WO2014119456A1 - Composition de résine méthacrylique, procédé pour produire une composition de résine méthacrylique, et article moulé - Google Patents

Composition de résine méthacrylique, procédé pour produire une composition de résine méthacrylique, et article moulé Download PDF

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WO2014119456A1
WO2014119456A1 PCT/JP2014/051313 JP2014051313W WO2014119456A1 WO 2014119456 A1 WO2014119456 A1 WO 2014119456A1 JP 2014051313 W JP2014051313 W JP 2014051313W WO 2014119456 A1 WO2014119456 A1 WO 2014119456A1
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methacrylic resin
resin composition
compound
group
carbon atoms
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PCT/JP2014/051313
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Japanese (ja)
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亮 中原
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住友化学株式会社
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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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds

Definitions

  • the present invention relates to a methacrylic resin composition, a method for producing a methacrylic resin composition, and a molded body. More specifically, the present invention relates to a methacrylic resin composition containing a methacrylic resin, an organic disulfide compound and a phosphine compound, a method for producing the methacrylic resin composition, and a molded body.
  • methacrylic resin Since methacrylic resin is excellent in transparency, it is used for various indoor and outdoor uses such as optical parts, signboards, lighting equipment, and nameplates. However, methacrylic resins have relatively low thermal stability. Therefore, the methacrylic resin has a problem that it tends to undergo thermal decomposition due to, for example, heat melting during molding.
  • Patent Document 1 discloses a methacrylic resin composition in which di-tert-alkyl disulfide is blended with a methacrylic resin.
  • the methacrylic resin composition disclosed in Patent Document 1 has a problem that coloring occurs during heating and melting. This is understood to be due to the modification of the disulfide compound that occurs during heating and melting.
  • Patent Document 2 discloses a methacrylic resin composition in which a methacrylic resin is mixed with a di-tert-alkyl disulfide and a phosphite compound. Yes.
  • the methacrylic resin composition disclosed in Patent Document 2 is not sufficiently improved in thermal stability, although coloring during heating and melting is suppressed.
  • the thermal stability of the methacrylic resin composition disclosed in Patent Document 2 is comparable to the thermal stability of the methacrylic resin itself.
  • An object of the present invention is to provide a methacrylic resin composition excellent in thermal stability and suppressed in coloring during heating and melting.
  • the present invention relates to the following (1) to (13).
  • (1) At least one compound selected from the group consisting of a methacrylic resin, an organic disulfide compound, a phosphine compound represented by the following formula (I), and a phosphine oxide compound represented by the following formula (II)
  • a methacrylic resin composition R 1 , R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an alkyl group having 6 to 12 carbon atoms.
  • R 4 , R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an alkyl group having 6 to 12 carbon atoms.
  • An alkylcycloalkyl group and an aryl group having 6 to 12 carbon atoms, and any hydrogen atom bonded to each carbon atom may be substituted with a substituent containing a hetero atom.
  • the said polymer composition is a composition obtained by mix
  • a methacrylic resin composition that is excellent in thermal stability and suppressed in coloring during heating and melting.
  • the methacrylic resin composition of the present invention has excellent thermal stability and suppresses coloring during heating and melting. Therefore, a molded article formed by molding the methacrylic resin composition of the present invention that has been melted by heating is excellent in transparency.
  • the methacrylic resin composition of the present invention comprises a methacrylic resin, an organic disulfide compound, a phosphine compound represented by the following formula (I) (hereinafter sometimes referred to as phosphine compound (I)), and the following formula (II): And at least one compound selected from the group consisting of phosphine oxide compounds (hereinafter sometimes referred to as phosphine oxide compounds (II)).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an alkyl group having 6 to 12 carbon atoms.
  • An alkylcycloalkyl group and an aryl group having 6 to 12 carbon atoms, and any hydrogen atom bonded to each carbon atom may be substituted with a substituent containing a hetero atom.
  • R 4 , R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an alkyl group having 6 to 12 carbon atoms.
  • An alkylcycloalkyl group and an aryl group having 6 to 12 carbon atoms, and any hydrogen atom bonded to each carbon atom may be substituted with a substituent containing a hetero atom.
