WO2014119456A1 - Methacrylic resin composition, method for producing methacrylic resin composition, and molded article - Google Patents

Methacrylic resin composition, method for producing methacrylic resin composition, and molded article 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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French (fr)
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.

Abstract

A methacrylic resin composition comprising: a methacrylic resin; an organic disulfide compound; and at least one compound selected from the group consisting of phosphine compounds each represented by formula (I) and phosphine oxide compounds each represented by formula (II).

Description

メタクリル樹脂組成物、メタクリル樹脂組成物の製造方法および成形体Methacrylic resin composition, method for producing methacrylic resin composition, and molded article
　本発明は、メタクリル樹脂組成物、メタクリル樹脂組成物の製造方法および成形体に関する。本発明は、より詳細には、メタクリル樹脂、有機ジスルフィド化合物およびホスフィン化合物を含有するメタクリル樹脂組成物、メタクリル樹脂組成物の製造方法および成形体に関する。 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.
　メタクリル樹脂は透明性に優れることから、例えば、光学部品、看板、照明器具、銘板など、屋内外の各種用途に用いられている。しかしながら、メタクリル樹脂は比較的熱安定性が低い。そのため、メタクリル樹脂には、例えば成形時の加熱溶融により熱分解を起こしやすいという問題がある。 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.
　熱安定性に優れるメタクリル樹脂組成物として、特許文献１には、メタクリル樹脂にジ−ｔｅｒｔ−アルキルジスルフィドが配合されたメタクリル樹脂組成物が開示されている。しかしながら、特許文献１に開示されたメタクリル樹脂組成物には、加熱溶融時に着色が生じるという問題がある。これは、加熱溶融の際に生じるジスルフィド化合物の変性によるものと理解される。 As a methacrylic resin composition having excellent thermal stability, Patent Document 1 discloses a methacrylic resin composition in which di-tert-alkyl disulfide is blended with a methacrylic resin. However, 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.
　加熱溶融時の着色が抑制されたメタクリル樹脂組成物として、特許文献２には、メタクリル樹脂にジ−ｔｅｒｔ−アルキルジスルフィドと、さらに亜リン酸エステル化合物が配合されたメタクリル樹脂組成物が開示されている。 As a methacrylic resin composition in which coloring at the time of heating and melting is suppressed, 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.
特開昭５１−３６２５８号公報Japanese Patent Laid-Open No. 51-36258 特開昭５４−１２２３５１号公報JP 54-122351 A
　しかしながら、特許文献２に開示されたメタクリル樹脂組成物は、加熱溶融時の着色は抑制されるものの、熱安定性の向上が十分ではない。特許文献２に開示されたメタクリル樹脂組成物の熱安定性は、メタクリル樹脂そのものの熱安定性と同程度である。 However, 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.
　本発明の課題は、熱安定性に優れ、かつ、加熱溶融時の着色が抑制されたメタクリル樹脂組成物を提供することである。 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.
　本発明は、下記（１）~（１３）に関する。
　（１）メタクリル樹脂と、有機ジスルフィド化合物と、以下の式（Ｉ）で表されるホスフィン化合物および以下の式（ＩＩ）で表されるホスフィンオキシド化合物からなる群より選択される少なくとも１種の化合物と、を含有するメタクリル樹脂組成物。
Figure JPOXMLDOC01-appb-I000003
（式（Ｉ）中、Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、水素原子、炭素数１~１２のアルキル基、炭素数５~１２のシクロアルキル基、炭素数６~１２のアルキルシクロアルキル基、炭素数６~１２のアリール基を表し、それぞれの炭素原子に結合した任意の水素原子はヘテロ原子を含む置換基で置換されていてもよい。）
Figure JPOXMLDOC01-appb-I000004
（式（ＩＩ）中、Ｒ４、Ｒ５およびＲ６は、それぞれ独立して、水素原子、炭素数１~１２のアルキル基、炭素数５~１２のシクロアルキル基、炭素数６~１２のアルキルシクロアルキル基、炭素数６~１２のアリール基を表し、それぞれの炭素原子に結合した任意の水素原子はヘテロ原子を含む置換基で置換されていてもよい。）
　（２）式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６が、同一の置換基である前記（１）に記載のメタクリル樹脂組成物。
　（３）式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６が、フェニル基である前記（１）または（２）に記載のメタクリル樹脂組成物。
　（４）有機ジスルフィド化合物が、ジアルキルジスルフィド化合物である前記（１）~（３）のいずれかに記載のメタクリル樹脂組成物。
　（５）有機ジスルフィド化合物が、ジ−ｔｅｒｔ−ドデシルジスルフィドである前記（１）~（４）のいずれかに記載のメタクリル樹脂組成物。
