US20020032285A1 - Methyl methacrylate resin composition and molded article thereof - Google Patents
Methyl methacrylate resin composition and molded article thereof Download PDFInfo
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- US20020032285A1 US20020032285A1 US09/910,900 US91090001A US2002032285A1 US 20020032285 A1 US20020032285 A1 US 20020032285A1 US 91090001 A US91090001 A US 91090001A US 2002032285 A1 US2002032285 A1 US 2002032285A1
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- methyl methacrylate
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- 0 *C.COC(=O)C(=Cc1ccccc1)C(=O)OC Chemical compound *C.COC(=O)C(=Cc1ccccc1)C(=O)OC 0.000 description 2
- WREFTMYLGIEGGB-UHFFFAOYSA-M CC1(C)CC2(CC(C)(C)N1)OC1(CCCCCCCCCCC1)N([Y])C2=O Chemical compound CC1(C)CC2(CC(C)(C)N1)OC1(CCCCCCCCCCC1)N([Y])C2=O WREFTMYLGIEGGB-UHFFFAOYSA-M 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/353—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
Definitions
- the present invention relates to a methyl methacrylate resin composition and a molded article thereof. More specifically, it relates to a methyl methacrylate resin composition containing an ultraviolet absorber, and a molded article thereof.
- a method including addition of an ultraviolet absorber to the composition is known.
- JETI, vol.46, No. 5, p.116-121 discloses use of a salicylate, cyano acrylate or benzotriazole compound as an ultraviolet absorber to be added to methyl methacrylate resins.
- An object of the present invention is to provide a methyl methacrylate resin composition exhibiting superior durability without impairing the transparency inherent to a methyl methacrylate resin.
- the present inventors made intensive have studied a methyl methacrylate resin composition exhibiting superior durability without impairing the transparency inherent to a methyl methacrylate resin, as a result, found that a methylmethacrylate resin composition containing a 2-(1-arylalkylidene) malonic acid ester exhibits superior durability without impairing the transparency inherent to a methyl methacrylate resin, and have completed the present invention.
- the present invention provides a methyl methacrylate resin composition
- a methyl methacrylate resin composition comprising a methyl methacrylate resin and a 2-(1-arylalkylidene) malonic acid ester in an amount of about 0.0005 to about 0.1 parts by weight per 100 parts by weight of the methyl methacrylate resin.
- the methyl methacrylate resin is a polymer comprising not less than about 50% by weight of methyl methacrylate as a monomer forming the resin.
- An example of such a polymer is a polymer comprising not less than about 50% by weight of poly methyl methacrylate, which is essentially a monopolymer of methyl methacrylate, or a copolymer comprising methyl methacrylate and not more than about 50% by weight of an unsaturated monomer, which is copolymerizable therewith.
- Examples of unsaturated monomers which are copolymerizable with methyl methacrylate include methacrylic acid esters such as ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate; unsaturated acids such as methacrylic acid and acrylic acid; styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, maleic acid anhydride, phenylmaleimide, and cyclohex
- alkyl acrylates such as methyl acrylate are preferred as the unsaturated monomer, which is copolymerizable with methyl methacrylate.
- the composition of the monomers used in the copolymer preferably comprises about 80 to about 99.5% by weight of methyl methacrylate and about 0.5 to about 20% by weight of the alkyl acrylate.
- styrene is preferred as the unsaturated monomer, which is copolymerizable with methyl methacrylate.
- the composition of the monomers used in the copolymer preferably comprises about 60 to about 90% by weight of methyl methacrylate and about 10 to about 40% by weight of styrene.
- a 2-(1-arylalkylidene) malonic acid ester is contained in the methyl methacrylate resin to provide a methyl methacrylate resin composition having superior transparency and durability.
- an amount of the 2-(1-arylalkylidene) malonic acid ester is not less than about 0.0005 parts by weight, preferably not less than about 0.003 parts by weight, more preferably not less than about 0.005 parts by weight, per 100 parts by weight of the methyl methacrylate resin.
- the content of the 2-(1-arylalkylidene) malonic acid ester is not more than about 1 part by weight, preferably not more than about 0.05 parts by weight, more preferably not more than about 0.03 parts by weight, per 100 parts by weight of the methyl methacrylate resin.
- X represents a hydrogen atom, an alkyl group having 1 to about 6 carbon atoms or an alkoxy group having 1 to about 6 carbon atoms
- R 1 and R 2 independently represent an alkyl group having 1 to about 6 carbon atoms.
- X is preferably a hydrogen atom, an alkyl group having 1 to about 4 carbon atoms or an alkoxy group having 1 to about 4 carbon atoms.
- the alkyl group represented by X or the alkyl group in the alkoxy group represented by X may be either in a straight-chain form or in a branched-chain form. Examples of such alkyl groups include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, and t-butyl group. More preferably, X is a methoxy group.
- R 1 and R 2 in the formula (1) are each an alkyl group having 1 to about 4 carbon atoms.