  • the methacrylic resin is a polymer obtained by polymerizing a monomer component mainly composed of a methacrylic acid ester.
  • the methacrylic resin may be a homopolymer of methacrylic acid ester or a copolymer of 50% by weight or more of methacrylic acid ester and 50% by weight or less of other monomers.
  • the methacrylic acid ester an alkyl ester of methacrylic acid is usually used.
  • the preferred composition of the monomer component is 50 to 100% by weight of methacrylic acid alkyl ester, 0 to 50% by weight of acrylic acid alkyl ester, and 0 to 49% by weight of other monomers based on the total monomers. More preferably, the alkyl methacrylate is 50 to 99.9% by weight, the acrylic acid alkyl ester is 0.1 to 50% by weight, and other monomers are 0 to 49% by weight. Preferably, methacrylic acid alkyl ester is 60 to 99.9% by weight, acrylic acid alkyl ester is 0.1 to 40% by weight, and other monomers are 0 to 39% by weight.
  • methacrylic acid alkyl ester examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and the like.
  • the carbon number of the alkyl group of the methacrylic acid alkyl ester is usually 1 to 8, preferably 1 to 4. Of these, methyl methacrylate is preferably used.
  • acrylic acid alkyl ester examples include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like.
  • the carbon number of the alkyl group of the acrylic acid alkyl ester is usually 1 to 8, preferably 1 to 4.
  • a monofunctional monomer that is, a compound having one polymerizable carbon-carbon double bond in the molecule
  • a polyfunctional monomer that is, a compound having at least two polymerizable carbon-carbon double bonds in the molecule
  • monofunctional monomers include styrene monomers such as styrene, ⁇ -methylstyrene, and vinyl toluene, alkenyl cyanides such as acrylonitrile and methacrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N- Examples thereof include substituted maleimides.
  • polyfunctional monomer examples include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, allyl acrylate, allyl methacrylate, allyl cinnamate.
  • Alkenyl esters of unsaturated carboxylic acids such as polyallyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate and triallyl isocyanurate, aromatic polyalkenyl compounds such as divinylbenzene, etc. .
  • methacrylic acid alkyl ester the acrylic acid alkyl ester, and monomers other than these may be used alone, or two or more of them may be used in combination as required.
  • the methacrylic resin is obtained by polymerizing at least one component selected from a monomer component and a partial polymer component thereof (hereinafter sometimes simply referred to as a monomer component) by a conventionally known polymerization method.
  • a monomer component a monomer component
  • a partial polymer component thereof (hereinafter sometimes simply referred to as a monomer component)
  • the polymerization method include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a cast polymerization method.
  • the partial polymer component is a mixture of a monomer component and a polymer component. In the partial polymer component, the content of the polymer component is preferably 10 to 70% by weight.
  • Polymerization is usually performed using a polymerization initiator.
  • a radical polymerization initiator is preferably used.
  • the radical initiator include azo compounds such as 2,2′-azobis (isobutyronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile), and 1,1-di (t -Peroxides such as -butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, benzoyl peroxide, lauroyl peroxide, and the like.
  • an accelerator such as amines may be used in combination.
  • a chain transfer agent may also be used.
  • chain transfer agent examples include methyl mercaptan, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, ethylhexyl thioglycolate and the like.
  • examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl- Alcohols such as 1-propanol and 2-methyl-2-propanol; aromatic compounds such as benzene, toluene and anisole; halogenated hydrocarbons such as chloroform and methylene chloride; ethers such as tetrahydrofuran and 1,4-dioxane; Acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, a mixed solvent of water and alcohol, and the like can be mentioned.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
  • additives such as light diffusing agents, colorants, reinforcing agents, fillers, release agents, stabilizers, UV absorbers, antioxidants, and antistatic agents are added to the monomer component as necessary. May be.
  • An additive may be used independently and may use 2 or more types together.