　（６）メタクリル樹脂と、有機ジスルフィド化合物と、式（Ｉ）で表されるホスフィン化合物および式（ＩＩ）で表されるホスフィンオキシド化合物からなる群より選択される少なくとも１種の化合物と、を混合する工程を含む、前記（１）~（５）のいずれかに記載のメタクリル樹脂組成物の製造方法。
　（７）前記混合が溶媒中で行われる前記（６）に記載の方法。
　（８）前記混合後、前記溶媒が除去される前記（７）に記載の方法。
　（９）前記溶媒が、メタクリル酸メチルを５０質量％以上含有する単量体、ケトン類、アルコール類およびエーテル類からなる群より選択される少なくとも１種の溶媒である前記（７）または（８）に記載の方法。
　（１０）前記溶媒が、メタクリル酸メチルを５０質量％以上含有する単量体、アセトンまたはこれらの混合溶媒である前記（７）~（９）に記載の方法。
　（１１）メタクリル樹脂および有機ジスルフィド化合物を含有する重合体組成物と、式（Ｉ）で表されるホスフィン化合物および式（ＩＩ）で表されるホスフィンオキシド化合物からなる群より選択される少なくとも１種の化合物とを混合する工程を含む、前記（１）~（５）のいずれかに記載のメタクリル樹脂組成物の製造方法。
　（１２）前記重合体組成物が、単量体成分からメタクリル樹脂を製造する際に、単量体成分に有機ジスルフィド化合物を配合して得られた組成物である、前記（１１）に記載の方法。
　（１３）前記（１）~（５）のいずれかに記載のメタクリル樹脂組成物を成形してなる成形体。 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) And a methacrylic resin composition.
Figure JPOXMLDOC01-appb-I000003
(In the formula (I), 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.)
Figure JPOXMLDOC01-appb-I000004
(In the formula (II), 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.)
(2) The methacrylic resin composition according to (1), wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same substituent.
(3) The methacrylic resin composition according to the above (1) or (2), wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are phenyl groups.
(4) The methacrylic resin composition according to any one of (1) to (3), wherein the organic disulfide compound is a dialkyl disulfide compound.
(5) The methacrylic resin composition according to any one of (1) to (4), wherein the organic disulfide compound is di-tert-dodecyl disulfide.
(6) Mixing a methacrylic resin, an organic disulfide compound, and at least one compound selected from the group consisting of a phosphine compound represented by formula (I) and a phosphine oxide compound represented by formula (II) The manufacturing method of the methacrylic resin composition in any one of said (1)-(5) including the process to do.
(7) The method according to (6), wherein the mixing is performed in a solvent.
(8) The method according to (7), wherein the solvent is removed after the mixing.
(9) The above (7) or (8), wherein the solvent is at least one solvent selected from the group consisting of monomers containing 50% by mass or more of methyl methacrylate, ketones, alcohols and ethers. ) Method.
(10) The method according to (7) to (9), wherein the solvent is a monomer containing 50% by mass or more of methyl methacrylate, acetone, or a mixed solvent thereof.
(11) At least one selected from the group consisting of a polymer composition containing a methacrylic resin and an organic disulfide compound, a phosphine compound represented by formula (I), and a phosphine oxide compound represented by formula (II) The method for producing a methacrylic resin composition according to any one of (1) to (5), comprising a step of mixing the compound.
(12) The said polymer composition is a composition obtained by mix | blending an organic disulfide compound with a monomer component, when manufacturing a methacryl resin from a monomer component, The said (11) description Method.
(13) A molded article obtained by molding the methacrylic resin composition according to any one of (1) to (5).
