(Meth)acrylates, resin composition using the same and ultraviolet-curing resin composite for transmission type screens

Abstract: This invention relates to (meth)acrylates represented by formula (1): wherein, R₁ and R₂ are each independently H or CH₃ and average value of n is 1 - 5; resin composite comprising (A) an urethane (meth)acrylate and/or epoxy (meth)acrylate, (B) a (meth)acrylate represented by formula (1) above, (C) an ethylenically unsaturated compound other than component (A) or (B), and (D) a photopolymerization initiator; and cured products of said resin composites. The cured products of said resin composites of this invention have high refractive index and are superior in mold release property, shape reproducibility, restorability, and scratch resistance and suited in particular for transmission type screens.

Description: This invention relates to novel (meth)acrylates, which are useful as components for ultraviolet- or electron beam-curing resin composites, or more specifically as components for resin composites for lens and light-controlling films, resin composites using said esters, and in particular ultraviolet-curing resin composites suitable for transmission type screen such as Fresnel lens and lenticular lens used in video projectors and projection televisions and cured products of said resins. Such types of lens have, heretofore, been formed by methods such as pressing and casting. The former has low productivity, since production by pressing is done through a cycle of heating, pressing and cooling. The latter requires long production time and high cost, since in casting, monomer is poured into metal molds and polymerized, and large number of molds are required. In order to solve such problems use of ultraviolet-curing resin composites have been variously proposed (see e.g. GB2230618). By using such ultraviolet-curing resin composites, a method to produce transmission type screen has been successful to some extent. But there has been no proposal to meet the requirements of thin types such as projection television. Makromol. Chem. Rapid Commun. 1, 1980, pp. 183-186 & Chemical Abstracts, vol. 93, 1980, abstr. no. 26926b which studies the order in polymers with biphenylyl residues in the side-groups, discloses a (meth)acrylic ester of the formula: US-A-4,745,137 which discloses the inclusion of a polymer containing rigid moieties in an active hydrogen-containing compound discloses a (meth)acrylic ester of the formula: In order to solve the above described problem, the inventors of this invention have, as a result of ardent endeavor, discovered (meth)acrylates which have less smell, high curing speed by ultraviolet, and high refractive index and give soft cured products, and resin composites using said (meth)acrylate and completed this invention. That is, this invention relates to: (1) (meth)acrylates represented by formula (1) wherein, R 1 and R 2 are each independently H or CH 3 , and average value of n is 1 - 5, with the exception of the compound : and with the exception of the compound : (2) (meth)acrylate described in paragraph (1), represented by formula (2) wherein, R 1 and R 2 are each independently H or CH 3 , and average value of n is 1 - 5, (3) (meth)acrylate described in paragraph (1), represented by formula (3) wherein, R 1 and R 2 are each independently H or CH 3 , and average value of n is 1 - 5, excepted the compounds specified under (1) above, (4) (meth)acrylate described in paragraph (1), represented by formula (4) wherein, average value of m is 1 - 4, (5) resin composites characterized by containing; (A) urethane (meth)acrylate and/or epoxy (meth)acrylate, (B) (meth)acrylate represented by formula (1) described in paragraph (1), (C) ethylenically unsaturated compound other than (A) or (B), and (D) photopolymerization initiator, (6) resin composites described in paragraph (5), wherein (B) (meth)acrylate is a compound represented by formula (2) described in paragraph (2), (7) resin composites described in paragraph (5), wherein (B) (meth)acrylate is a compound represented by formula (3) described in paragraph (3), (8) resin composites described in paragraph (5), wherein (B) (meth)acrylate is a compound represented by formula (4) described in paragraph (4), (9) cured products of resin composites described in paragraph (5), (6), (7), or (8), (10) ultraviolet-curing resin composites for transmission screen, comprising resin composites described in paragraph (5), (6), (7) or (8), (11) cured products of ultraviolet curing resin composites for transmission screens described in paragraph (10). The (B) novel (meth)acrylate of this invention represented by formula (1) can be prepared by reacting a compound represented by formula (5), wherein, R 1 is H or CH 3 and average value of n is 1 - 5, with (meth)acrylic acid. The compounds represented by formula (5) are products formed, for example, by reaction between p-phenylphenol, o-phenylphenol or m-phenylphenol and ethylene oxide or propylene oxide. These products are readily available at the market. For example, there are Sanyo Chemical's product Newpol OPE-10 (product of reaction between 1 mol of o-phenylphenol and 1 mol of ethylene oxide), Newpol OPE-20 (product of reaction between 1 mol of o-phenylphenol and 2 mol of ethylene oxide), and Newpol OPE-40 (product of reaction between 1 mol of o-phenylphenol and 4 mol of ethylene oxide). The reaction between compounds represented by formula (5) and (meth)acrylic acid can be carried out in the presence of esterification catalyst such as p-toluenesulfonic acid or sulfuric acid and polymerization inhibitor such as hydroquinone, phenothiazine or methylhydroquinone, preferably under presence of solvent (for example toluene, benzene, cyclohexane, n-hexane, n-heptane and others), and preferably at temperature of 70 - 150°C. The amount of (meth)acrylic acid to be used per mol of compounds represented by formula (5) is normally 1 - 5 mol, preferably 1.05 - 2 mol. Esterification catalyst is added at concentration of normally 0.1 - 15 mol%, preferably 1 - 6 mol% based on (meth)acrylic acid used. (Meth)acrylate of this invention have little smell and high refractive index, and when used as component of ultraviolet- or electron beam-curing resin composite, provides soft cured product. The resin composites of this invention use (A) urethane (meth)acrylate and/or epoxy (meth)acrylate. As actual examples of urethane (meth)acrylates, reaction products of polyols such as ethylene glycol, 1,4-butane-diol, neopentyl glycol, polycaprolactone-polyol, polyester-polyol, polycarbonate-diol, polytetramethylene-glycol, organic polyisocyanates such as hexamethylen-diisocyanate, isoholon-diisocyanate, tolylenediisocyanete, xylylenediisocyanate, 4-4'-diphenylmethanediisocyanate and hydroxyl group-containing ethylenically unsaturated compounds such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, ε-caprolactone addition product of 2-hydroxyethyl (meth)acrylate, pentaerythrytol tri(meth)acrylate, can be mentioned. The above described urethane (meth)acrylate can be obtained by preparing urethane oligomer by reacting preferably 1.1 - 2.0 equivalent of isocyanate group of the organic polyisocyanates with 1 equivalent of hydroxyl group of polyols at preferably 70 - 90°C, followed by reacting preferably 1 - 1.5 equivalent of hydroxyl group of the hydroxyl group-containing ethylenically unsaturated compounds with 1 equivalent of isocyanate group of the urethane oligomer at preferably 70 - 90°C. As preferable urethane (meth)acrylate, polyester-urethane acrylate, polycaprolactone-urethane acrylate, polytetramethylene-urethane acrylate may be given. The number average molecular weight of urethane (meth)acrylate used in this invention is preferably 500 - 10,000. As concrete examples of epoxy (meth)acrylate, reaction products of epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenolnovolac-type epoxy resin, glycidyl-end-ether of bisphenol A-type propylen oxide addition product and fluorene-epoxy resin with (meth)acrylic acid may be given. The reaction of epoxy resins and (meth)acrylic acid is carried out at the ratio of preferably 0.8 - 1.5 equivalent, most preferably 0.9 - 1.1 equivalent of (meth)acrylic acid with 1 equivalent of epoxy group of the epoxy resins, using photopolymerizing vinyl monomer such as 2-hydroxyethyl (meth)acrylate, 2-hydroxylbutyl (meth)acrylate, trimetylolpropane tri(meth)acrylate, acryloylmorphorine, N-vinylpyrolidone, (meth)acrylic ester of phenyl glycidyl ether, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate as diluent during the reaction, preferably using catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, triphenylstibine) to accelerate the reaction. Amount of said catalyst used is preferably 0.1 - 10 wt.