- the alkyl group represented by R 1 or R 2 may be either in a straight-chain form or in a branched-chain form. Examples of such alkyl groups include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, and t-butyl group. More preferably, R 1 and R 2 are each a methyl group.
- the composition of the present invention may contain a hindered amine such as a compound having a 2,2,6,6-tetraalkylpiperidine skeleton for further improved durability.
- a hindered amine such as a compound having a 2,2,6,6-tetraalkylpiperidine skeleton for further improved durability.
- the content of such a hindered amine is usually not less than about 0.0001 parts by weight, preferably not less than about 0.001 parts by weight, more preferably not less than about 0.003 parts by weight, per 100 parts by weight of the methyl methacrylate resin.
- an amount of the hindered amine is usually not more than about 0.1 parts by weight, preferably not more than about 0.05 parts by weight, more preferably not more than about 0.03 parts by weight.
- the content of the hindered amine per 100 parts by weight of the 2-(1-arylalkylidene) malonic acid ester is usually not more than about 100 parts by weight, preferably in the range of about 10
- hindered amines include a polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly((6-(1,1,3,3-tetramethylbutyl)imino-1,3, 5-triazine -2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl)imino)) hexamethylene ((2,2,6,6-tetramethyl- 4-piperidyl)imino, 2-(2,3-di-t-butyl-4-hydroxybenzyl)-2-n-bis(1,2,2,6,6-pentamethyl-4-piperidyl) butylmalonic acid, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-bis(1,2,2,6,6-pentamethyl-4-piperidyl) butylmalonic acid, a condensate of N,N′-
- Y represents a hydrogen atom, an alkyl group having 1 to about 20 carbon atoms, a carboxyalkyl group having 2 to about 20 carbon atoms, an alkoxyalkyl group having 2 to about 25 carbon atoms, or an alkoxycarbonylalkyl group having 3 to about 25 carbon atoms.
- Two or more of these hindered amines may be used in combination if necessary. Among them, the compounds represented by the general formula (2) are preferable.
- each of the alkyl group, carboxyalkyl group, two alkyl groups in the alkoxyalkyl group (the alkyl group in the alkoxy group and the alkyl groups substituted with the alkoxy group), and two alkyl groups in the alkoxycarbonylalkyl group (the alkyl group in the alkoxy group and the alkyl groups substituted with the alkoxycarbonyl group) may be either in a straight-chain form or a branched-chain form.
- Y is preferably a hydrogen atom or an alkoxycarbonylalkyl group having about 5 to about 24 carbon atoms.
- a hydrogen atom or an alkoxycarbonylethyl group is more preferable as Y.
- alkoxycarbonylethyl groups include dodecyloxycarbonylethyl group, tetradecyloxycarbonylethyl group, hexadecyloxycarbonylethyl group, and octadecyloxycarbonylethyl group.
- the composition of the present invention may contain various additives if necessary.
- additives include light diffusing agents or matting agents such as siloxane cross linking resin particles, styrene cross linking resin particles, acrylic cross linking resin particles, glass particles, talc, calcium carbonate, and barium sulfate; antistatic agents such as sodium alkyl sulfonate, sodium alkylsulfate, stearic acid monoglyceride, and polyether esteramide; antioxidants such as hindered phenols; flame-retardants such as phosphoric acid esters; and lubricants such as palmitic acid and stearyl alcohol. These additives may be used in combination of two or more of them.
- composition of the present invention As a method for preparing the composition of the present invention, there can be mentioned a method in which the methyl methacrylate resin, 2-(1-arylalkylidene) malonic acid ester, and, if necessary, a hindered amine or other additives are melt-kneaded with use of a single-or twin-screw extruder, or any one of various kneaders.
- composition in a pellet form, a plate form or a like form by mixing a monomer forming the methyl methacrylate resin or a syrup containing a partial polymer of the monomer, the 2-(1-arylalkylidene) malonic acid ester, and, if necessary, a hindered amine or other additives together to allow bulk polymerization to proceed either batch-wise or continuously.
- the composition of the present invention can be formed into various molded articles by molding processes such as extrusion molding, injection molding, and press molding.
- molded articles include a signboard, a carport roof, an lighting cover, a front sheet for vending machines, a showcase, a toy, a lens, a prism, and a light guide.
- optical articles such as lens, prism, and light guide are preferable.
- a light transmittance of a molded article made from the composition with respect to light having a wavelength of 400 nm through a 30 cm-long optical path is usually not less than about 50%, preferably not less than about 70%.
- An average light transmittance of such a molded article with respect to light in the visible light range is usually not less than about 75%, preferably not less than about 80%.
- the composition of the present invention can be suitably used for light guides, in particular, among optical articles.
- a cold cathode fluorescent lamp exhibiting high efficiency and high luminance has been developed as a light source for a backlight of a liquid crystal display device, and with the development of such a cold cathode fluorescent lamp large-scale liquid display devices exhibiting increasing luminance are developed.
- light guides made from conventional methyl methacrylate resin compositions sometimes do not satisfy the requirement of transparency or durability.
