JP2558930B2 - Photoselective functional resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition having photoselective functionality, and more particularly to a resin composition that selectively absorbs light in a wavelength band near a wavelength of 580 nm.

[Prior Art] As a resin composition having a photoselective function, a resin composition utilizing a property that a neodymium compound selectively absorbs a light beam having a wavelength of about 580 nm has been conventionally known. For example, the photoselective absorptive resin composition disclosed in JP-A-58-225148 is one in which neodymium oxide powder or the like is dispersed in a transparent plastic substrate such as methacrylic resin. Further, the neodymium-containing transparent resin described in JP-A-60-161458 is composed of a monomer such as alkyl methacrylate or styrene, a neodymium compound such as neodymium acrylate, a solvent for the neodymium compound such as carboxylic acid, and a polymerization initiator. The mixture is polymerized by the cell casting method.

These resin compositions have the property of selectively absorbing light in the wavelength region near the wavelength of 580 nm as described above.
Specific applications such as filters for color display devices such as CRTs, screen plates, and lighting equipment can be considered.

However, in the case where the neodymium oxide powder is dispersed in the transparent plastic substrate, the transparency and the light transmittance are lowered because it is a dispersion system of the inorganic powder, and the absorption peak is broad and the amount of absorbed light is small. There is.

Further, in the resin composition of JP-A-60-161458, since the neodymium compound and the solvent are molecularly bound or dissolved in the polymer, the mechanical properties of the polymer itself are changed, and the polymer is optically sufficient. If an attempt is made to include a large amount of neodymium compound, there is a disadvantage that the characteristics of the resin composition are significantly deteriorated.

[Problems to be Solved by the Invention] Accordingly, an object of the present invention is to provide a light-selective functional resin composition having sharp absorption characteristics without causing inconveniences such as a decrease in transparency and light transmittance and deterioration of characteristics of the resin composition. To get things.

[Means for Solving the Problem] This problem is solved by a transparent polymer containing a neodymium compound in a dissolved state or in a copolymerized bond with the transparent polymer and having a particle size of 0.01 μm to 5 mm and having a light-selective functionality. It is solved by dispersing beads (hereinafter, may be abbreviated as transparent beads or beads) in a transparent resin composition.

 Hereinafter, the present invention will be described in detail.

First, the light-selective functional transparent beads used in the present invention are particles in which a neodymium compound is contained in a transparent polymer in a dissolved state or in a copolymerized state with the transparent polymer. The particle size of the beads is 5 mm or less and 0.01 μm or more. This particle size varies greatly depending on the application of the beads. The neodymium compound in the beads may be chemically bound to the transparent polymer by means such as copolymerization, or may be dissolved in the transparent polymer. Also, the beads themselves need to be transparent.

Next, this light-selective functional transparent bead will be described by its manufacturing method.

The method for producing the transparent beads having photoselective functionality is to carry out suspension polymerization of a mixture of a double salt obtained from neodymium carboxylate and carboxylic acid and a polymerizable monomer which makes the polymerized polymer transparent.

Neodymium carboxylate as this neodymium compound,
It may be polymerizable or non-polymerizable. Examples of the polymerizable neodymium carboxylate include neodymium methacrylate, neodymium acrylate, neodymium α-chloroacrylate, α-ethyl neodymium methacrylate, neodymium maleate, neodymium fumarate, neodymium itaconate and the like. Further, as the non-polymerizable neodymium carboxylate, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, n-caproic acid, n-caprylic acid, n-capric acid, α-ethylhexane Neodymium salts of saturated fatty acids such as acids, lauric acid, stearic acid and oleic acid, linoleic acid, linolenic acid, ricinoleic acid, benzoic acid, phthalic acid, succinic acid, maleic acid, itaconic acid, itaconic acid monoalkyl ester, naphthenic acid Unsaturated fatty acids such as, repurinic acid, oxocarboxylic acids such as acetylvaleric acid, lactic acid, glycolic acid ethyl ether, hydroxycarboxylic acids such as glycolic acid butyl ether, butyl acid phosphate, phosphoric acid such as ethyl acid phosphate, Examples thereof include neodymium salts of aliphatic and aromatic sulfonic acids. These neodymium carboxylate may be used alone or in combination of two or more, and may be a mixture of a polymerizable compound and a non-polymerizable compound.

First, such neodymium carboxylate is reacted with a carboxylic acid to form a double salt. This is because neodymium carboxylate is generally sparingly soluble in the polymerizable monomer and can be easily dissolved in the polymerizable monomer by forming a double salt.

Examples of the carboxylic acid for this purpose include polymerizable unsaturated carboxylic acids such as methacrylic acid and acrylic acid, and propionic acid, isobutyric acid, n-butyric acid, caproic acid, caprylic acid, capric acid, 2-ethylhexanoic acid, and stearic acid. And saturated or unsaturated aliphatics such as octanoic acid and naphthenic acid. One or more of these are used in combination.