　本発明によれば、熱安定性に優れ、かつ、加熱溶融時の着色が抑制されたメタクリル樹脂組成物が提供される。 According to the present invention, there is provided a methacrylic resin composition that is excellent in thermal stability and suppressed in coloring during heating and melting.
　本発明のメタクリル樹脂組成物は、熱安定性に優れ、かつ、加熱溶融時の着色が抑制される。そのため、加熱溶融した本発明のメタクリル樹脂組成物を成形してなる成形体は透明性に優れる。 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.
　本発明のメタクリル樹脂組成物は、メタクリル樹脂と、有機ジスルフィド化合物と、以下の式（Ｉ）で表されるホスフィン化合物（以下、ホスフィン化合物（Ｉ）ということがある）および以下の式（ＩＩ）で表されるホスフィンオキシド化合物（以下、ホスフィンオキシド化合物（ＩＩ）ということがある）からなる群より選択される少なくとも１種の化合物と、を含有する。 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)).
Figure JPOXMLDOC01-appb-I000005
（式（Ｉ）中、Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、水素原子、炭素数１~１２のアルキル基、炭素数５~１２のシクロアルキル基、炭素数６~１２のアルキルシクロアルキル基、炭素数６~１２のアリール基を表し、それぞれの炭素原子に結合した任意の水素原子はヘテロ原子を含む置換基で置換されていてもよい。）
Figure JPOXMLDOC01-appb-I000005
(In the formula (I), 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.)
Figure JPOXMLDOC01-appb-I000006
（式（ＩＩ）中、Ｒ４、Ｒ５およびＲ６は、それぞれ独立して、水素原子、炭素数１~１２のアルキル基、炭素数５~１２のシクロアルキル基、炭素数６~１２のアルキルシクロアルキル基、炭素数６~１２のアリール基を表し、それぞれの炭素原子に結合した任意の水素原子はヘテロ原子を含む置換基で置換されていてもよい。）
Figure JPOXMLDOC01-appb-I000006
(In the formula (II), 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.)
　メタクリル樹脂は、メタクリル酸エステルを主成分とする単量体成分を重合してなる重合体である。メタクリル樹脂は、メタクリル酸エステルの単独重合体であってもよいし、メタクリル酸エステル５０重量％以上とこれ以外の単量体５０重量％以下との共重合体であってもよい。ここで、メタクリル酸エステルとしては、通常、メタクリル酸のアルキルエステルが用いられる。 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. Here, as the methacrylic acid ester, an alkyl ester of methacrylic acid is usually used.
　単量体成分の好ましい組成は、全単量体を基準として、メタクリル酸アルキルエステルが５０~１００重量％、アクリル酸アルキルエステルが０~５０重量％、これら以外の単量体が０~４９重量％であり、より好ましくは、メタクリル酸アルキルエステルが５０~９９．９重量％、アクリル酸アルキルエステルが０．１~５０重量％、これら以外の単量体が０~４９重量％であり、さらに好ましくは、メタクリル酸アルキルエステルが６０~９９．９重量％、アクリル酸アルキルエステルが０．１~４０重量％、これら以外の単量体が０~３９重量％である。 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.
　メタクリル酸アルキルエステルとしては、例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸２−エチルヘキシルなどが挙げられる。メタクリル酸アルキルエステルのアルキル基の炭素数は通常１~８、好ましくは１~４である。中でもメタクリル酸メチルが好ましく用いられる。 Examples of the methacrylic acid alkyl ester 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.
　アクリル酸アルキルエステルとしては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２−エチルヘキシルなどが挙げられる。アクリル酸アルキルエステルのアルキル基の炭素数は通常１~８、好ましくは１~４である。 Examples of the acrylic acid alkyl ester 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.