  • organic disulfide compound examples include diethyl disulfide, di-n-propyl disulfide, di-n-butyl disulfide, di-sec-butyl disulfide, di-tert-butyl disulfide, di-n-amyl disulfide, di-tert- Amyl disulfide, di-tert-hexyl disulfide, di-n-octyl disulfide, di-tert-octyl disulfide, di-n-dodecyl disulfide, di-tert-dodecyl disulfide, di-n-stearate disulfide, ethyl-n-propyl Dialkyl disulfide compounds such as disulfide, ethyl-tert-butyl disulfide, ethyl-sec-butyl disulfide, n-propyl-isopropyl disulfide;
  • dialkyl disulfide compounds are preferable.
  • dialkyl disulfide compounds di-tert-alkyl disulfide is more preferable, and di-tert-dodecyl disulfide is more preferable.
  • An organic disulfide compound may be used independently and may use 2 or more types together.
  • the content of the organic disulfide compound is not particularly limited, but it is preferably 0 with respect to 100 parts by weight of the methacrylic resin from the viewpoint of being excellent in thermal stability and obtaining an effect commensurate with the content and economically advantageous. 0.0001 to 1.0 part by weight, more preferably 0.0001 to 0.01 part by weight.
  • the methacrylic resin composition contains a methacrylic resin and an organic disulfide compound, and further includes at least one compound selected from the group consisting of a phosphine compound (I) and a phosphine oxide compound (II) (hereinafter referred to as a phosphine compound). Contain).
  • the methacrylic resin composition may be a composition containing one or more phosphine compounds (I) and not containing a phosphine oxide compound (II), or containing one or more phosphine oxide compounds (II).
  • the composition may not contain the phosphine compound (I), or may be a composition containing one or more phosphine compounds (I) and one or more phosphine oxide compounds (II). .
  • examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group.
  • examples of an alkyl group having 3 to 12 carbon atoms all structural isomers are included.
  • a propyl group includes an n-propyl group and an isopropyl group
  • a butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • examples of the cycloalkyl group having 5 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a cyclododecyl group.
  • examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include a methylcyclopentyl group, a methylcyclohexyl group, a methylcyclooctyl group, and a methylcyclododecyl group.
  • examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a benzyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a phenethyl group, a tolylmethyl group, and a phenylbutyl group.
  • Etc. The aromatic ring of the aryl group may have an arbitrary substituent containing a hetero atom, such as a methoxy group, an ethoxy group, a hydroxy group, a carboxyl group, a fluoro group, a chloro group, or a bromo group. May be.
  • Examples of such an aryl group include a 4-methoxyphenyl group and a pentafluorophenyl group.
  • the aromatic ring of the aryl group may form a polycycle, and examples of such an aryl group include a naphthyl group.
  • Examples of the phosphine compound (I) include trimethylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, tris- (3-hydroxypropyl) phosphine, tri-n-hexylphosphine, tricyclohexylphosphine, tri- n-octylphosphine, diethylphenylphosphine methyldiphenylphosphine, ethyldiphenylphosphine, diphenylpropylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris -(4-methoxyphenyl) phosphine and the like. Of these, triphenylphosphine is preferable from the viewpoint of ease of handling.
  • the content of the phosphine compound (I) is not particularly limited, but is preferably 0.0001 to 1.0 weight with respect to 100 parts by weight of the methacrylic resin from the viewpoint of thermal stability and suppression of coloring during heating and melting. Part, more preferably 0.0001 to 0.1 part by weight, still more preferably 0.0005 to 0.01 part by weight.
  • examples of the alkyl group having 1 to 12 carbon atoms include the same groups as those exemplified as the alkyl group having 1 to 12 carbon atoms in the phosphine compound (I).
  • examples of the cycloalkyl group having 5 to 12 carbon atoms include the same groups as those exemplified as the alkyl group having 5 to 12 carbon atoms in the phosphine compound (I).
  • examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include the same groups as those exemplified as the alkylcycloalkyl group having 6 to 12 carbon atoms in the phosphine compound (I).
  • examples of the aryl group having 6 to 12 carbon atoms include the same groups as those exemplified as the aryl group having 6 to 12 carbon atoms in the phosphine compound (I).