The mixing ratio of neodymium carboxylate and carboxylic acid is such that when the total amount of both is 100% by weight, carboxylic acid is 10 to 40%.
It is preferably in the range of wt%. The amount of carboxylic acid
If it exceeds 40% by weight, the content of neodymium in the beads is lowered, and the mechanical properties and thermal properties of the beads are lowered, which is not preferable.

In order to further improve the solubility of neodymium carboxylate, unsaturated alcohols such as α-hydroxyethyl acrylate and α-hydroxyethyl methacrylate, saturated aliphatic alcohols such as propyl alcohol and cyclohexyl alcohol, ethylene glycol, diethylene glycol and propylene glycol. And other polyhydric alcohols can be used in combination with the carboxylic acid. The amount of this alcohol used is as a mixture with carboxylic acid,
As above, the content is 10 to 40% by weight.

In addition, (meth) acrylic acid ester and styrene are typical examples of the polymerizable monomer having a transparent polymer.

Examples of the (meth) acrylic acid ester include alkyl (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate or cyclohexyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, (meth) acrylic acid Benzyl, phenyl (meth) acrylate, allyl (meth) acrylate, methallyl (meth) acrylate, β-naphthyl (meth) acrylate, β-aminoethyl (meth) acrylate, 2-methoxy (meth) acrylate Ethyl, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4 butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, penta Erythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, and halogen-substituted (meth) acrylates thereof.

Further, as the polymerizable monomer, a copolymerizable monomer can be used to the extent that the transparency of the obtained beads is not impaired. Examples of such a copolymerizable monomer include vinyl acetate, acrylonitrile, and methacrylonitrile. In addition, cross-linkable beads can be formed by adding a polyfunctional acrylate such as ethylene glycol diacrylate or diethylene glycol dimethacrylate.

Formation of a double salt of neodymium carboxylate and carboxylic acid is
It is carried out by adding neodymium carboxylate and carboxylic acid to the polymerizable monomer, stirring and mixing. This mixture is
It is performed at room temperature or under a temperature condition of heating to a temperature of 100 ° C. or less, and by stirring for 0.5 to 5 hours, a double salt is produced and dissolved in the polymerizable monomer. By this operation, a polymerizable mixed solution in which neodymium carboxylate, carboxylic acid and polymerizable monomer are uniformly dissolved is obtained.

Next, the polymerizable mixture solution thus obtained is subjected to suspension polymerization to obtain the target photoselective functional transparent beads.
For the suspension polymerization, a method in which the above-mentioned polymerizable mixed solution and the polymerization initiator are suspended in a normal aqueous phase is used.

As polymerization initiators, α, α′-azobisisobutyronitrile, α, α′-azobis (2,4-dimethylvaleronitrile), α, α′-azobis (2,4-dimethyl-4-yl)
Azobis compounds such as methoxyvaleronitrile are used.

This polymerization initiator can be used alone or in combination of two or more kinds. The amount of the polymerization initiator used depends on the amount of the polymerizable component in the polymerizable solution.
0.001 to 1 part by weight based on 100 parts by weight.

In order to stabilize the suspended particles, a protective colloid such as polyvinyl alcohol, carboxymethyl cellulose, sodium polyacrylate, alginic acid, and gelatin can be appropriately added.

The polymerization conditions are preferably set to a temperature of 30 to 90 ° C. and a time of about 1 to 10 hours, but are not limited to this range.The polymerization is performed first at a low temperature, and then the temperature is increased to continue the polymerization. A method is also used.

After the polymerization is completed, the polymer particles are dehydrated, washed with water and dried by a conventional method to obtain transparent spherical spherical photoselective functional beads.

The light-selective functional transparent beads are classified into a desired particle size range by a classifier such as a wind micron separator and dispersed in the transparent resin composition.

The light-selective functional transparent beads thus obtained are
The neodymium compound is contained in the transparent polymer in the state of being copolymerized with the transparent polymer or dissolved therein, and the beads themselves become transparent. Further, due to the presence of the neodymium compound, there is light absorption in the vicinity of 580 nm, and since the neodymium compound is in the state of copolymerization bond with the transparent polymer or in the dissolved state, sharp absorption with a large absorptivity is observed. Furthermore, since the beads themselves are not required to have mechanical properties so severely, the content of neodymium can be made sufficiently high, for example, the content can be increased to about 15% by weight. Furthermore, by appropriately changing the polymerization conditions, various particle sizes can be obtained,
The refractive index of the beads themselves can be changed according to the intended use by changing the polymerizable monomer, neodymium carboxylic acid, carboxylic acid type, blending ratio, and the like.