　メタクリル酸アルキルエステルおよびアクリル酸アルキルエステル以外の単量体としては、例えば、単官能単量体、すなわち分子内に重合性の炭素−炭素二重結合を１個有する化合物であってもよいし、多官能単量体、すなわち分子内に重合性の炭素−炭素二重結合を少なくとも２個有する化合物であってもよいが、単官能単量体が好ましく用いられる。
　単官能単量体としては、例えば、スチレン、α−メチルスチレン、ビニルトルエンなどのスチレン系単量体、アクリロニトリル、メタクリロニトリルなどのシアン化アルケニル、アクリル酸、メタクリル酸、無水マレイン酸、Ｎ−置換マレイミドなどが挙げられる。
　多官能単量体としては、例えば、エチレングリコールジメタクリレート、ブタンジオールジメタクリレート、トリメチロールプロパントリアクリレートなどの多価アルコールのポリ不飽和カルボン酸エステル、アクリル酸アリル、メタクリル酸アリル、ケイ皮酸アリルなどの不飽和カルボン酸のアルケニルエステル、フタル酸ジアリル、マレイン酸ジアリル、トリアリルシアヌレート、トリアリルイソシアヌレートなどの多塩基酸のポリアルケニルエステル、ジビニルベンゼンなどの芳香族ポリアルケニル化合物などが挙げられる。 As monomers other than methacrylic acid alkyl ester and acrylic acid alkyl ester, for example, a monofunctional monomer, that is, a compound having one polymerizable carbon-carbon double bond in the molecule, Although it may be a polyfunctional monomer, that is, a compound having at least two polymerizable carbon-carbon double bonds in the molecule, a monofunctional monomer is preferably used.
Examples of monofunctional monomers include styrene monomers such as styrene, α-methylstyrene, and vinyl toluene, alkenyl cyanides such as acrylonitrile and methacrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N- Examples thereof include substituted maleimides.
Examples of the polyfunctional monomer 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. .
　なお、メタクリル酸アルキルエステル、アクリル酸アルキルエステル、およびこれら以外の単量体は、それぞれ、単独で用いてもよく、必要に応じてそれらの２種以上を併用してもよい。 In addition, the 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.
　メタクリル樹脂は、単量体成分およびその部分重合体成分から選択される少なくとも１種の成分（以下、まとめて単に、単量体成分ということがある）を、従来公知の重合方法で重合することで製造することができる。重合方法としては、例えば、塊状重合法、溶液重合法、乳化重合法、懸濁重合法、注型重合法などが挙げられる。
　部分重合体成分は、単量体成分と重合体成分の混合物である。部分重合体成分において、重合体成分の含有率が１０~７０重量％であることが好ましい。 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. Can be manufactured. Examples of 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.
　重合は、通常、重合開始剤を用いて行われる。重合開始剤としては、ラジカル重合開始剤が好ましく用いられる。ラジカル開始剤としては、例えば、２，２’−アゾビス（イソブチロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）のようなアゾ化合物や、１，１−ジ（ｔ−ブチルパーオキシ）シクロヘキサン、１，１−ジ（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、ベンゾイルパーオキサイド、ラウロイルパーオキサイドのような過酸化物などが挙げられる。必要に応じて、アミン類のような促進剤を併用してもよい。また、連鎖移動剤を用いてもよい。連鎖移動剤としては、例えば、メチルメルカプタン、ブチルメルカプタン、オクチルメルカプタン、ドデシルメルカプタン、エチルヘキシルチオグリコレートなどが挙げられる。 Polymerization is usually performed using a polymerization initiator. As the polymerization initiator, a radical polymerization initiator is preferably used. Examples of 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. If necessary, an accelerator such as amines may be used in combination. A chain transfer agent may also be used. Examples of the chain transfer agent include methyl mercaptan, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, ethylhexyl thioglycolate and the like.
　重合方法が溶液重合法である場合、溶媒としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類；メタノール、エタノール、１−プロパノール、イソプロパノール、１−ブタノール、２−ブタノール、２−メチル−１−プロパノール、２−メチル−２−プロパノールなどのアルコール類；ベンゼン、トルエン、アニソールなどの芳香族化合物；クロロホルム、塩化メチレンなどのハロゲン化炭化水素；テトラヒドロフラン、１，４−ジオキサンなどのエーテル類；アセトニトリル、ジメチルスルホキシド、Ｎ，Ｎ−ジメチルホルムアミド、水とアルコールとの混合溶媒などが挙げられる。 When the polymerization method is a solution polymerization method, 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.
　単量体成分には、必要に応じて、光拡散剤、着色剤、補強剤、充填剤、離型剤、安定剤、紫外線吸収剤、酸化防止剤、帯電防止剤などの各種添加剤を添加してもよい。添加剤は、単独で用いてもよく、２種以上を併用してもよい。 Various 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.