  • Examples of the phosphine oxide compound (II) include trimethylphosphine oxide, tri-n-butylphosphine oxide, tri-tert-butylphosphine oxide, tris- (3-hydroxypropyl) phosphine oxide, tri-n-hexylphosphine oxide, Tricyclohexylphosphine oxide, tri-n-octylphosphine oxide, diethylphenylphosphine methyldiphenylphosphine oxide, ethyldiphenylphosphine oxide, diphenylpropylphosphine oxide, diphenylcyclohexylphosphine oxide, triphenylphosphine oxide, tri-o-tolylphosphine oxide, tri -M-tolylphosphine oxide, tri-p-tolylphosphine oxide, tris- (4-meth Shifeniru) phosphine oxide. Of these, triphenyl
  • the phosphine oxide compound (II) can be obtained by oxidizing the phosphine compound (I) having a corresponding substituent. That is, when the phosphine oxide compound (II) is contained in the methacrylic resin composition, the phosphine oxide compound (II) may be used directly in the method for producing a methacrylic resin composition described later, or first, the corresponding substituent. A phosphine oxide compound (II) may be blended, and then a part or all of the blended phosphine compound (I) may be oxidized to obtain a phosphine oxide compound (II).
  • triphenylphosphine oxide if triphenylphosphine oxide is contained in a methacrylic resin composition, triphenylphosphine oxide may be used in a method for producing a methacrylic resin composition described later, First, triphenylphosphine may be blended, and then the blended triphenylphosphine may be oxidized to obtain triphenylphosphine oxide.
  • the phosphine compound (I) is easily oxidized by applying heat in the presence of oxygen.
  • phosphine oxide compound (II) in order to incorporate the phosphine oxide compound (II) in the methacrylic resin composition by blending the phosphine compound (I) having the corresponding substituent and then oxidizing the blended phosphine compound (I), phosphine A step of oxidizing the phosphine compound (I) may be provided after compounding the compound (I). Examples of such an oxidation process include a polymerization process, a devolatilization process, and an extrusion process described later. Among these, the phosphine compound (I) is easily oxidized to the phosphine oxide compound (II) in the polymerization step. Moreover, when the phosphine compound (I) is contained in the methacrylic resin composition, a methacrylic resin composition containing the phosphine oxide compound (II) may be obtained as a result of spontaneous oxidation in the system.
  • the content of the phosphine oxide compound (II) is not particularly limited, but is preferably 0.0001 to 1.0 with respect to 100 parts by weight of the methacrylic resin from the viewpoint of thermal stability and suppression of coloring during heating and melting. Parts by weight, more preferably 0.0001 to 0.1 parts by weight, and still more preferably 0.0005 to 0.01 parts by weight.
  • the methacrylic resin composition contains at least one phosphine compound (I) and phosphine oxide compound (II), the total of the content of phosphine compound (I) and the content of phosphine oxide compound (II)
  • the amount is preferably 0.0001 to 1.0 part by weight, more preferably 0.0001 to 0.1 part by weight with respect to 100 parts by weight of the methacrylic resin, from the viewpoint of thermal stability and suppression of coloring during heat melting. Part, more preferably 0.0005 to 0.05 part by weight.
  • the molar ratio of the organic disulfide compound and the phosphine compound contained in the methacrylic resin composition is preferably 1 to 500 from the viewpoints of thermal stability and suppression of coloring during heating and melting. More preferably, it is 3 to 100, still more preferably 5 to 50, and particularly preferably 10 to 20. It is preferable that the content of the organic disulfide compound and the phosphine compound with respect to the methacrylic resin is in the predetermined range, respectively, and the molar ratio of the organic disulfide compound and the phosphine compound is in the predetermined range.
  • the methacrylic resin composition may contain other components as necessary, for example, crosslinked polymer particles, light diffusing agent, ultraviolet absorber, organic dye, inorganic dye, pigment, antioxidant, antistatic agent, surface active agent. You may mix
  • the shape of the methacrylic resin composition is not particularly limited, and examples thereof include powder and pellets.
  • the methacrylic resin composition of the present invention can be produced by a method including a step of mixing a methacrylic resin, an organic disulfide compound and a phosphine compound.