The light-selective functional transparent beads thus obtained are
The photoselective functional resin composition of the present invention is obtained by being dispersed in a transparent resin composition.

As the transparent resin composition here, if it has transparency, it is used regardless of whether it is thermoplastic or thermosetting, polymethylmethacrylate, polystyrene, polyvinyl chloride, acrylonitrile-styrene copolymer, Polycarbonate, cellulosic plastic, etc. are used.

Examples of the molding method include extrusion molding, injection molding, and calendar molding. In these molding methods, pre-polymerized polystyrene, polyvinyl chloride or polymethylmethacrylate pellets and the like are mixed with a predetermined amount of the above beads, and after mixing, a sheet, a film or an extruder, an injection molding machine, or a calendar is used. Molded articles of various shapes. When an acrylate such as polymethylmethacrylate is used as the transparent resin composition, a molded product can be obtained by a so-called cell cast method. That is, the beads are added to the acrylate partial polymer, and the mixture is injected into a mold to perform polymerization.

In addition to this transparent resin composition, a transparent molded article can be obtained by matching the refractive index of the beads with the refractive index of the transparent resin composition that serves as a matrix. Further, if the particle diameter of the beads is 0.2 μm or less, good transparency can be obtained even if the two have different refractive indices. Also, when beads with a particle size of 0.5 mm to 2 mm are added, it has a rough appearance, and with beads with a particle size of 50 to 100 μm, it has a frosted or milky (semi-translucent) appearance. Present. It is also possible to use other light-diffusing materials such as titanium oxide, talc, and barium sulfate in combination to achieve a semi-tone milk.

The amount of the light-selective functional transparent beads added to the transparent resin composition depends on the neodymium content in the beads and the use of the molded article, but the transparent resin composition 10
The amount is usually 2 to 30 parts by weight with respect to 0 parts by weight. In the case where the resin product contains neodymium in the form of beads containing such a neodymium compound, the mechanical properties of the transparent resin composition itself as the matrix do not deteriorate, and as a result, a large amount of neodymium is added. It becomes possible to exist in the final resin product, the photoselective functionality of neodymium can be fully exerted, and the mechanical properties and the like of the final resin product are hardly deteriorated.

Further, a colored molded article can be prepared by using a coloring agent such as a pigment or a dye together. When using this colorant together,
Wavelengths 380-420nm, 480-530nm, 560-610nm and 640-7
A coloring agent having an absorption in at least one wavelength range of 80 nm and having little or no absorption with respect to visible light in a wavelength range other than the above is blended, thereby supplementing selective absorption by the neodymium compound. Alternatively, selective absorption can be performed in the visible light wavelength range in which the neodymium compound has no absorption. Examples of the colorant having such an action include dyes, pigments, and ultraviolet absorbers described below.

Colorants having a main absorption in the wavelength range of 380 to 420 nm include phenyl salicylate and para-te-salicylate.
salicylic acid esters such as rt-butylphenyl, 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-
benzotriazoles such as tert-butylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2,2'-dihydroxy-4-octo There are ultraviolet absorbers such as benzophenones such as xylbenzophenone.

Colorants having a main absorption in the wavelength range of 480 to 530 nm include Hostazol Red GG (manufactured by Hoechst), Variogen Red 3730 (manufactured by BASF), and Diaresin Red HS (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) ), Diaresin Red S (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), Amablast Pink P4B (manufactured by American Aniline Co., Ltd.), and orange C-type (manufactured by Hercules Co., Ltd.).

Colorants having a main absorption in the wavelength range of 640 to 780 nm include Yuvinyl Blue 702 (manufactured by BASF), Oil Blue 615 (manufactured by Orient Chemical Industry Co., Ltd.),
Blue dyes such as Macrolex Green 513 (manufactured by Bayer), Seikagen O Blue GK-1200 (manufactured by Dainichiseika Kogyo Co., Ltd.), Sumitoncyanine Blue HB-1 (manufactured by Sumitomo Chemical Co., Ltd.) There is.

There is no suitable coloring agent having absorption mainly in the wavelength range of 560 to 610 nm, but among the coloring agents having absorption mainly in the above three wavelength ranges, those having absorption also in the wavelength range of 560 to 610 nm. Is preferably used. Such a coloring agent is, for example, Euvinyl Blue 702 (manufactured by BASF).

With such a colorant, light other than the three primary colors of red, green, and blue light is absorbed, and especially the color
When used as a filter for covering the light emitting surface of a CRT or the like, the color purity of the light emitted from the phosphor is improved, the color reproducibility is improved, and it is possible to prevent deterioration of contrast while maintaining high brightness.

The resin molded product having such light selection functionality is used for, for example, filters, lenses, lighting covers, image screens such as rear projection screens, signboards, and glazing.