　有機ジスルフィド化合物としては、例えば、ジエチルジスルフィド、ジ−ｎ−プロピルジスルフィド、ジ−ｎ−ブチルジスルフィド、ジ−ｓｅｃ−ブチルジスルフィド、ジ−ｔｅｒｔ−ブチルジスルフィド、ジ−ｎ−アミルジスルフィド、ジ−ｔｅｒｔ−アミルジスルフィド、ジ−ｔｅｒｔ−ヘキシルジスルフィド、ジ−ｎ−オクチルジスルフィド、ジ−ｔｅｒｔ−オクチルジスルフィド、ジ−ｎ−ドデシルジスルフィド、ジ−ｔｅｒｔ−ドデシルジスルフィド、ジ−ｎ−ステアリンジスルフィド、エチル−ｎ−プロピルジスルフィド、エチル−ｔｅｒｔ−ブチルジスルフィド、エチル−ｓｅｃ−ブチルジスルフィド、ｎ−プロピル−イソプロピルジスルフィド等のジアルキルジスルフィド化合物；ジフェニルジスルフィド、ジベンジルジスルフィド、ジ−ｐ−トリルジスルフィド等の芳香族ジスルフィド化合物；ジトリメチレンジスルフィド、ジテトラメチレンジスルフィド、ジシクロヘキシルジスルフィド等の環状ジスルフィド化合物；シスチン、ジアミノジフェニルジスルフィド等のアミノ基を有するジスルフィド化合物；ジチオジクリコール酸、ジチオジプロピオン酸、ジチオジクリコール酸−２−エチルヘキシル等のカルボン酸およびカルボン酸誘導体のジスルフィド類；ジアリルジスルフィド等の不飽和結合を有するジスルフィド化合物などが挙げられる。これら有機ジスルフィド化合物の中でも、ジアルキルジスルフィド化合物が好ましい。ジアルキルジスルフィド化合物の中でも、ジ−ｔｅｒｔ−アルキルジスルフィドがより好ましく、ジ−ｔｅｒｔ−ドデシルジスルフィドがさらに好ましい。有機ジスルフィド化合物は、単独で用いてもよく、２種以上を併用してもよい。 Examples of the organic disulfide compound 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; diphenyl disulfide, dibenzyl disulfide Aromatic disulfide compounds such as rufide and di-p-tolyl disulfide; cyclic disulfide compounds such as ditrimethylene disulfide, ditetramethylene disulfide and dicyclohexyl disulfide; disulfide compounds having an amino group such as cystine and diaminodiphenyl disulfide; dithiodiglycolic acid And disulfides of carboxylic acid and carboxylic acid derivatives such as dithiodipropionic acid and dithiodiglycolate-2-ethylhexyl; disulfide compounds having an unsaturated bond such as diallyl disulfide. Among these organic disulfide compounds, dialkyl disulfide compounds are preferable. Among 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.
　有機ジスルフィド化合物の含有量は特に制限されないが、熱安定性に優れ、かつ、含有量に見合った効果が得られ、経済的に有利となる観点から、メタクリル樹脂１００重量部に対して好ましくは０．０００１~１．０重量部であり、より好ましくは０．０００１~０．０１重量部である。 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.
　メタクリル樹脂組成物は、メタクリル樹脂および有機ジスルフィド化合物を含有し、さらに、ホスフィン化合物（Ｉ）およびホスフィンオキシド化合物（ＩＩ）からなる群より選択される少なくとも１種の化合物（以下、ホスフィン系化合物ということがある）を含有する。メタクリル樹脂組成物としては、１種以上のホスフィン化合物（Ｉ）を含有し、ホスフィンオキシド化合物（ＩＩ）を含有しない組成物であってもよいし、１種以上のホスフィンオキシド化合物（ＩＩ）を含有し、ホスフィン化合物（Ｉ）を含有しない組成物であってもよいし、１種以上のホスフィン化合物（Ｉ）と１種以上のホスフィンオキシド化合物（ＩＩ）とを含有する組成物であってもよい。 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). .
