JP2667878C - - Google Patents
Info
- Publication number
- JP2667878C JP2667878C JP2667878C JP 2667878 C JP2667878 C JP 2667878C JP 2667878 C JP2667878 C JP 2667878C
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- light
- refractive index
- resin
- transparent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000010419 fine particle Substances 0.000 claims description 59
- 239000002245 particle Substances 0.000 claims description 33
- 229920003023 plastic Polymers 0.000 claims description 20
- 239000004033 plastic Substances 0.000 claims description 13
- 239000011324 bead Substances 0.000 description 25
- 239000011347 resin Substances 0.000 description 25
- 229920005989 resin Polymers 0.000 description 25
- 239000000463 material Substances 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- 238000009792 diffusion process Methods 0.000 description 15
- 239000011521 glass Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- 239000000113 methacrylic resin Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000006188 syrup Substances 0.000 description 3
- 235000020357 syrup Nutrition 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-Butanediol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L Barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M Lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000001186 cumulative Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical Effects 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing Effects 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K Aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 241000209134 Arundinaria Species 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N Azobisisobutyronitrile Chemical compound N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 229960003563 Calcium Carbonate Drugs 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L Calcium fluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N Diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229940117969 NEOPENTYL GLYCOL Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- -1 acryl groups Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N butylene glycol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- BHBPJIPGXGQMTE-UHFFFAOYSA-N ethane-1,2-diol;2-methylprop-2-enoic acid Chemical compound OCCO.CC(=C)C(O)=O.CC(=C)C(O)=O BHBPJIPGXGQMTE-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- YZUUTMGDONTGTN-UHFFFAOYSA-N nonaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCO YZUUTMGDONTGTN-UHFFFAOYSA-N 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910001929 titanium oxide Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
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ãã¯ãåŸãããšãå¯èœãšãªã£ããDescription: TECHNICAL FIELD The present invention relates to a light-diffusing plastic suitable for a member for the purpose of diffusing light, such as a lighting cover, a lighting sign, a glazing, various displays or a transmission screen. is there. (Prior art) Conventionally, as a light diffusing material such as a lighting cover or a display screen, a material in which inorganic or organic transparent fine particles are dispersed in a transparent plastic such as an acrylic resin or a styrene resin, or a transparent plastic surface is used. Materials and the like that have been rented by some method are known, and it is known to use them in combination. In recent years, many efforts have been made for higher performance materials, especially as the need for light-diffusing plastics, which require high performance such as screens for rear projection televisions, increases. The desired performance of these light-diffusing materials is to diffuse light uniformly and brightly over as wide a range as possible. However, since the amount of light emitted from the light source is constant, these requirements are mutually contradictory requirements. Therefore, in practice, it is selected and used so as to obtain the most preferable luminance and spread by a method such as changing the concentration of the diffusion material as necessary. In a method of obtaining a light diffusing material by dispersing a light diffusing material in a transparent plastic, as an index for obtaining a suitable combination of the light diffusing material and the transparent plastic, the particle diameter of the light diffusing material fine particles and the light diffusing material fine particles are mainly used. And the difference in the refractive index of transparent plastic has been used. For example,
In the publication No. -10515, the difference in refractive index from the base transparent resin is 0.05 to 0.3,
A method of using crosslinked fine particles having an average diameter of 0.5 to 5 Ό as a light diffusing material is described, and Japanese Patent Application Laid-Open No. 48-43333 discloses a refraction that is 0.05 to 0.5 larger than a base resin. A method of blending a crystal powder having a refractive index of 10 Όm or less is described. Further, JP-A-60-139758 discloses that a difference in refractive index is 0.02.