- a light guide made from the composition of the present invention is excellent in both transparency and durability and hence can advantageously be used in a back lighting system incorporating a cold cathode fluorescent lamp having high luminance without causing deterioration of its own and of peripheral articles.
- the composition may be molded into a sheet shape by extrusion molding using a T die or a roll unit, or may be molded into a sheet shape or a wedge shape by injection molding or press molding.
- the composition in a sheet shape may be prepared by cast polymerization.
- a light guide made from the composition of the present invention is suitably used in the backlighting system of a liquid crystal display device with its screen having a width across corners measuring not less than about 14 inches, preferably not less than about 20 inches.
- Roll three polishing rolls, vertical type
- a methyl methacrylate resin (a copolymer of methyl methacrylate and methyl acrylate, having a weight ratio of 96/4 and a refractive index of 1.49) in an amount of 100 parts by weight, and a compound, the type and the amount (part(s) by weight) of which are shown in Table 1, were mixed together in a polyethylene bag, and then the resulting mixture was melt-kneaded using the extruder apparatus at an extrusion resin temperature of 250° C., to form a sheet having a thickness of 3.5 mm and a width of 22 cm. The sheet thus obtained was cut to a size of a width of 7 cm and a length of 30 cm and mirror-polished at edge faces, to give a test piece( 7 cm(W) ⁇ 30 cm(L) ⁇ 3.5 mm(T)).
- Example 4 and Comparative Example 1 were tested as to their durability for respective periods shown in Table 2 using ATLAS-UVCON (manufactured by Toyo Seiki Seisaku-sho, Ltd.) at 60° C. under the cyclic irradiation condition of 4 hours' UV irradiation and 4 hours' pure water mist spraying.
- ATLAS-UVCON manufactured by Toyo Seiki Seisaku-sho, Ltd.
- a methyl methacrylate resin (a copolymer of methyl methacrylate and methyl acrylate, having a weight ratio of 96/4 and a refractive index of 1.49) in an amount of 100 parts by weight, and a compound, the type and the amount (part(s) by weight) of which are shown in Table 3, were mixed together in a polyethylene bag, and then the resulting mixture was melt-kneaded using the extruder apparatus at an extrusion resin temperature of 260° C., to form a sheet having a thickness of 3.5 mm and a width of 22 cm. The sheet thus obtained was cut to a size of a width of 7 cm and a length of 30 cm and mirror-polished at edge faces, to give a test piece.
- test pieces thus obtained were tested as to their durability for the period shown in Table 4 using ATLAS-UVCON (manufactured by Toyo Seiki Seisaku-sho, Ltd.) at 60° C. under the continuous UV irradiation condition instead of the cyclic UV irradiation performed in Example 4 and Comparative Example 1.
- a methyl methacrylate resin (a copolymer of methyl methacrylate and styrene, having a weight ratio of 77/23 and a refractive index of 1.53) in an amount of 100 parts by weight, and a compound, the type and the amount (part(s) by weight) of which are shown in Table 5, were mixed together in a polyethylene bag, and then the resulting mixture was melt-kneaded using the extruder apparatus at an extrusion resin temperature of 260° C., to form a sheet having a thickness of 3.5 mm and a width of 22 cm. The sheet thus obtained was cut to a size of a width of 7 cm and a length of 30 cm and mirror-polished at edge faces, to give a test piece.
- test pieces thus obtained were tested as to their durability for the period shown in Table 6 using ATLAS-UVCON (manufactured by Toyo Seiki Seisaku-sho, Ltd.) at 60° C. under the condition of continuous UV irradiation.
- the present invention provides a methyl methacrylate resin composition exhibiting superior transparency and durability and also provides a useful molded article having these properties, for example, an optical article such as a light guide.
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Abstract
The present invention provides a methyl methacrylate resin composition exhibiting superior durability without impairing the transparency inherent to a methyl methacrylate resin, which comprises a methyl methacrylate resin and a 2-(1-arylalkylidene) malonic acid ester in an amount of 0.0005 to 0.1 parts by weight per 100 parts by weight of the methyl methacrylate resin.
Description
- 1. Field of the Invention
- The present invention relates to a methyl methacrylate resin composition and a molded article thereof. More specifically, it relates to a methyl methacrylate resin composition containing an ultraviolet absorber, and a molded article thereof.
- 2. Description of the Related Art
- As a conventional method to improve the durability of a methyl methacrylate resin composition, a method including addition of an ultraviolet absorber to the composition is known. For instance, JETI, vol.46, No. 5, p.116-121 (1998) discloses use of a salicylate, cyano acrylate or benzotriazole compound as an ultraviolet absorber to be added to methyl methacrylate resins.
- In the case where a methyl methacrylate resin blended with ultraviolet absorbers conventionally used is molded into an optical article, however, light transmitted through the optical article may be somewhat colored presumably due to the power absorbing viewable light of the ultraviolet absorbers used, hence, the transparency of the molded optical article may be insufficient. This problem becomes noticeable particularly when a transmitted optical path length of the molded optical article is long.
- An object of the present invention is to provide a methyl methacrylate resin composition exhibiting superior durability without impairing the transparency inherent to a methyl methacrylate resin.