　ホスフィン化合物（Ｉ）において、炭素数１~１２のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、オクチル基などが挙げられる。なお、炭素数３~１２のアルキル基の場合は、全ての構造異性体を含む。例えば、プロピル基は、ｎ−プロピル基およびイソプロピル基を含み、ブチル基は、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基およびｔｅｒｔ−ブチル基を含む。 In the phosphine compound (I), 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. In the case of an alkyl group having 3 to 12 carbon atoms, all structural isomers are included. For example, a propyl group includes an n-propyl group and an isopropyl group, and a butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
　ホスフィン化合物（Ｉ）において、炭素数５~１２のシクロアルキル基としては、例えば、シクロペンチル基、シクロヘキシル基、シクロオクチル基、シクロドデシル基などが挙げられる。 In the phosphine compound (I), 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.
　ホスフィン化合物（Ｉ）において、炭素数６~１２のアルキルシクロアルキル基としては、例えば、メチルシクロペンチル基、メチルシクロヘキシル基、メチルシクロオクチル基、メチルシクロドデシル基などが挙げられる。 In the phosphine compound (I), 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.
　ホスフィン化合物（Ｉ）において、炭素数６~１２のアリール基としては、例えば、フェニル基、ベンジル基、ｏ−トリル基、ｍ−トリル基、ｐ−トリル基、フェネチル基、トリルメチル基、フェニルブチル基などが挙げられる。アリール基の芳香環上にはヘテロ原子を含む任意の置換基を有していてもよく、例えばメトキシ基、エトキシ基、ヒドロキシ基、カルボキシル基、フルオロ基、クロロ基、ブロモ基などを有していてもよい。そのようなアリール基としては、例えば、４−メトキシフェニル基やペンタフルオロフェニル基などが挙げられる。アリール基の芳香環は多環を形成していてもよく、そのようなアリール基としては、例えば、ナフチル基などが挙げられる。 In the phosphine compound (I), 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.
　ホスフィン化合物（Ｉ）としては、例えば、トリメチルホスフィン、トリ−ｎ−ブチルホスフィン、トリ−ｔｅｒｔ−ブチルホスフィン、トリス−（３−ヒドロキシプロピル）ホスフィン、トリ−ｎ−ヘキシルホスフィン、トリシクロヘキシルホスフィン、トリ−ｎ−オクチルホスフィン、ジエチルフェニルホスフィンメチルジフェニルホスフィン、エチルジフェニルホスフィン、ジフェニルプロピルホスフィン、ジフェニルシクロヘキシルホスフィン、トリフェニルホスフィン、トリ−ｏ−トリルホスフィン、トリ−ｍ−トリルホスフィン、トリ−ｐ−トリルホスフィン、トリス−（４−メトキシフェニル）ホスフィンなどが挙げられる。中でも、取り扱いの容易さの観点から、トリフェニルホスフィンが好ましい。ホスフィン化合物（Ｉ）は、単独で用いてもよく、２種以上を併用してもよい。 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 phosphine compound (I) may be used alone or in combination of two or more.
　ホスフィン化合物（Ｉ）の含有量は特に制限されるものではないが、熱安定性と加熱溶融時の着色抑制の観点から、メタクリル樹脂１００重量部に対して好ましくは０．０００１~１．０重量部であり、より好ましくは０．０００１~０．１重量部であり、さらに好ましくは０．０００５~０．０１重量部である。 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.
　ホスフィンオキシド化合物（ＩＩ）において、炭素数１~１２のアルキル基としては、ホスフィン化合物（Ｉ）における炭素数１~１２のアルキル基として例示した基と同じものが挙げられる。 In the phosphine oxide compound (II), 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).
　ホスフィンオキシド化合物（ＩＩ）において、炭素数５~１２のシクロアルキル基としては、ホスフィン化合物（Ｉ）における炭素数５~１２のアルキル基として例示した基と同じ基が挙げられる。 In the phosphine oxide compound (II), 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).
　ホスフィンオキシド化合物（ＩＩ）において、炭素数６~１２のアルキルシクロアルキル基としては、ホスフィン化合物（Ｉ）における炭素数６~１２のアルキルシクロアルキル基として例示した基と同じ基が挙げられる。 In the phosphine oxide compound (II), 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).
　ホスフィンオキシド化合物（ＩＩ）において、炭素数６~１２のアリール基としては、ホスフィン化合物（Ｉ）における炭素数６~１２のアリール基として例示した基と同じ基が挙げられる。 In the phosphine oxide compound (II), 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).