%, most preferably 0.3 - 5 wt.% based on the reaction mixture. It is preferable to use polymerization inhibitor (for example, methoquinone, hydroquinone, phenothiazine) to prevent polymerization during reaction. The amount of use is preferably 0.01 - 1 wt.%, more preferably 0.05 - 0.5 wt.% based on the reaction mixture. The reaction temperature is preferably 60 - 150°C, more preferably 80 - 120°C. Bisphenol A-type epoxy acrylate and bisphenol F-type epoxy acrylate may be given as preferred epoxy (meth)acrylate. The number average molecular weight of epoxy (meth)acrylate used in this invention is preferably 400 - 5,000. (B) (Meth)acrylate of the resin composite of this invention can be any compound represented by above described formula (1), but the compounds especially preferred are compounds represented by above described formula (4). As concrete examples of (C) ethylenically unsaturated compounds, which are component used in resin composite of this invention other than the (A) or (B), for example, N-vinyl-caprolactam, acryloylmorphorine, 2-hydroxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, phenylglycidyl-ether (meth)acrylate, isobornyl (meth)acrylate, tribromophenyl (meth)acrylate, tribromobenzyl (meth)acrylate, tribromo-phenyloxyethyl (meth)acrylate, dibromophenyl-glycidyl-ether (meth)acrylate, dicyclopentanyl (meth)acrylate, polyethoxy di(meth)acrylate of tetrabromobisphenol A, tetraethoxy di(meth)acrylate of bisphenol A, tetraethoxy di(meth)acrylate of bisphenol F, tricyclodecanedimethylol di(meth)acrylate, di(meth)acrylate of ε-caprolactone addition product of neopentyl glycol hydroxypivalinate may be given. Preferred (C) ethylenically unsaturated compounds are phenoxyethyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, acrylic ester of phenyl glycidyl ether, tribromophenyl methacrylate, tribromophenyloxyethyl acrylate, tetraethoxy diacrylate of bisphenol A. As (D) photopolymerization initiators, for example, copolymerizing photopolymerization initiators such as and benzoin, benzoin methy ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacepophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morphorino-propane-1-one, N,N-dimethylaminoacetophenone, 2-methyl-anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthra-quinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,4-demethylthioxanthone, 2,4-diethylthioxantone, 2,4-diisopropylthioxantone, acetophenone dimethylketal, benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone may be given. These may be used alone or as mixture of two or more. As especially preferred (D) photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one may be mentioned. Moreover, these (D) photopolymerization initiators may be used in combination with one or two or more publicly known and conventionally used photo sensitizers such as ethyl ester of N,N-dimethylaminobenzoic acid, iso-amyl ester of N,N-dimethylaminobenzoic acid, triethanolamine, and triethylamine. Preferred ratio of the components used for the resin composite of this invention is, (A) urethane (meth)acrylate and/or epoxy (metha)acrylate 10 - 50 wt.%, (B) (meth)acrylate 10 - 40 wt.%, (C) ethylenically unsaturated compound 10 - 70 wt.% and (D) photopolymerization initiator 0.1 -10 wt.