- The present inventors made intensive have studied a methyl methacrylate resin composition exhibiting superior durability without impairing the transparency inherent to a methyl methacrylate resin, as a result, found that a methylmethacrylate resin composition containing a 2-(1-arylalkylidene) malonic acid ester exhibits superior durability without impairing the transparency inherent to a methyl methacrylate resin, and have completed the present invention.
- That is, the present invention provides a methyl methacrylate resin composition comprising a methyl methacrylate resin and a 2-(1-arylalkylidene) malonic acid ester in an amount of about 0.0005 to about 0.1 parts by weight per 100 parts by weight of the methyl methacrylate resin.
- The present invention will hereinafter be described in detail.
- In the present invention, the methyl methacrylate resin is a polymer comprising not less than about 50% by weight of methyl methacrylate as a monomer forming the resin. An example of such a polymer is a polymer comprising not less than about 50% by weight of poly methyl methacrylate, which is essentially a monopolymer of methyl methacrylate, or a copolymer comprising methyl methacrylate and not more than about 50% by weight of an unsaturated monomer, which is copolymerizable therewith.
- Examples of unsaturated monomers which are copolymerizable with methyl methacrylate include methacrylic acid esters such as ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate; unsaturated acids such as methacrylic acid and acrylic acid; styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, maleic acid anhydride, phenylmaleimide, and cyclohexylmaleimide. Two or more of these unsaturated monomers may be used in combination if necessary. The aforementioned copolymer may contain a glutaric acid anhydride unit or a glutarimide unit.
- In terms of moldability, alkyl acrylates such as methyl acrylate are preferred as the unsaturated monomer, which is copolymerizable with methyl methacrylate. When such an alkyl acrylate is contained as the unsaturated monomer, the composition of the monomers used in the copolymer preferably comprises about 80 to about 99.5% by weight of methyl methacrylate and about 0.5 to about 20% by weight of the alkyl acrylate.
- In terms of its lower water absorption property, styrene is preferred as the unsaturated monomer, which is copolymerizable with methyl methacrylate. When styrene is contained as the unsaturated monomer, the composition of the monomers used in the copolymer preferably comprises about 60 to about 90% by weight of methyl methacrylate and about 10 to about 40% by weight of styrene.
- According to the present invention, a 2-(1-arylalkylidene) malonic acid ester is contained in the methyl methacrylate resin to provide a methyl methacrylate resin composition having superior transparency and durability. In terms of durability, an amount of the 2-(1-arylalkylidene) malonic acid ester is not less than about 0.0005 parts by weight, preferably not less than about 0.003 parts by weight, more preferably not less than about 0.005 parts by weight, per 100 parts by weight of the methyl methacrylate resin. In terms of transparency, the content of the 2-(1-arylalkylidene) malonic acid ester is not more than about 1 part by weight, preferably not more than about 0.05 parts by weight, more preferably not more than about 0.03 parts by weight, per 100 parts by weight of the methyl methacrylate resin.
-
- wherein X represents a hydrogen atom, an alkyl group having 1 to about 6 carbon atoms or an alkoxy group having 1 to about 6 carbon atoms, and R1 and R2 independently represent an alkyl group having 1 to about 6 carbon atoms.
- In the formula (1), X is preferably a hydrogen atom, an alkyl group having 1 to about 4 carbon atoms or an alkoxy group having 1 to about 4 carbon atoms. The alkyl group represented by X or the alkyl group in the alkoxy group represented by X may be either in a straight-chain form or in a branched-chain form. Examples of such alkyl groups include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, and t-butyl group. More preferably, X is a methoxy group.
- Preferably, R1 and R2 in the formula (1) are each an alkyl group having 1 to about 4 carbon atoms. The alkyl group represented by R1 or R2 may be either in a straight-chain form or in a branched-chain form. Examples of such alkyl groups include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, and t-butyl group. More preferably, R1 and R2 are each a methyl group.
- The composition of the present invention may contain a hindered amine such as a compound having a 2,2,6,6-tetraalkylpiperidine skeleton for further improved durability. In this case, the content of such a hindered amine is usually not less than about 0.0001 parts by weight, preferably not less than about 0.001 parts by weight, more preferably not less than about 0.003 parts by weight, per 100 parts by weight of the methyl methacrylate resin. In terms of cost and transparency, an amount of the hindered amine is usually not more than about 0.1 parts by weight, preferably not more than about 0.05 parts by weight, more preferably not more than about 0.03 parts by weight. The content of the hindered amine per 100 parts by weight of the 2-(1-arylalkylidene) malonic acid ester is usually not more than about 100 parts by weight, preferably in the range of about 10 to about 80 parts by weight.