　ホスフィンオキシド化合物（ＩＩ）としては、例えば、トリメチルホスフィンオキシド、トリ−ｎ−ブチルホスフィンオキシド、トリ−ｔｅｒｔ−ブチルホスフィンオキシド、トリス−（３−ヒドロキシプロピル）ホスフィンオキシド、トリ−ｎ−ヘキシルホスフィンオキシド、トリシクロヘキシルホスフィンオキシド、トリ−ｎ−オクチルホスフィンオキシド、ジエチルフェニルホスフィンメチルジフェニルホスフィンオキシド、エチルジフェニルホスフィンオキシド、ジフェニルプロピルホスフィンオキシド、ジフェニルシクロヘキシルホスフィンオキシド、トリフェニルホスフィンオキシド、トリ−ｏ−トリルホスフィンオキシド、トリ−ｍ−トリルホスフィンオキシド、トリ−ｐ−トリルホスフィンオキシド、トリス−（４−メトキシフェニル）ホスフィンオキシドなどが挙げられる。中でも、取扱いの容易さの観点から、トリフェニルホスフィンオキシドが好ましい。ホスフィンオキシド化合物（ＩＩ）は、単独で用いてもよく、２種以上を併用してもよい。 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, triphenylphosphine oxide is preferable from the viewpoint of easy handling. A phosphine oxide compound (II) may be used independently and may use 2 or more types together.
　ホスフィンオキシド化合物（ＩＩ）は、該当する置換基を有するホスフィン化合物（Ｉ）が酸化することによって得ることができる。すなわち、ホスフィンオキシド化合物（ＩＩ）をメタクリル樹脂組成物に含有させるとき、後述するメタクリル樹脂組成物を製造する方法において、ホスフィンオキシド化合物（ＩＩ）を直接使用してもよいし、まず該当する置換基を有するホスフィン化合物（Ｉ）を配合し、次いで配合したホスフィン化合物（Ｉ）の一部または全部を酸化させてホスフィンオキシド化合物（ＩＩ）としてもよい。
　例えば、ホスフィンオキシド化合物（ＩＩ）として、トリフェニルホスフィンオキシドをメタクリル樹脂組成物に含有させるのであれば、後述するメタクリル樹脂組成物を製造する方法において、トリフェニルホスフィンオキシドを使用してもよいし、まずトリフェニルホスフィンを配合し、次いで配合したトリフェニルホスフィンを酸化させてトリフェニルホスフィンオキシドとしてもよい。ここで、ホスフィン化合物（Ｉ）は、酸素存在下で熱が付与されることにより酸化されやすい。そこで、該当する置換基を有するホスフィン化合物（Ｉ）を配合し、次いで配合したホスフィン化合物（Ｉ）を酸化させることで、ホスフィンオキシド化合物（ＩＩ）をメタクリル樹脂組成物中に含有させるには、ホスフィン化合物（Ｉ）を配合した後に、ホスフィン化合物（Ｉ）を酸化する工程を設ければよい。このような酸化工程としては、後述する重合工程、脱揮工程、押出工程などが挙げられる。中でも、ホスフィン化合物（Ｉ）は、重合工程において、ホスフィンオキシド化合物（ＩＩ）へと酸化されやすい。また、ホスフィン化合物（Ｉ）をメタクリル樹脂組成物に含有せしめた際に系中で自発的に酸化された結果としてホスフィンオキシド化合物（ＩＩ）を含有するメタクリル樹脂組成物を得てもよい。 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).
For example, as a phosphine oxide compound (II), 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. Here, the phosphine compound (I) is easily oxidized by applying heat in the presence of oxygen. Therefore, 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.