  • the methacrylic resin composition of the present invention can also be produced by a method of mixing a polymer composition containing a methacrylic resin and an organic disulfide compound and a phosphine compound.
  • the monomer component when producing a methacrylic resin, the monomer component is blended with one of an organic disulfide compound and a phosphine compound, and contains the methacrylic resin and the one compound.
  • a polymer composition may be obtained, and the obtained polymer composition may be mixed with the other compound.
  • an organic disulfide compound and a phosphine compound are added to the monomer component. May be.
  • a method of mixing a phosphine compound after the step of polymerizing the monomer component as a raw material of the methacrylic resin is preferable.
  • a method in which a methacrylic resin, an organic disulfide compound and a phosphine compound are mixed is preferable.
  • an organic disulfide compound is added to the monomer component, and the methacrylic resin and the organic disulfide compound are mixed.
  • a method of mixing the obtained polymer composition and a phosphine compound is preferable.
  • a methacrylic resin, an organic disulfide compound and a phosphine compound are mixed in a solvent, and the solvent may be removed after mixing.
  • the solvent include monomers containing 50% by mass or more of methyl methacrylate, ketones, alcohols, ethers and the like. Among these, monomers and ketones containing 50% by mass or more of methyl methacrylate are preferable, and acetone is preferable as the ketones.
  • a solvent may be used independently and may use 2 or more types together.
  • the methacrylic resin, the organic disulfide compound and the phosphine compound may be performed in any order. These components may be mixed at once, or a mixture is obtained by mixing a methacrylic resin with one of an organic disulfide compound and a phosphine compound, and then the resulting mixture and the other compound And may be mixed.
  • the methacrylic resin may be a resin produced by previously polymerizing monomer components by the above-described conventionally known polymerization method, and may be a commercially available methacrylic resin.
  • one of an organic disulfide compound and a phosphine compound is added to the monomer component to obtain a polymer composition containing the methacrylic resin and the one compound.
  • the method of mixing the obtained polymer composition and the other compound is, as described above, from the viewpoint of suppressing coloring during heating and melting, after adding an organic disulfide compound to the monomer component.
  • a polymer composition containing a methacrylic resin and an organic disulfide compound is obtained by polymerization using a conventionally known polymerization method, and a method of mixing the obtained polymer composition and a phosphine compound is preferable. Suppression of coloring during heating and melting by this method is more effective when the polymerization method is bulk polymerization.
  • a devolatilization step for devolatilizing unreacted monomer components after mixing the polymer composition and the other compound, a devolatilization step for devolatilizing unreacted monomer components, an extrusion step for melt extrusion of the composition to obtain pellets, and melt extrusion while devolatilization A devolatilizing extrusion step or the like may be provided.
  • each of these processes may be provided immediately after mixing, for example, may be provided immediately after obtaining a polymer composition.
  • devolatilization step for devolatilizing the unreacted monomer component
  • devolatilization A devolatilizing extrusion process for melt extrusion may be provided.
  • the methacrylic resin composition of the present invention is excellent in thermal stability, it is difficult to be thermally decomposed during heating and melting, and coloring during heating and melting is suppressed. Therefore, the methacrylic resin composition of the present invention is difficult to be colored when heated and melted to be molded, and can be suitably used for various indoor and outdoor uses such as optical parts, signboards, lighting equipment, nameplates, automobile parts, Among these, it can be particularly preferably used for applications requiring excellent transparency.
  • the methacrylic resin composition of the present invention may be heated and melt-kneaded with a kneader and then molded with a molding machine.
  • a molding method an injection molding machine is used as a molding machine, an injection molding method is performed by injection into a mold, an extrusion molding machine is used as an molding machine, an extrusion molding method is performed by extrusion from a die, and a press is used as a molding machine. And a press molding method in which a press is filled and pressed into a press machine.
  • the methacrylic resin is usually molded at about 230 to 290 ° C.
  • the methacrylic resin may be decomposed, so that molding may not be performed. Since the methacrylic resin composition of the present invention is excellent in thermal stability, it can be molded without being decomposed even when the molding temperature exceeds 290 ° C. Furthermore, since the coloring at the time of heat-melting is suppressed, the molded product excellent in transparency is obtained for the methacrylic resin composition of the present invention.