- Examples of such hindered amines include a polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly((6-(1,1,3,3-tetramethylbutyl)imino-1,3, 5-triazine -2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl)imino)) hexamethylene ((2,2,6,6-tetramethyl- 4-piperidyl)imino, 2-(2,3-di-t-butyl-4-hydroxybenzyl)-2-n-bis(1,2,2,6,6-pentamethyl-4-piperidyl) butylmalonic acid, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-bis(1,2,2,6,6-pentamethyl-4-piperidyl) butylmalonic acid, a condensate of N,N′-bis(3-aminopropyl)ethylenediamine and 2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl) amino)- 6-chloro-1,3,5-triazine, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, and compounds represented by the following general formula (2);
- wherein Y represents a hydrogen atom, an alkyl group having 1 to about 20 carbon atoms, a carboxyalkyl group having 2 to about 20 carbon atoms, an alkoxyalkyl group having 2 to about 25 carbon atoms, or an alkoxycarbonylalkyl group having 3 to about 25 carbon atoms. Two or more of these hindered amines may be used in combination if necessary. Among them, the compounds represented by the general formula (2) are preferable.
- In the compounds of the above formula (2), each of the alkyl group, carboxyalkyl group, two alkyl groups in the alkoxyalkyl group (the alkyl group in the alkoxy group and the alkyl groups substituted with the alkoxy group), and two alkyl groups in the alkoxycarbonylalkyl group (the alkyl group in the alkoxy group and the alkyl groups substituted with the alkoxycarbonyl group) may be either in a straight-chain form or a branched-chain form. In the formula (2), Y is preferably a hydrogen atom or an alkoxycarbonylalkyl group having about 5 to about 24 carbon atoms. Particularly, a hydrogen atom or an alkoxycarbonylethyl group is more preferable as Y. Examples of such alkoxycarbonylethyl groups include dodecyloxycarbonylethyl group, tetradecyloxycarbonylethyl group, hexadecyloxycarbonylethyl group, and octadecyloxycarbonylethyl group.
- The composition of the present invention may contain various additives if necessary. Examples of such additives include light diffusing agents or matting agents such as siloxane cross linking resin particles, styrene cross linking resin particles, acrylic cross linking resin particles, glass particles, talc, calcium carbonate, and barium sulfate; antistatic agents such as sodium alkyl sulfonate, sodium alkylsulfate, stearic acid monoglyceride, and polyether esteramide; antioxidants such as hindered phenols; flame-retardants such as phosphoric acid esters; and lubricants such as palmitic acid and stearyl alcohol. These additives may be used in combination of two or more of them.
- As a method for preparing the composition of the present invention, there can be mentioned a method in which the methyl methacrylate resin, 2-(1-arylalkylidene) malonic acid ester, and, if necessary, a hindered amine or other additives are melt-kneaded with use of a single-or twin-screw extruder, or any one of various kneaders. Alternatively, it is possible to obtain the composition in a pellet form, a plate form or a like form by mixing a monomer forming the methyl methacrylate resin or a syrup containing a partial polymer of the monomer, the 2-(1-arylalkylidene) malonic acid ester, and, if necessary, a hindered amine or other additives together to allow bulk polymerization to proceed either batch-wise or continuously.
- The composition of the present invention can be formed into various molded articles by molding processes such as extrusion molding, injection molding, and press molding. Examples of such molded articles include a signboard, a carport roof, an lighting cover, a front sheet for vending machines, a showcase, a toy, a lens, a prism, and a light guide. Among them, optical articles such as lens, prism, and light guide are preferable.
- When the composition of the present invention is used for applications as optical articles in particular, a light transmittance of a molded article made from the composition with respect to light having a wavelength of 400 nm through a 30 cm-long optical path is usually not less than about 50%, preferably not less than about 70%. An average light transmittance of such a molded article with respect to light in the visible light range (the wavelength range of about 380 to about 780 nm) is usually not less than about 75%, preferably not less than about 80%.
- The composition of the present invention can be suitably used for light guides, in particular, among optical articles. In recent years, a cold cathode fluorescent lamp exhibiting high efficiency and high luminance has been developed as a light source for a backlight of a liquid crystal display device, and with the development of such a cold cathode fluorescent lamp large-scale liquid display devices exhibiting increasing luminance are developed. Under such situations, light guides made from conventional methyl methacrylate resin compositions sometimes do not satisfy the requirement of transparency or durability. A light guide made from the composition of the present invention is excellent in both transparency and durability and hence can advantageously be used in a back lighting system incorporating a cold cathode fluorescent lamp having high luminance without causing deterioration of its own and of peripheral articles.
- In molding the composition into a light guide, the composition may be molded into a sheet shape by extrusion molding using a T die or a roll unit, or may be molded into a sheet shape or a wedge shape by injection molding or press molding. Alternatively, the composition in a sheet shape may be prepared by cast polymerization.
- A light guide made from the composition of the present invention is suitably used in the backlighting system of a liquid crystal display device with its screen having a width across corners measuring not less than about 14 inches, preferably not less than about 20 inches.
- Hereinafter, the present invention will be more specifically described by way of examples, which should not be construed as limitative of the present invention.
- The following compounds (A) to (F) were used as a compound added into a methyl methacrylate resin.