%. In the resin composite of this invention, in addition to above described components, mold release agent, antifoaming agent, leveling agent, photostabilizer (for example, hindered amine), antioxidant, polymerization inhibitor, and antistatic agent may be used. The resin composite of this invention can be prepared by mixing and dissolving all the components. The resin composite of this invention is especially useful in transmission screen such as Fresnel lens and lenticular lens, but it is also useful in various coating agent, potting agent and adhesives. Cured product of the resin composite of this invention can be obtained by curing by ultraviolet irradiation conventional methods. Actually, the resin composite of this invention is applied onto, for example, a stamper with a shape of Fresnel lens or lenticular lens, to form a layer of said resin composite, hard transparent base board is placed on the layer, at this configuration ultraviolet light is irradiated on the said hard transparent base board side by high voltage mercury lamp or others to cure said resin composite, and removed from said stamper. In this manner, soft transmission type screen such as Fresnel lens or lenticular lens of refractive index (23°C) of normally 1.55 or above, under preferable conditions of 1.56 or above can be obtained. In the following, this invention will be more concretely explained by examples and applied examples. Evaluations in the applied examples were carried out as follows. "Part" in the examples means part by weight. (1) Release properties from mold: Ease of removal of cured resin from mold. ○ Removed from mold easily ▵ Removed from mold with some difficulty X Difficult to remove or stuck residue on mold (2) Shape reproducibility: Surface feature of cured ultraviolet curing resin and surface feature of metal mold are observed. ○ Good reproducibility X Poor reproducibility (3) Restorability: Finger nail is pressed on the surface, which was facing the metal mold, of the cured ultraviolet-curing resin and the surface was observed after allowed to stand for 30 minutes. ○ Scar of nail pressing not observed ▵ Slight scar faintly visible X Scar remaining. (4) Refractive index (23°C): Measurement of refractive index (23°C) of cured ultraviolet curing resin. (5) Scratch resistance: On the surface, which was facing the metal mold, of the cured ultraviolet-curing resin, an acrylic plate (width 15 mm, length 100 mm, thickness 2 mm) is vertically pressed on strongly, and the plate is moved between a distance of 100 mm at a speed of one go-and-back movement per second and ten back-and-forth movements are made. The scratches on the surface are observed. ○○ No scratches observed ○ A few line scars are observed ▵ Partial belt shape scars observed X Belt shape scars on whole test area Synthesis example of (A) urethane (meth)acrylate Synthesis example 1 120 parts of polyesterdiol (polyesterdiol of neopentyl glycol and adipic acid, molecular weight 2,000, OH value 56.1), 2.48 parts of ethylene glycol. 34.8 parts of tolylene-diisocyanate were charged, heated to 80°C and allowed to react for ten hours. 24.4 parts of 2-hydroxyethyl acrylate and 0.1 part of methoquinone were added and after ten hours of reaction at 80°C, urethane acrylate was obtained. Synthesis example 2 130 parts of poly(tetramethylen glycol) (molecular weight 650, OH value 172.6), 49.6 parts of ethylene glycol, and 348 parts of tolylenediisocyanate were charged and allowed to react for ten hours at 80°C. Then, 243.6 parts of 2-hydroxyethyl acrylate and 0.4 parts of methoquinone were added and after ten hours of reaction at 80°C, urethane acrylate was obtained. Examples of (B) (metha)acrylate represented by formula (1) Example 1 258 parts of a compound represented by formula (6) (produced by Sanyo Chemical Industries, Ltd., reaction product of 1 mol of o-phenylphenol and 2 mol of ethylene oxide, trade name: Newpol OPE-20, OH value 217.5), 86.5 parts of acrylic acid, 300 parts of toluene, 21 parts of sulfuric acid and 5 parts of hydroquinone were charged and the mixture was heated. The produced water was distilled out together with the solvent, condensed and collected in a separator. When 18 parts of water was collected at the separator, the reaction mixture was cooled. The reaction temperature was 130 - 140°C. The reaction mixture was solved in 500 parts of toluene, neutralized by 20% NaOH aqueous solution, and washed three times with 100 parts of 20% NaCl aqueous solution. By distilling off the solvent under reduced pressure, 303 parts of and acrylate represented by formula (7) was obtained. The viscosity (25°C) was 204 CPS and refractive