  • the thermal stability and thermal colorability of the methacrylic resin composition were evaluated by the following methods.
  • TG-DTA device (“TG / DTA6300” manufactured by SII Nano Technology Co., Ltd.), a bead or pellet from 40 ° C. to 510 ° C. at a nitrogen flow rate of 200 mL / min and a heating rate of 2 ° C./min.
  • the temperature change of the methacrylic resin composition was measured while the temperature was raised, and the thermal decomposition rate (% by weight / min) per unit time at 290 ° C. and 300 ° C. was calculated. It shows that a methacrylic resin composition is excellent in thermal stability, so that the value of a thermal decomposition rate is small.
  • the yellowness (YI value) of each pellet-shaped methacrylic resin composition obtained in Examples 4 to 6 and Comparative Examples 4 to 5 was measured by the following method. Using an injection molding device (“IS-130” manufactured by Toshiba Machine Co., Ltd.), the pellet-shaped methacrylic resin composition was filled in a cylinder having a cylinder temperature of 260 ° C. and allowed to stay for 10 minutes, and then the methacrylic resin composition. The product was injected to obtain a plate-like molded body having a thickness of 3 mm.
  • the operation of injecting after the methacrylic resin composition is filled and retained is repeated three times so that the plate-like molded body obtained by the third injection has a plate shape having a long side of 70 mm and a short side of 25 mm. It cut
  • the yellowness degree (YI value) at the time of long side optical path (optical path length 70mm) transmission was measured using the spectrophotometer (The Hitachi Ltd. make, "Hitachi Spectrophotometer U-4000"). .
  • the YI value is smaller, the methacrylic resin composition is suppressed from being colored when heated and melted, and the molded product is more excellent in transparency.
  • each methacrylic resin composition in pellet form obtained in Examples 7 to 8 and Comparative Example 6 yellowness (YI value) was measured by the following method. Using an injection molding device (“M140 / 370-SJ” manufactured by Meiki Seisakusho Co., Ltd.), the pellet-shaped methacrylic resin composition is retained in a cylinder having a cylinder temperature of 260 ° C. for 6 minutes, and then the methacrylic resin. The composition was injected to obtain a dumbbell-shaped molded body having the same shape as a JIS K 7162 1A type test piece, having a long side of 170 mm, a short side of 20 mm, and a thickness of 4 mm.
  • M140 / 370-SJ manufactured by Meiki Seisakusho Co., Ltd.
  • the operation of injecting the methacrylic resin composition after being filled and retained was repeated 12 times, and the end face of each dumbbell-shaped molded body obtained by the 11th and 12th injections was polished to obtain an evaluation sample.
  • the yellowness (YI value) at the time of transmission through the long side optical path (optical path length 170 mm) was measured using a spectrophotometer (manufactured by Hitachi, Ltd., “Hitachi Spectrophotometer U-4000”). Measurement was performed to calculate an average YI value between the YI value of the evaluation sample obtained by the 11th injection and the YI value of the evaluation sample obtained by the 12th injection.
  • the smaller the average YI value the more the methacrylic resin composition is suppressed from being colored when heated and melted, and the molded product is more excellent in transparency.
  • Example 1 96 parts by weight of methyl methacrylate, 4 parts by weight of methyl acrylate, 0.3 parts by weight of octyl mercaptan as a chain transfer agent, 0.2 parts by weight of lauroyl peroxide as a polymerization initiator, di-tert-dodecyl disulfide (hereinafter referred to as DDS) 0.0005 part by weight and 0.05 part by weight of triphenylphosphine (hereinafter referred to as TPP) were mixed and subjected to suspension polymerization to obtain a methacrylic resin composition. Furthermore, the obtained methacrylic resin composition was dried under reduced pressure at 80 ° C. for 1 day to obtain a bead-like methacrylic resin composition. Table 1 shows the results of evaluating the blending amounts of DDS and TPP and the thermal stability of the obtained bead-like methacrylic resin composition.