 Specific examples will be shown below.

Production Examples 1 to 7 (Production of Light-Selective Functional Transparent Beads) (Production Example 1) 34% by Weight of Neodymium Methacrylate in Methyl Methacrylate
42% by weight, 15% by weight of lauric acid, and 9% by weight of propylene glycol were placed in a flask and heated to 65 ° C. with stirring and dissolved in about 2 hours.

Then, a stirrer, 100 parts by weight of the neodymium monomer mixture in an autoclave container with a nitrogen gas inlet,
0.5 parts by weight of azobisisobutyronitrile, 3.0 parts by weight of polyvinyl alcohol, and 800 parts by weight of water were replaced with nitrogen gas under high speed stirring, and then the container was heated to carry out the first stage polymerization at 75 ° C. for 4 hours.
The polymerization was completed by heating the second stage polymerization at 90 ° C. for 1 hour.

Thereafter, dehydration, washing with water and drying were performed as usual to obtain transparent spherical beads. This was classified with a wind micro separator to obtain beads having a desired particle size.

(Production Examples 2 to 7) Neodymium methacrylate and lauric acid or octanoic acid were mixed at the mixing ratio shown in column A of Table 1 and heated and dissolved at 65 ° C. Next, a predetermined amount of the monomer shown in column B of Table 1 is added and dissolved at room temperature. After removing a small amount of insoluble matter, suspension polymerization was performed in an autoclave in the same manner as in Production Example 1 to obtain beads.

Examples (Examples 1 to 6) As a polymerization catalyst, a partial polymer of methyl methacrylate (polymerization rate: 20%) and 100 parts by weight of a monomer copolymerizable therewith were used as a polymerization catalyst. Dimethyl valeronitrile) 0.04 part by weight, dioctyl sulfosuccinate sodium salt as a releasing agent 0.005 part by weight, and the neodymium-containing beads obtained in Production Examples 1 and 4 were added, mixed and degassed in the composition shown in Table 2. Thereafter, it was poured into a mold composed of a reinforced glass whose thickness was previously set to 3 mm and a soft vinyl chloride gasket, and immersed in 70 ° C. hot water for 80 minutes. It was then placed in a 130 ° C. air bath for 80 minutes to complete the polymerization. The optical performance and the spectral transmittance curve of the cast sheet obtained by removing the mold are as shown in Table 2 and FIG. The cast sheet thus obtained has light diffusivity and strong absorption near a wavelength of 580 nm. Therefore, when used as a lamp cover for an incandescent lamp or a halogen lamp, the color rendering effect is increased and it is found to be useful as a lighting fixture.

(Examples 7 to 9, Comparative Example 1) Acrypet VH (methacrylic resin pellets manufactured by Mitsubishi Rayon Co., Ltd.) and the neodymium-containing beads obtained in Production Examples 3 and 6 were blended so as to have the composition shown in Table 3. After mixing thoroughly with a tumbler and homogenizing, use an extruder to
It was extruded from a die under the condition of 260 ° C. and passed through three mirror-finished rolls for cooling to obtain a resin plate having a plate thickness of 3 mm. Table 3 shows the optical performance. From the results in Table 3, it is possible to add transparent polymer beads having a refractive index different from the refractive index of the inorganic diffusing agent or the base material, if necessary. Absorption of light is observed, and by constructing the cover of the light source with these, a colorful lighting fixture can be obtained.

(Examples 10 to 12 and Comparative Examples 2 and 3) Cast sheets (Examples 10 and 11 and Comparative Examples 2 and 3) were cast by the same casting polymerization method as shown in Example 1 so as to have the structure shown in Table 4. An extruded sheet (Example 12) was produced by the same extrusion method as described in Example 7. The sheets of any of the examples are light diffusive in which the neodymium-containing polymer beads are uniformly dispersed, while the sheets of the comparative examples do not contain neodymium. The chemical performance of these sheets is shown in Table 4.

[Effects of the Invention] As described above, the photoselective functional resin composition of the present invention contains a large amount of a neodymium compound, and the transparent resin composition is a photoselective functional transparent bead exhibiting sharp absorption near a wavelength of 580 nm. In addition to having excellent photoselective functionality, even when the neodymium content is sufficiently increased, mechanical properties and the like are not deteriorated.

[Brief description of drawings]

1 and 2 are spectra showing the spectral characteristics of the resin sheet obtained by the present invention.

Claims (1)

(57) [Claims] 1. A transparent resin composition containing light-selective functional transparent beads having a particle diameter of 0.01 μm to 5 mm, which is obtained by containing a neodymium compound in a transparent polymer in a dissolved state or in a copolymerized state with the transparent polymer. A photoselective functional resin composition characterized by the above.