index (23°C) was 1.567. The product was almost odorless. The results of high resolution NMR measurement of the product are shown below. No. ppm No. ppm 1 166.355 6 138.735 2 166.116 7 138.697 3 155.988 8 138.417 4 155.931 9 138.476 5 155.601 10 131.304 11 131.223 29 113.078 12 131.176 30 77.6764 13 131.127 31 77.2515 14 131.063 32 76.8249 15 129.814 33 70.9181 16 129.706 34 70.7309 17 128.775 35 70.6585 18 128.446 36 69.7294 19 128.310 37 69.6619 20 128.089 38 69.3804 21 128.033 39 69.1516 22 127.079 40 68.4765 23 127.035 41 68.4124 24 126.976 42 66.6048 25 121.878 43 63.8007 26 121.496 44 63.7501 27 121.433 45 62.7957 28 113.397 46 0.0000 The above measurement was done with tetramethylsilane as standard material and deuterochloroform as solvent and by proton decoupling method. Example 2 346 parts of a compound represented by formula (8) (produced by Sanyo Chemical Industries, Ltd., reaction product of 1 mol of o-phenylphenol and 4 mol of ethylene oxide, trade name: Newpol OPE-40, OH value 162), 86.5 parts of acrylic acid, 400 parts of toluene, 21 parts of sulfuric acid and 6 parts of hydroquinone were charged and the mixture were heated. The produced water was distilled out together with the solvent, condensed and collected in a separator. When 18 parts of water was collected at the separator, the reaction mixture was cooled. The reaction temperature was 130 - 140°C. The reaction mixture was solved in 500 parts of toluene, and 380 parts of an acrylate represented by formula (9) was obtained in the same manner as in Example 1. The viscosity (25°C) was 120 CPS and refractive index was 1.543. The product was almost odorless. Results of NMR measurement No. ppm No. ppm 1 166.357 24 126.988 2 166.118 25 121.880 3 155.990 26 121.498 4 155.933 27 121.435 5 155.603 28 113.399 6 138.737 2g 113.080 7 138.698 30 77.6766 8 138.419 31 77.2517 9 131.478 32 76.8281 10 131.306 33 70.9153 11 131.225 34 70.7311 12 131.178 35 70.6587 13 131.129 36 69.7296 14 131.065 37 69.6621 15 129.816 38 69.3806 16 129.706 39 69.1563 17 128.777 40 68.4767 18 128.448 41 68.4126 19 128.313 42 66.6050 20 128.092 43 63.8009 21 128.035 44 63.7503 22 127.082 45 62.7959 23 127.037 46 0.0000 Example 3 214 parts of a compound represented by formula (10), 86.5 parts of acrylic acid, 300 parts of toluene, 21 parts of sulfuric acid and 5 parts of hydroquinone were charged and the reaction was effected in the same manner as in Example 1. The reaction mixture was cooled when 18 parts of water was collected. 257 parts of an acrylate represented by formula (11) was obtained in the same manner as in Example 1. The viscosity (25°C) was 127 CPS and refractive index (23°C) was 1.576. The product was almost odorless. Results of NMR measurement No. ppm No. ppm 1 166.144 6 131.254 2 155.624 7 129.731 3 138.440 8 128.797 4 131.498 9 128.330 5 131.313 10 128.245 11 128.112 18 76.8080 12 127.101 19 66.6200 13 121.964 20 62.8143 14 121.897 21 59.8314 15 113.405 22 33.6902 16 77.6595 23 0.0000 17 77.2330 Example 4 241 parts of a compound represented by formula (12), 129 parts of methacrylic acid, 300 parts of toluene, 25 parts of sulfuric acid and 5 parts of hydroquinone was charged and the reaction was carried out in the same manner as in Example 1. The reaction mixture was cooled when 18 parts of water was collected. 316 parts of a methacrylate represented by formula (13) was obtained, in the same manner as in Example 1. The viscosity (25°C) was 190 CPS and refractive index (23°C) was 1560. The product was almost odorless. Results of NMR measurement No. ppm No. ppm 1 167.035 23 77.2515 2 166.951 24 76.8249 3 156.551 25 75.4962 4 156.502 26 75.4506 5 155.993 27 75.3056 6 135.244 28 75.0898 7 135.207 29 73.5452 8 135.005 30 73.4508 9 126.775 31 73.1692 10 126.446 32 73.0900 11 126.310 33 71.8978 12 126.089 34 71.8270 13 126.033 35 71.6415 14 125.079 36 70.1880 15 125.036 37 70.1425 16 124.975 38 70.0177 17 120.578 39 18.105 18 120.352 40 17.2970 19 120.035 41 17.1604 20 113.397 42 16.7524 21 113.053 43 0.0000 22 77.6764 Applied examples of the resin composite of this invention Applied Examples 5 - 11 Ultraviolet-curing resin composites of compositions shown in Table 