A particle size of 10 to 50 ÎŒm and a particle size of 4 to 10 ÎŒm are proposed in JP-A-60-184559. 61
As disclosed in Japanese Patent No. 4762, the particle size is 4 to 50 ÎŒm and the refractive index is 0.02
A method is also described in which fine particles having a particle size of 4 to 50 ÎŒm and a refractive index of 0.02 to 0.1 are used in combination with fine particles having a particle size of 0.1 to 0.1. In addition, JP-B-60-21662 or JP-A-62-174261 discloses that the refractive index is 0.0
A method of dispersing fine particles having a small average particle diameter of 1 to 10 ÎŒm and 1 to 10 ÎŒm has also been proposed. In addition, the combinations of the base resin and the light diffusing material with specific descriptions are extremely diverse, and it is difficult to describe all of them. For example, methacrylic resin (
When the base resin has a refractive index of 1.492), crystalline silica (refractive index 1.5
4) amorphous silica (refractive index 1.46), calcium carbonate (refractive index 1.58),
Aluminum hydroxide (refractive index 1.57), glass beads GB-210 (refractive index 1
. 521), glass spheres (refractive index 1.46), calcium fluoride (refractive index 1.43)
), Lithium fluoride (refractive index: 1.39), barium sulfate (refractive index: 1.64), alumina powder (refractive index: 1.7), other refractive indexes are unknown, but magnesium oxide, titanium oxide, talc and crosslinked Even when a polymer or the like is used and a base resin is a polystyrene resin (refractive index: 1.59), polyvinyl chloride resin (refractive index: 1.55) or polycarbonate resin (refractive index: 1.59), various inorganic materials are used. Fine particles are used. As described above, when the technologies that have been disclosed in the past are arranged, the refractive index difference,
Although many methods have been proposed for the particle size, a very wide range has been proposed, and it is currently difficult to determine which combination is preferred. In fact, additional tests have shown that these existing technologies are still inadequate against the ever increasing demands for screens and the like for rear projection televisions in recent years. (Problems to be Solved by the Invention) The present invention has excellent light diffusion performance in such a cluttered technical flow, that is, the maximum luminance Go is as large as possible, and the half-value angle (luminance is 1). It is an object of the present invention to provide a light-diffusing material which has as large an angle as possible (down to / 2), and in which transmitted light does not have a reddish tint. (Means for Solving the Problems) In the present invention, the following formulas (I) and (
II) 0.02 ⊠âNpâNsâ ⊠0.04 (I) Average particle diameter d (micron) satisfying 7 ⊠d <30 (II), refractive index Np, and voids inside By dispersing the transparent spherical inorganic fine particles in which the ratio of the particles having the total fine particles to the total fine particles is 3% by weight or less, the ratio of the non-spherical particles in the transparent fine particles to the total transparent fine particles is 10% by weight or less. This is preferably achieved. As a substantially transparent plastic, methacrylic resin or methyl methacrylate (hereinafter MM)
A) and a styrene copolymer resin, MMA and polyfunctional (meth) acrylate or fine particles of MMA, styrene and polyfunctional (meth) are used as fine particles.
The above object can be achieved by using crosslinked copolymer fine particles containing acrylate as a component. (Action) The present inventors have comprehensively studied the relationship between the refractive index difference between the base transparent resin and the transparent fine particles, the particle size of the transparent fine particles, and the diffusion performance, and have reached the present invention. That is, in the present invention, the absolute difference | NpâNs between the refractive index Ns of the base transparent resin and the refractive index Np of the transparent fine particles.
| Is 0.02 or more and 0.04 or less. The present inventors have prepared various flat plates in which the refractive index difference between the base resin and the transparent fine particles and the particle size of the transparent fine particles are changed, and a parallel light is incident from the rear of the flat plate, and the angular distribution of the brightness of the light emitted forward. Was measured, and a gain G was calculated from the illuminance on the flat plate surface and each luminance by the following equation. G = Luminance (Foot Lambert) / Illuminance (Foot Candle) (VI) The gain shows the highest value in front of the diffuser, and as the angle between the diffuser and the normal increases, as shown in FIG. Becomes smaller. The highest value of cane and be represented by the peak gain and called G o, the gain is to be represented by α is referred to as half-value angle angle becomes 1/2 of Bikukein, object of the present invention is larger both the Go and α Is to do. However, in general, the light diffusion plate is not always used in the form of a simple flat plate, and often achieves its purpose by giving various lens shapes or by using another light diffusion imparting means such as surface treatment. , G o , α, etc. also vary depending on their type and degree, and it is not appropriate to express the objective performance of the present invention by the values of G o and α by such measuring means. However, when a large combination of Go and α measured with a flat light diffusing plate is employed in this way, it can be