- (A): 2-(paramethoxybenzylidene) dimethylmalonate [a compound of the formula (1) where X is a methoxy group, which is substituted at para-position, and R1 and R2 are each a methyl group; produced by Clariant Co. under the trade name: Sanduvor PR-25]
- (B): 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole [produced by Sumitomo Chemical Co., Ltd. under the trade name: SUMISORB 200]
- (C): 2,4-dihydroxybenzophenone [produced by Sipuro Kasei Co., Ltd. under the trade name: SEASORB 100]
- (D): 2,2′-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-((2H-benzotriazole-2-yl) phenol) [produced by Asahi Denka Co., Ltd. under the trade name: ADEKASUTABU LA31]
- (E): a mixture of dodecyl ester and tetradecyl ester of 2,2,4,4-tetramethyl-21-oxo-7-oxa-3,20-diazadispyro[5.1.11. 2]-heneicosane-20-propanoic acid [a mixture of a compound of the formula (2) where Y is a dodecyloxycarbonylethyl group and a compound of the formula (2) where Y is tetradecyloxycarbonylethyl group; produced by Clariant Co., Ltd. under the trade name: Hostavin N24]
- (F): bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate [produced by Chiba-Geigy Co., Ltd. under the trade name: CHINUBIN 770]
- The configuration of an extruder apparatus used in forming sheets is as follows.
- Extruder: screw diameter=40 mm, single screw, vented (manufactured by Tanabe Plastics Machinery Co., Ltd.)
- Die: T die, lip width=250 mm, lip gap=6 mm
- Roll: three polishing rolls, vertical type
- The values of the following optical properties were calculated from the results of measurements of a light transmittance at a wavelength ranging from 300 to 800 nm at every 5 nm through a 30 cm-long optical path.
- Average light transmittance in the wavelength range of 380 to 780 nm
- x value calculated from the CIE-XYZ color specification system
- [x=X/(X+Y+Z)]
- y value calculated from the CIE-XYZ color specification system
- [y=Y/(X+Y+Z)]
- A methyl methacrylate resin (a copolymer of methyl methacrylate and methyl acrylate, having a weight ratio of 96/4 and a refractive index of 1.49) in an amount of 100 parts by weight, and a compound, the type and the amount (part(s) by weight) of which are shown in Table 1, were mixed together in a polyethylene bag, and then the resulting mixture was melt-kneaded using the extruder apparatus at an extrusion resin temperature of 250° C., to form a sheet having a thickness of 3.5 mm and a width of 22 cm. The sheet thus obtained was cut to a size of a width of 7 cm and a length of 30 cm and mirror-polished at edge faces, to give a test piece( 7 cm(W)×30 cm(L)×3.5 mm(T)).
- The values of the optical properties of each test piece are shown in Table 1.
- Further, the test pieces of Example 4 and Comparative Example 1 were tested as to their durability for respective periods shown in Table 2 using ATLAS-UVCON (manufactured by Toyo Seiki Seisaku-sho, Ltd.) at 60° C. under the cyclic irradiation condition of 4 hours' UV irradiation and 4 hours' pure water mist spraying.
- The values of the optical properties of each test piece having undergone the test are shown in Table 2.
TABLE 1 Average Light light Compound trans- trans- (type: part(s) mittance mittance in by weight) at 400 nm 380˜780 nm x value y value Example 1 (A): 0.0010 80% 84% 0.313 0.319 Example 2 (A): 0.0030 81% 85% 0.312 0.319 Example 3 (A): 0.0070 81% 85% 0.312 0.319 Example 4 (A): 0.0100 80% 84% 0.313 0.319 Example 5 (A): 0.0150 75% 80% 0.314 0.321 Comparative — 81% 84% 0.313 0.319 example 1 Comparative (B): 0.0100 39% 78% 0.314 0.321 example 2 Comparative (C): 0.0100 36% 78% 0.315 0.323 example 3 Comparative (D): 0.0100 3% 76% 0.314 0.323 example 4 -
TABLE 2 Average Light light trans- trans- mittance mittance in Test period at 400 nm 380˜780 nm x value y value Example 4 42 days 78% 82% 0.312 0.320 Comparative 10 days 26% 76% 0.336 0.367 example 1 - A methyl methacrylate resin (a copolymer of methyl methacrylate and methyl acrylate, having a weight ratio of 96/4 and a refractive index of 1.49) in an amount of 100 parts by weight, and a compound, the type and the amount (part(s) by weight) of which are shown in Table 3, were mixed together in a polyethylene bag, and then the resulting mixture was melt-kneaded using the extruder apparatus at an extrusion resin temperature of 260° C., to form a sheet having a thickness of 3.5 mm and a width of 22 cm. The sheet thus obtained was cut to a size of a width of 7 cm and a length of 30 cm and mirror-polished at edge faces, to give a test piece.
- The values of the optical properties of each test piece are shown in Table 3.
- Further, these test pieces thus obtained were tested as to their durability for the period shown in Table 4 using ATLAS-UVCON (manufactured by Toyo Seiki Seisaku-sho, Ltd.) at 60° C. under the continuous UV irradiation condition instead of the cyclic UV irradiation performed in Example 4 and Comparative Example 1.