1 (figures are weight parts) were placed between a Fresnel-lens metal mold and a 2.5 mm thick acrylic resin board (primer layer applied). Fresnel lens were obtained by curing with ultraviolet irradiation. Applied Example (A) component 5 6 7 8 9 10 11 Urethane acrylate obtained by Synthesis Example 1 30 25 20 25 Urethane acrylate obtained by Synthesis Example 2 30 20 30 KAYARAD R-114 30 10 10 (B) component Compound obtained by Example 1 15 20 15 Compound obtained by Example 2 15 20 Compound obtained by Example 3 35 20 Compound obtained by Example 4 10 (C) component KAYARAD R-551 45 45 30 30 35 35 33 tribromophenyl methacrylate 10 15 10 tribromophenyloxyethyl acrylate 10 20 (D) component Ilgacure 184 3 3 3 3 3 3 3 Release properties o o o o o o o Shape reproducibility o o o o o o o Restorability o o ▵ o o o o Refractive index (23°C) 1.5740 1.5728 1.5770 1.5752 1.5720 1.5775 1.578 Scratch resistance oo oo o oo oo oo oo As is clear from the evaluation results in Table 1, cured products of the resin composites of this invention are superior in mold release property, shape reproducibility, restorability, and scratch resistance, and have high refractive index (23°C) of 1.57 or above. The (meth)acrylates of this invention have little odor, high refractive index, and are useful as component of ultraviolet- and/or electron beam-curing resin composites, in particular resin composites for lens (for example, Fresnel lens and lenticular lens). The resin composites and the cured products of the ultraviolet-curing resin composites for transmission-type screen of this invention have high refractive index and are superior in mold release property, shape reproducibility, restorability and scratch resistance and suitable for transmission type screen.

Claims: A (meth)acrylate represented by formula (1): wherein, R 1 and R 2 are each independently H or CH 3 and average value of n is 1 - 5, with the exception of the compound : and with the exception of the compound : A (meth)acrylate described in Claim 1, represented by formula (2): wherein, R 1 and R 2 are each independently H or CH 3 and average value of n is 1 - 5. A (meth)acrylate described in Claim 1, represented by formula (3): wherein, R 1 and R 2 are each independently H or CH 3 and, average value of n is 1 - 5, excepted the compounds specified in claim 1. A (meth)acrylate described in Claim 1, represented by formula (4): wherein, average value of m is 1 - 4. A resin composite comprising (A) an urethane (meth)acrylate and/or epoxy (meth)acrylate, (B) a (meth)acrylate represented by formula (1): wherein, R 1 and R 2 are each independently H or CH 3 and average value of n is 1 - 5, (C) an ethylenically unsaturated compound other than (A) or (B), and (D) a photopolymerization initiator. A resin composition described in Claim 5, containing 10 - 50 wt.% of (A) the urethane (meth)acrylate and/or epoxy (meth)acrylate, 10 - 40 wt.% of (B) the (meth)acrylate ester, 10 - 70 wt.% of (C) the ethylenically unsaturated compound and 0.1 - 10 wt.% of (D) the photopolymerization initiator. A resin composite of Claim 5 or 6, wherein, (B) the (meth)acrylate is a compound represented by formula (2): wherein, R 1 and R 2 are each independently H or CH 3 and average value of n is 1 - 5. A resin composite of Claim 5 or 6, wherein, (B) the (meth)acrylate is a compound represented by formula (3): wherein, R 1 and R 2 are each independently H or CH 3 and average value of n is 1 - 5. A resin composite of Claim 5 or 6, wherein, (B) the (meth)acrylate is a compound represented by formula (4): wherein, average value of m is 1 - 4. A cured product of a resin composite of Claim 5, 6, 7, 8 or 9. An ultraviolet curing resin composite for transmission screens comprising a resin composite of Claim 5, 6, 7, 8 or 9. A cured product of an ultraviolet curing resin composite for transmission screens described in Claim 11.

Inventors: NAKAYAMA KENJI, SHIMURA KATSUNORI, TANIGUCHI NOBUO, YOKOSHIMA MINORU, NAKAYAMA, KENJI, SHIMURA, KATSUNORI, TANIGUCHI, NOBUO, YOKOSHIMA, MINORU
Applicants: NIPPON KAYAKU KK, NIPPON KAYAKU KABUSHIKI KAISHA
Application year: 1992
Main classification: C07C69
IPC codes: C07C69, C08F20