  • Example 2 In Example 1, a bead-like methacrylic resin composition was obtained in the same manner as in Example 1 except that 0.05 parts by weight of tri-n-butylphosphine (hereinafter referred to as TBP) was mixed instead of TPP. It was. Table 1 shows the results of evaluating the blending amounts of DDS and TBP and the thermal stability of the obtained bead-like methacrylic resin composition.
  • TBP tri-n-butylphosphine
  • Example 3 a bead-like methacrylic resin composition was obtained in the same manner as in Example 1 except that 0.05 parts by weight of tri-n-octylphosphine (hereinafter referred to as TOP) was mixed instead of TPP. It was. Table 1 shows the results of evaluating the blending amounts of DDS and TOP and the thermal stability of the obtained bead-like methacrylic resin composition.
  • TOP tri-n-octylphosphine
  • Example 1 a bead-shaped methacrylic resin composition was obtained in the same manner as in Example 1 except that DDS and TPP were not mixed. Table 1 shows the results of evaluating the thermal stability of the obtained bead-like methacrylic resin composition.
  • Example 2 In Example 1, a bead-like methacrylic resin composition was obtained in the same manner as in Example 1 except that TPP was not mixed. Table 1 shows the results of evaluating the blending amount of DDS and the thermal stability of the obtained bead-like methacrylic resin composition.
  • Example 3 a bead-like methacrylic resin composition was obtained in the same manner as in Example 1 except that 0.05 part by weight of triphenyl phosphite (hereinafter referred to as TPOP) was mixed instead of TPP. .
  • Table 1 shows the results of evaluating the blending amounts of DDS and TPOP and the thermal stability of the obtained bead-like methacrylic resin composition.
  • Example 4 96 parts by weight of methyl methacrylate, 4 parts by weight of methyl acrylate, 0.3 parts by weight of octyl mercaptan as a chain transfer agent, 0.1 parts by weight of ethylene glycol dimethacrylate, 1,1-di (t-butylperoxide as a polymerization initiator Oxy) cyclohexane 0.01 part by weight, DDS 0.0005 part by weight, and TPP 0.005 part by weight were mixed and bulk polymerized to obtain a methacrylic resin composition. Subsequently, the obtained methacrylic resin composition was supplied to a devolatilizing extruder to obtain a pellet-shaped methacrylic resin composition. Table 2 shows the results of evaluating the blending amounts of DDS and TPP, and the thermal colorability and thermal stability of the resulting pellet-like methacrylic resin composition.
  • Example 5 A pellet-shaped methacrylic resin composition was obtained in the same manner as in Example 4 except that the amount of TPP mixed in Example 4 was changed from 0.005 parts by weight to 0.05 parts by weight.
  • Table 2 shows the results of evaluating the blending amounts of DDS and TPP, and the thermal colorability and thermal stability of the resulting pellet-like methacrylic resin composition.
  • Example 6 96 parts by weight of methyl methacrylate, 4 parts by weight of methyl acrylate, 0.3 parts by weight of octyl mercaptan as a chain transfer agent, 0.1 parts by weight of ethylene glycol dimethacrylate, 1,1-di (t-butylperoxide as a polymerization initiator Oxy) cyclohexane 0.01 part by weight and DDS 0.0005 part by weight were mixed and bulk polymerized to obtain a polymer composition.
  • 100 parts by weight of the obtained polymer composition and 0.05 parts by weight of TPP were mixed and supplied to a devolatilizing extruder to obtain a pellet-shaped methacrylic resin composition.
  • Table 2 shows the results of evaluating the blending amounts of DDS and TPP, and the thermal colorability and thermal stability of the resulting pellet-like methacrylic resin composition.
  • Example 4 a pellet-shaped methacrylic resin composition was obtained in the same manner as in Example 4 except that DDS and TPP were not mixed. Table 2 shows the results of evaluating the thermal colorability and thermal stability of the obtained pellet-like methacrylic resin composition.
  • Example 5 a pellet-like methacrylic resin composition was obtained in the same manner as in Example 4 except that TPP was not mixed.