experimentally confirmed that excellent performance can be obtained in other shapes. Mainly adopted a flat plate method in which the light diffusion performance of the light diffusion material can be easily compared and evaluated. In combination with certain substrate resin and the light diffusing material, changing the concentration of the light diffusion material, accompanied connexion G o increasing concentration as in the second view is reduced, alpha increases. Therefore, as a means for selecting a good light diffusing material, the concentration of the light diffusing material is changed to select a concentration at which a constant Go is obtained, and a material having a large half-value angle α at that concentration is a preferable light diffusing plastic. I thought. As a result of the experiment, the refractive index difference was 0.02
It has been found that when the ratio is 0.04 or less, a light-diffusing plastic having an extremely high α at a certain Go is obtained. Furthermore, in the present invention, it is necessary that the average particle diameter of the light diffusing transparent fine particles is 7 Όm or more and less than 30 Όm. Πis reduced at a certain G o If the mean particle diameter is outside this range. In particular, when the average particle diameter does not reach 7 Όm, when the concentration of fine particles is low, a large amount of light travels at a limited solid angle in the straight traveling direction, and this light is reddish. When Yuku gaining particle concentration, but the light reddish straightness is reduced, G o is the abnormal light does not go away until the very low value. This light is perceived as so-called scale when observed by human eyes. The human eye can usually be distinguished at a viewing angle of 1 minute (= 1/60 degrees), and measuring this invisibility phenomenon with an optical measuring device (luminance meter) is comparable to that of the human eye. It is necessary to use a device having a viewing angle of. Conventionally, there is no correlation between the data of the angular distribution of luminance and the scale in literatures, etc.,
This is probably due to the difference in viewing angle between the human eye and the luminance meter. At present, the viewing angles of commercially available luminance meters are 2, 1, 1/3, 0.2 degrees, etc., all of which are larger than 1/60 degrees. Considering that the viewing angle is as small as possible and that stable measurement can be performed, the inventors of the present invention have used a Minolta luminance meter nt1 / 3 ° manufactured by Minolta with a viewing angle of 1/3 °.
The measurement was performed using P. As a result, it was possible to measure intense light concentrated in an extremely narrow angle range in response to the phenomenon of invisibility, and it was found that it was reflected to some extent on the values of Go and α. When the average particle diameter of the fine particles is less than 7 Όm, it is necessary to increase the concentration of the light diffusing material until the maximum luminance becomes extremely low in order to prevent skein, and to obtain a light diffusion plate having no skein and a large gain. Not suitable for Average particle size is 30
If the particle size is more than Όm, the concentration of the fine particles used becomes too large, which is not only economically disadvantageous from the viewpoint of production technology, but also reduces the half-value angle as compared with the case of a particle size within the range of the present invention. There are various definitions for the average particle diameter. The average particle diameter in the present invention is represented by a weight median diameter, that is, a particle diameter at which the cumulative weight fraction becomes 50% in a weight cumulative curve. Methods for measuring the particle size distribution include a Coulter counter method, a sedimentation method, a counting method using a micrograph or an electron micrograph, and the like, and any method may be used. In the present invention, factors relating to the shape of the light diffusing fine particles are very important. That is, the light-diffusing fine particles need to have a ratio of the hollow fine particles in the fine particles of 3% by weight or less, preferably substantially spherical fine particles which do not substantially contain the hollow fine particles. Although glass beads are generally well-known spherical fine particles, the present inventors have studied that, by applying the above-described refractive index difference and particle size range, the performance can be improved even when glass beads are used. Was found to be inferior to that of crosslinked plastic beads having the same particle diameter and refractive index as described below. In addition, there are various crushed inorganic powders as fine particles substantially containing no hollow portion, and by using these in a range that satisfies the above conditions, an excellent light diffusing plastic can be obtained, but fine particles having a spherical shape can be obtained. who is, as compared with such amorphous particles, the half value angle α increases in the diffusion plate at a concentration giving the same peak Kane G o, more preferably. In the case of glass beads, etc., it is common that crushed fine particles and spherical fine particles are mixed,
Further, for the purpose of reducing the ratio of hollow beads, it is also possible to improve the performance by mixing crushed fine particles into ordinary glass beads, and it is actually effective, but preferably the ratio of spherical fine particles is high as described above. Is more preferred. Non-spherical fine particles are preferably 3
