrile) 0.057 parts dicumyl peroxide 0.5 parts, and heat at 80℃. After passing through a hot water shower zone for 28 minutes, the system passes through a far-infrared heater heating zone that heats up to a maximum temperature of 110°C and a slow cooling zone for 14 minutes, allowing a slightly bluish color with a thickness of 3 mm to be continuously produced downstream. A transparent resin plate with a clear color was obtained. The visible light transmittance of this resin plate was 61.0%, the solar radiation transmittance was 48.5%, and it had excellent solar radiation absorption ability and anti-glare properties. Further, the heat distortion temperature of this resin plate was 103.3°C, and the absorbance a at 450 nm was 0.859. When this resin plate was heated for 30 minutes in a hot air circulating oven heated to 140°C, there was almost no change in the appearance of the resin plate due to heating, and the visible light transmittance of the resin plate after heating was 61.1%, solar radiation transmittance is
48.6% and absorbance at 450 nm a=0.859, with virtually no change observed. Comparative Example 6 The same operation as Example 7 was repeated except that dicumyl peroxide was removed from the composition to be injected.
A transparent resin plate with a slightly bluish color and a thickness of 3 mm was obtained. The visible light transmittance of this resin plate was 62.1%, the solar radiation transmittance was 50.5%, and it had excellent solar radiation absorption ability and anti-glare properties. The heat distortion temperature of this resin plate was 103.6°C, and the absorbance a at 450 nm was 0.848. When this resin plate was heated for 30 minutes in a hot air circulation oven heated to 140° C. in the same manner as in Example 7, the resin plate became significantly yellowish. Note that the absorbance a at 450 nm after heating was 1.33.

Claims (1)

[Scope of Claims] 1. An organic compound containing divalent copper ions based on 100 parts by weight of a methacrylic resin selected from polymethyl methacrylate or a methacrylic polymer containing 50% by weight or more of methyl methacrylate units. 0.01 to 5 parts by weight of (A) converted to the weight of copper ions and 0.01 to 5 parts by weight of dialkyl peroxide (B),
and the following formula (In the formula, R ¹ is selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group, an aralkyl group, an alkenyl group, an acryloyloxyalkyl group, and a methacryloyloxyalkyl group, and n is 1 or The phosphoric acid derivative (C) represented by 2) is an organic compound containing the divalent copper ion.
(A) A methacrylic resin material with excellent solar radiation absorbing ability, containing an amount of 0.1 to 10 moles per mole. 2. The organic compound (A) containing divalent copper ions is selected from the group consisting of salts of carboxylic acid and divalent copper ions, and complex salts of acetylacetone or acetoacetic acid and divalent copper ions. A methacrylic resin material with excellent solar radiation absorption ability as set forth in claim 1, characterized by: 3 The dialkyl peroxide (B) is tertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, α,α'-bis(tertiary butyl peroxy)-p-diisopropylbenzene, 2,5 -dimethyl-2,5-di(tertiarybutylperoxy)hexane, 2,5-dimethyl-2,5-di(tertiarybutylperoxy)hexyne-3. A methacrylic resin material with excellent solar radiation absorption ability as set forth in claim 1. 4 Containing divalent copper ions based on 100 parts by weight of a polymerization raw material consisting of methyl methacrylate alone, a polymerizable unsaturated monomer mixture containing 50% by weight or more of methyl methacrylate, or a partial polymer thereof. Convert organic compound (A) to the weight of copper ions
0.01 to 5 parts by weight and the following formula (In the formula, R ¹ is selected from an alkyl group having 1 to 18 carbon atoms, an allyl group, an aryl group, an aralkyl group, an alkenyl group, an acryloyloxyalkyl group, and a methacryloyloxyalkyl group, and n is 1 or The phosphoric acid derivative (C) represented by 2) is an organic compound containing the divalent copper ion.
(A) in an amount of 0.1 to 10 moles per mole, and a composition formed by coexisting dialkyl peroxide (B) in the presence of a radical polymerization initiator,
Methacrylic resin 100 made of a polymer of the polymerizable raw material from which the dialkyl peroxide (B) was obtained
A method for producing a methacrylic resin material having excellent solar radiation absorption ability, characterized in that the content is 0.01 to 5 parts by weight. 5. The organic compound (A) containing divalent copper ions is selected from the group consisting of salts of carboxylic acid and divalent copper ions, and complex salts of acetylacetone or acetoacetic acid and divalent copper ions. A method for producing a methacrylic resin material with excellent solar radiation absorption ability according to claim 4, characterized in that: 6 The dialkyl peroxide (B) is tertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, α, α′-bis(tertiary butyl peroxy)-p-diisopropylbenzene, 2,5 -dimethyl-2,5-di(tertiarybutylperoxy)hexane, 2,5-dimethyl-2,5-di(tertiarybutylperoxy)hexyne-3. A method for producing a methacrylic resin material having excellent solar radiation absorption ability as set forth in claim 4.