  • Table 2 shows the results of evaluating the blending amount of DDS, and the thermal colorability and thermal stability of the obtained pellet-shaped methacrylic resin composition.
  • Example 7 88 parts by weight of methyl methacrylate, 7 parts by weight of methyl acrylate, 0.3 parts by weight of octyl mercaptan as a chain transfer agent, 0.01 parts by weight of tert-amylperoxy-2-ethylhexanoate as a polymerization initiator, DDS 0. 0005 parts by weight were mixed and bulk polymerized to obtain a polymer composition. Next, 95 parts by weight of the obtained polymer composition and 0.005 parts by weight of TPP were mixed and supplied to a devolatilizing extruder to obtain a pellet-shaped methacrylic resin composition. Table 3 shows the results of evaluating the blending amounts of DDS and TPP, and the thermal colorability and thermal stability of the obtained pellet-like methacrylic resin composition.
  • Example 8 a pellet-like methacrylic resin composition was obtained in the same manner as in Example 7 except that 0.005 parts by weight of triphenylphosphine oxide (hereinafter referred to as TPPO) was mixed instead of TPP.
  • TPPO triphenylphosphine oxide
  • Example 7 (Comparative Example 6) In Example 7, a pellet-shaped methacrylic resin composition was obtained in the same manner as in Example 7 except that TPP was not mixed. Table 3 shows the results of evaluating the blending amount of DDS, the thermal colorability and the thermal stability of the obtained pellet-shaped methacrylic resin composition.
  • the methacryl resin composition which was excellent in thermal stability and the coloring at the time of heat-melting was suppressed is provided.
  • the methacrylic resin composition of the present invention is excellent in thermal stability and suppresses coloring during heating and melting. Therefore, a molded article formed by molding the methacrylic resin composition of the present invention that has been melted by heating is excellent in transparency.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne une composition de résine méthacrylique comprenant: une résine méthacrylique; un composé disulfure organique; et au moins un composé choisi dans le groupe comprenant des composés de phosphine représentés chacun par la formule (I) et des compositions d'oxyde de phosphine représentés chacun par la formule (II).
PCT/JP2014/051313 2013-01-29 2014-01-16 Composition de résine méthacrylique, procédé pour produire une composition de résine méthacrylique, et article moulé WO2014119456A1 (fr)

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CN104403250B (zh) * 2014-11-28 2016-09-14 上海金山锦湖日丽塑料有限公司 一种热稳定性优异的甲基丙烯酸甲酯树脂
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04185605A (ja) * 1990-11-20 1992-07-02 Mitsubishi Rayon Co Ltd 耐溶剤性に優れたメタクリル樹脂板の製造方法
JPH07166020A (ja) * 1993-12-13 1995-06-27 Sumitomo Chem Co Ltd メタクリル樹脂組成物及びその製造方法
JP2002348309A (ja) * 2001-05-28 2002-12-04 Mitsubishi Rayon Co Ltd メタクリル系樹脂組成物およびメタクリル系樹脂成形品の製造方法
JP2005324391A (ja) * 2004-05-13 2005-11-24 Sumitomo Chemical Co Ltd メタクリル樹脂製導光体の製造方法
JP2006104376A (ja) * 2004-10-07 2006-04-20 Sumitomo Chemical Co Ltd メタクリル樹脂組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04185605A (ja) * 1990-11-20 1992-07-02 Mitsubishi Rayon Co Ltd 耐溶剤性に優れたメタクリル樹脂板の製造方法
JPH07166020A (ja) * 1993-12-13 1995-06-27 Sumitomo Chem Co Ltd メタクリル樹脂組成物及びその製造方法
JP2002348309A (ja) * 2001-05-28 2002-12-04 Mitsubishi Rayon Co Ltd メタクリル系樹脂組成物およびメタクリル系樹脂成形品の製造方法
JP2005324391A (ja) * 2004-05-13 2005-11-24 Sumitomo Chemical Co Ltd メタクリル樹脂製導光体の製造方法
JP2006104376A (ja) * 2004-10-07 2006-04-20 Sumitomo Chemical Co Ltd メタクリル樹脂組成物

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