- The values of the optical properties of each test piece having undergone the test are shown in Table 4.
TABLE 3 Average Light light Compound trans- trans- (type: part(s) mittance mittance in by weight) at 400 nm 380-780 nm x value y value Example 6 (A): 0.0080 79% 83% 0.313 0.320 Example 7 (A): 0.0150 79% 83% 0.313 0.320 Example 8 (A): 0.0080 78% 82% 0.313 0.320 (E): 0.0060 Example 9 (A): 0.0150 79% 83% 0.313 0.320 (E): 0.0060 Comparative — 78% 82% 0.313 0.320 example 5 Comparative (E): 0.0060 78% 83% 0.313 0.320 example 6 -
TABLE 4 Average Light light trans- trans- mittance mittance in Test period at 400 nm 380-780 x value y value Example 6 6 days 5% 59% 0.383 0.413 Example 7 6 days 46% 78% 0.324 0.340 Example 8 6 days 36% 74% 0.332 0.350 Example 9 6 days 61% 81% 0.318 0.330 Comparative 6 days 0% 43% 0.453 0.455 example 5 Comparative 6 days 6% 35% 0.492 0.464 example 6 - A methyl methacrylate resin (a copolymer of methyl methacrylate and styrene, having a weight ratio of 77/23 and a refractive index of 1.53) in an amount of 100 parts by weight, and a compound, the type and the amount (part(s) by weight) of which are shown in Table 5, were mixed together in a polyethylene bag, and then the resulting mixture was melt-kneaded using the extruder apparatus at an extrusion resin temperature of 260° C., to form a sheet having a thickness of 3.5 mm and a width of 22 cm. The sheet thus obtained was cut to a size of a width of 7 cm and a length of 30 cm and mirror-polished at edge faces, to give a test piece.
- The values of the optical properties of each test piece are shown in Table 5.
- Further, these test pieces thus obtained were tested as to their durability for the period shown in Table 6 using ATLAS-UVCON (manufactured by Toyo Seiki Seisaku-sho, Ltd.) at 60° C. under the condition of continuous UV irradiation.
- The values of the optical properties of each test piece having undergone the test are shown in Table 6.
TABLE 5 Average Light light Compound trans- trans- (type: part(s) mittance mittance in by weight) at 400 nm 380-780 nm x value y value Example 10 (A): 0.0160 78% 87% 0.313 0.322 Example 11 (A): 0.0300 73% 84% 0.314 0.322 Example 12 (A): 0.0160 78% 87% 0.313 0.322 (E): 0.0060 Example 13 (A): 0.0300 76% 86% 0.313 0.322 (E): 0.0060 Example 14 (A): 0.0160 74% 84% 0.314 0.322 (E): 0.0120 Example 15 (A): 0.0300 76% 84% 0.315 0.323 (E): 0.0120 Comparative — 78% 87% 0.314 0.322 example 7 Comparative (E): 0.0120 77% 86% 0.314 0.323 example 8 Comparative (F): 0.0120 75% 85% 0.314 0.322 example 9 Comparative (B): 0.0300 20% 81% 0.317 0.327 example 10 (E): 0.0120 -
TABLE 6 Average Light light trans- trans- mittance mittance in Test period at 400 nm 380-780 nm x value y value Example 10 6 days 9% 63% 0.398 0.426 Example 11 6 days 21% 68% 0.367 0.393 Example 12 6 days 18% 68% 0.371 0.398 Example 13 6 days 45% 77% 0.336 0.353 Example 14 6 days 21% 69% 0.370 0.395 Example 15 6 days 7% 71% 0.355 0.380 Comparative 6 days 0% 58% 0.428 0.455 example 7 Comparative 6 days 0% 54% 0.422 0.449 example 8 Comparative 6 days 0% 49% 0.453 0.467 example 9 Comparative 6 days 7% 69% 0.366 0.386 example 10 - As described above, the present invention provides a methyl methacrylate resin composition exhibiting superior transparency and durability and also provides a useful molded article having these properties, for example, an optical article such as a light guide.
Claims (11)
1. A methyl methacrylate resin composition comprising a methyl methacrylate resin and a 2-( 1-arylalkylidene) malonic acid ester in an amount of about 0.0005 to about 0.1 parts by weight per 100 parts by weight of the methyl methacrylate resin.
2. The methyl methacrylate resin composition according to claim 1 , wherein the 2-(1-arylalkylidene) malonic acid ester is a compound represented by the formula (1);
wherein X represents a hydrogen atom, an alkyl group having 1 to about 6 carbon atoms or an alkoxy group having 1 to about 6 carbon atoms, and R1 and R2 independently represent an alkyl group having 1 to about 6 carbon atoms.
3. The methyl methacrylate resin composition according to claim 1 or 2, wherein the 2-(1-arylalkylidene) malonic acid ester is 2-(paramethoxybenzylidene)dimethylmalonate.
4. The methyl methacrylate resin composition according to claim 1 , wherein the methyl methacrylate resin composition further comprises a hindered amine.