0% or less, more preferably 10% or less, and most preferably substantially not contained. In order to satisfy the above-mentioned conditions of the difference in refractive index, particle diameter and shape, it is advantageous and preferable to use a polymer, particularly a crosslinked polymer, as the transparent fine particles. In the case of crosslinked polymer fine particles, the refractive index can be adjusted by the polymer composition, and by an appropriate polymerization method, substantially no hollow portion can be obtained, and substantially spherical fine particles can be obtained. . In general, light-diffusing plastics are prepared by melting and kneading light-diffusing fine particles and a substrate resin and extruding, or by pressing, or, in some cases, dispersing the light-diffusing fine particles in a polymerizable monomer or partially polymerized polymerizable monomer syrup. It is made by a method of polymerizing. Therefore, it is necessary that the light diffusing fine particles do not change into an undesired shape due to melting, melting, etc. during the process of producing the light diffusing plastic. For this purpose, it is possible to use a method in which the molecular weight of the polymer is sufficiently high, but it is more preferable to provide appropriate crosslinking. As the base resin of the light diffusing plastic, a transparent resin having a high light transmittance, that is, methacryl resin, polystyrene resin, polycarbonate resin, epoxy resin, polyvinyl chloride resin and the like are used. Among them, methacrylic resin is a preferable resin because of its excellent durability and physical properties. Normally, methacrylic resin copolymerizes an alkyl acrylate in addition to MMA for the purpose of improving heat resistance, moldability, durability, and the like, or adds a lubricant and an ultraviolet absorber. MMA refers to all resins mainly composed of MMA. When the base resin is a methacrylic resin, it is preferable to use fine particles which are cross-linked resins containing MMA, styrene and polyfunctional (meth) acrylate as constituents. Since ordinary methacrylic resin has a refractive index of about 1.49, the refractive index of the light diffusing agent fine particles is 1.51 to 1.
It is preferably about 53. Of course, the refractive index may be slightly higher or lower depending on the type of methacrylic resin as the base resin . The polyfunctional (meth) acrylate is a compound having two or more acryl groups or methacryl groups in one molecule, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate. ) Acrylates, (poly) ethylene glycol di (meth) acrylates such as nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate. A) acrylate, hexamethylene di (meth) acrylate, glycol di (meth) acrylate such as neopentyl glycol di (meth) acrylate, as well as trimethylolpropane tri (meth) acrylate, pentaerythr There Toll tetra (meth) polyhydric polyalcohols such as acrylates (meth) acrylate. These polyfunctional (meth) acrylates serve to prevent the transparent fine particles from impairing the shape of the fine particles in the process of producing the light-diffusing plastic, and 2% to 60% of the total monomers constituting the transparent fine particles. % Is appropriately selected. When a copolymer of styrene and MMA is used as the base resin, the refractive index is increased, and the effect as a lens is enhanced, which may be advantageous. In such a case,
It is desirable to use a crosslinked copolymer similar to the transparent fine particles used for the methacrylic resin. However, an appropriate refractive index may be adjusted according to the refractive index of the styrene-MMA resin. The polymer beads described above can be synthesized by a suspension polymerization method. For example, it can be produced by dispersing a monomer finely with a disperser or the like using polyvinyl alcohol as a dispersant, and then polymerizing, filtering, washing and drying. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Reference Example 1 34 parts of MMA, 16 parts of styrene, 50 parts of ethylene glycol dimethacrylate, and 0.2 part of lauroyl peroxide were mixed with polyvinyl alcohol (Kuraray Co., Ltd.)
VA-420) was mixed with 300 parts of water containing 0.4%, and dispersed with a laboratory disperser. This solution was stirred at 70 ° C. for 20 minutes in a nitrogen atmosphere and at 95 ° C. for 5 minutes.
Heated for 0 minutes. The resulting dispersion was filtered and washed repeatedly with water, and finally washed with methanol and dried. When the particle size distribution of the crosslinked fine particles thus obtained was measured with a particle size distribution meter (Microphotosizer-SKA-5000, manufactured by Seishin Enterprise), the weight median diameter was 10.58 ÎŒm. As the specific gravity at this time, a value (1.1891) measured separately by preparing a polymer having the same composition was used. The refractive index was measured by a method of observing the movement behavior of the Becke line under a microscope, and was found to be 1.5174. Also, the beads were substantially all spherical and free of hollow particles. Using these crosslinked beads, methacrylic resin plates having a thickness of 1 mm and containing beads at various weight fractions were prepared by the following method. Acrylic resin beads obtained by copolymerizing 8.5% of ethyl acrylate in a mixture of 11.9 parts by weight of ethyl acrylate and 128.1 parts of MMA (F-1 manufactured by Kyowa Gas Chemical Industry Co., Ltd.)