5. The methyl methacrylate resin composition according to claim 4 , wherein the hindered amine is a mixture of dodecyl ester and tetradecyl ester of 2,2,4,4-tetramethyl-21-oxo-7-oxa-3, 20-diazadispyro[5.1.11.2]-heneicosane-20-propanoic acid.
6. The methyl methacrylate resin composition according to claim 4 , wherein the hindered amine is bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate.
7. The methyl methacrylate resin composition according to claim 4 , wherein an amount of the hindered amine is not less than about 0.0001 parts by weight and not more than about 0.1 parts by weight per 100 parts by weight of the methyl methacrylate resin.
8. A molded article made from a methyl methacrylate resin composition comprising a methyl methacrylate resin and a 2- (1-arylalkylidene) malonic acid ester in an amount of 0.0005 to 0.1 parts by weight per 100 parts by weight of the methyl methacrylate resin.
9. The molded article according to claim 8 , wherein the methyl methacrylate resin composition further comprises a hindered amine.
10. The molded article according to claim 8 , wherein a light transmittance of the molded article is not less than 50% with respect to light having a wavelength of 400 nm through a 30 cm-long optical path of the molded article.
11. The molded article according to claim 8 , wherein the molded article is a light guide.
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JP2000226679 | 2000-07-27 | ||
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JP2001-068341 | 2001-03-12 | ||
JP2001068341A JP3661600B2 (en) | 2000-07-27 | 2001-03-12 | Methyl methacrylate resin composition and molded article thereof |
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Cited By (3)
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US20060051704A1 (en) * | 2004-09-03 | 2006-03-09 | Sumitomo Chemical Company, Limited | Resin plate |
US20130240020A1 (en) * | 2012-03-16 | 2013-09-19 | Au Optronics Corporation | Ultraviolet light-absorbing solar module and fabricating method thereof |
CN103562242A (en) * | 2011-05-30 | 2014-02-05 | 三菱丽阳株式会社 | Molding material and molding |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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JP3669299B2 (en) * | 2001-07-12 | 2005-07-06 | 住友化学株式会社 | Methyl methacrylate resin composition and molded article thereof |
TWI329652B (en) * | 2003-03-26 | 2010-09-01 | Sumitomo Chemical Co | Resin composition and molded article thereof |
US20040191550A1 (en) * | 2003-03-27 | 2004-09-30 | Sumitomo Chemical Company, Limited | Resin plate |
DE10319761A1 (en) * | 2003-04-30 | 2004-11-18 | Röhm GmbH & Co. KG | Stretching agent for the production of synthetic filaments of melt-spinnable fiber-forming matrix polymers |
US20080032101A1 (en) * | 2006-07-24 | 2008-02-07 | Jack Reilly | Multilayer UV resistant thermoplastic composition |
DE102008043707A1 (en) | 2008-11-13 | 2010-05-20 | Evonik Röhm Gmbh | Production of solar cell modules |
DE102008043720A1 (en) | 2008-11-13 | 2010-05-20 | Evonik Röhm Gmbh | Molding compounds for the production of solar cell modules |
JP2010248408A (en) * | 2009-04-17 | 2010-11-04 | Kaneka Corp | Curable composition |
KR100943233B1 (en) * | 2009-06-03 | 2010-02-18 | 주식회사 우즈필 | Diffusion Ink Composition |
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CA1028088A (en) * | 1972-10-10 | 1978-03-14 | Charles E. Ring | Striae-free plastic lens of a copolymer of diethylene glycol bis (allyl carbonate) and methacrylate ester |
JPS5984907A (en) * | 1982-11-05 | 1984-05-16 | Agency Of Ind Science & Technol | Novel chelate resin and production thereof |
EP0206810B1 (en) * | 1985-06-24 | 1990-04-04 | Tokuyama Soda Kabushiki Kaisha | Acrylate compound and composition containing the same |
JP3209604B2 (en) * | 1993-02-25 | 2001-09-17 | ダイセル化学工業株式会社 | Active energy ray-curable resin composition |
US6054606A (en) * | 1996-05-22 | 2000-04-25 | Nippon Paint Co., Ltd. | Method for preparing malonate group-containing acrylate monomers |
JPH10109034A (en) * | 1996-05-22 | 1998-04-28 | Nippon Paint Co Ltd | Acrylic monomer bonded with malonate group and its production |
US6262153B1 (en) * | 1998-10-12 | 2001-07-17 | Clariant Finance (Bvi) Limited | Colored wax articles |
-
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US20060051704A1 (en) * | 2004-09-03 | 2006-03-09 | Sumitomo Chemical Company, Limited | Resin plate |
CN103562242A (en) * | 2011-05-30 | 2014-02-05 | 三菱丽阳株式会社 | Molding material and molding |
US20130240020A1 (en) * | 2012-03-16 | 2013-09-19 | Au Optronics Corporation | Ultraviolet light-absorbing solar module and fabricating method thereof |
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JP2002105271A (en) | 2002-04-10 |
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TWI238171B (en) | 2005-08-21 |
JP3661600B2 (en) | 2005-06-15 |
US6433044B1 (en) | 2002-08-13 |
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