(000B refractive index 1.4920) 60 parts by weight were dissolved to prepare an acrylic resin syrup. The required amount of the crosslinked beads was dispersed in this syrup while taking care not to aggregate. 0.02 parts by weight of azobisisobutyronitrile was dissolved therein, put into two glass plates equipped with gaskets, degassed, and heated at 80 ° C. for 2 hours and further at 120 ° C. for 2 hours. Polymerized. The thickness was adjusted so as to be 1 mm. After the completion of the polymerization, an acrylic plate containing fine particle beads was taken out from the glass plate. The collimated light of the halogen lamp was incident on the fine-particle-containing acrylic resin plate (light diffusion plate) thus obtained from the rear. A luminance meter (Minolta luminance meter nt1 / 3 ° P) was installed 1.5 m ahead of the light diffusion plate, and the luminance was measured. The position of the luminance meter was shifted, the angle was changed, and the operation of measuring the same portion was repeated, and the angular distribution of luminance was measured. On the other hand, the illuminance at the position of the light diffusing plate was separately measured by an illuminometer, and the gain was calculated from the ratio of the luminance to the illuminance by the equation (VI). As gain G o of the front, the angle at which Kane is 1/2 of the G o alpha, indicating the value of each concentration shown in Table 1. When this result is plotted on a log-logarithmic graph in which the vertical axis is G o and the horizontal axis is α,
It looks like the figure. From this figure, α is 7.8 ° at the concentration where Go is 20. This value is larger than the value shown in a comparative example described later, and this light diffusion plate is an excellent material having a large diffusion half-value angle at a constant peak gain. In the same manner as in Reference Examples 2 to 4 and Comparative Examples 1 and 2, a light-diffusing plastic was produced using various fine particles and a base resin as shown in Table 2, and the light-diffusing performance was measured. Second measurement result
It is shown in the table. Example 1 The same glass beads GB-210 (manufactured by Toshiba Barotini) used in Comparative Example 1 were prepared from a mixture of 1,1,2,2-tetrabromoniethane and monochlorobenzene with a specific gravity of 2.424. When the glass beads were immersed in the liquid and centrifuged, the glass beads were separated into those that floated on the upper layer and those that settled on the lower part. Each phase is separated, washed and dried, and a mixture of methylene iodide and carbon tetrachloride having a refractive index of about 1.
When placed in the liquid of No. 521 and observed with an optical microscope, the glass beads in the sedimentation part were seen through the boundary between the liquid and the beads, while the glass beads in the floating part were clearly observed with the core part black and clear. This was similar to the case where the hollow beads were separately observed in the same manner. The weight of the beads at the floating portion thus obtained was 4.7% of the weight of the beads before separation. Table 2 shows the results of the light diffusing plate obtained by the same method as in Reference Example 1 using the glass beads in the settled portion obtained by this method as a light diffusing agent. Compared with the case of Comparative Example 1, α at the time when the peak quin was 20 was large, and the performance as a light diffusing agent was improved. (Effects of the Invention) According to the present invention, it has become possible to obtain a light-diffusing plastic having a high front luminance and a large diffusion half-value angle.
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ãã瞊軞ã暪軞ãšãã«å¯Ÿæ°ç®çã§ç€ºããŠãããBRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the angular distribution of the gain at each crosslinked bead concentration in Reference Example 1 , where the vertical axis is a logarithmic scale and the horizontal axis is an equally spaced scale. FIG. 2 is a graph showing the peak gain and the half-value angle of Example 1 , Reference Examples 1 to 4 and Comparative Examples 1 and 2, and both the vertical and horizontal axes are shown on a logarithmic scale.
Claims (1)
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ããã¯ã [Claim 1] In a transparent plastic having a refractive index Ns, the following formula (I):
And (II) 0.02 ⊠| NpâNs | ⊠0.04 (I) having a refractive index Np and an average particle diameter d (ÎŒm) satisfying 7 ⊠d <30 (II). A light-diffusing plastic obtained by dispersing transparent spherical inorganic fine particles such that the proportion of voids is 3% by weight or less. 2. The ratio of non-spherical fine particles to all fine particles among fine particles is 10%.
2. The light diffusing property according to claim 1, wherein the light diffusing property is not more than% by weight.
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