　ホスフィンオキシド化合物（ＩＩ）の含有量は特に制限されるものではないが、熱安定性と加熱溶融時の着色抑制の観点から、メタクリル樹脂１００重量部に対して好ましくは０．０００１~１．０重量部であり、より好ましくは０．０００１~０．１重量部であり、さらに好ましくは０．０００５~０．０１重量部である。
　メタクリル樹脂組成物が、ホスフィン化合物（Ｉ）とホスフィンオキシド化合物（ＩＩ）とを、それぞれ１種以上含有する場合、ホスフィン化合物（Ｉ）の含有量とホスフィンオキシド化合物（ＩＩ）の含有量との合計量は、熱安定性と加熱溶融時の着色抑制の観点から、メタクリル樹脂１００重量部に対して好ましくは０．０００１~１．０重量部であり、より好ましくは０．０００１~０．１重量部であり、さらに好ましくは０．０００５~０．０５重量部である。 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.
When 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.
　メタクリル樹脂組成物に含有される有機ジスルフィド化合物とホスフィン系化合物のモル比（ホスフィン系化合物／有機ジスルフィド化合物）は、熱安定性と加熱溶融時の着色抑制の観点から、好ましくは１~５００であり、より好ましくは３~１００であり、さらに好ましくは５~５０であり、特に好ましくは１０~２０である。
　メタクリル樹脂に対する有機ジスルフィド化合物およびホスフィン系化合物の含有量が、それぞれ上記所定の範囲であって、かつ有機ジスルフィド化合物とホスフィン系化合物のモル比が上記所定の範囲であることが好ましい。 The molar ratio of the organic disulfide compound and the phosphine compound contained in the methacrylic resin composition (phosphine compound / organic disulfide compound) 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.
　メタクリル樹脂組成物には、必要に応じて他の成分、例えば、架橋重合体粒子、光拡散剤、紫外線吸収剤、有機系染料、無機系染料、顔料、酸化防止剤、帯電防止剤、界面活性剤などを配合してもよい。メタクリル樹脂組成物を製造する際に、メタクリル樹脂組成物へ他の成分を配合することができる。メタクリル樹脂組成物の形状は、特に制限されず、例えば、粉状、ペレット状などが挙げられる。 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 | blend an agent etc. When manufacturing a methacrylic resin composition, another component can be mix | blended with a methacrylic resin composition. The shape of the methacrylic resin composition is not particularly limited, and examples thereof include powder and pellets.
　本発明のメタクリル樹脂組成物は、メタクリル樹脂、有機ジスルフィド化合物およびホスフィン系化合物を混合する工程を含む方法によって製造することができる。
　本発明のメタクリル樹脂組成物は、メタクリル樹脂および有機ジスルフィド化合物を含有する重合体組成物と、ホスフィン系化合物とを混合する方法によっても製造することができる。
　本発明の方法において、メタクリル樹脂を製造する際に、単量体成分に、有機ジスルフィド化合物およびホスフィン系化合物のうちいずれか一方の化合物を配合して、メタクリル樹脂と該一方の化合物とを含有する重合体組成物を得、得られた重合体組成物と他方の化合物を混合してもよいし、メタクリル樹脂を製造する際に、単量体成分に、有機ジスルフィド化合物およびホスフィン系化合物を配合してもよい。中でも、加熱溶融時の着色を抑制する観点からは、メタクリル樹脂の原料としての単量体成分を重合する工程後に、ホスフィン系化合物を混合する方法が好ましい。具体的には、メタクリル樹脂、有機ジスルフィド化合物およびホスフィン系化合物を混合する方法が好ましく、メタクリル樹脂を製造する際に、単量体成分に、有機ジスルフィド化合物を配合して、メタクリル樹脂と有機ジスルフィド化合物とを含有する重合体組成物を得、得られた重合体組成物とホスフィン系化合物を混合する方法が好ましい。 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.
In the method of the present invention, 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. When a methacrylic resin is produced, an organic disulfide compound and a phosphine compound are added to the monomer component. May be. Among these, from the viewpoint of suppressing coloring during heating and melting, 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. Specifically, a method in which a methacrylic resin, an organic disulfide compound and a phosphine compound are mixed is preferable. When a methacrylic resin is produced, an organic disulfide compound is added to the monomer component, and the methacrylic resin and the organic disulfide compound are mixed. And a method of mixing the obtained polymer composition and a phosphine compound is preferable.
　メタクリル樹脂、有機ジスルフィド化合物およびホスフィン系化合物を混合する方法としては、従来公知の方法が挙げられ、混合機による混合、混練機による溶融混練、溶媒混練などが挙げられる。この方法において、各成分を混合した後に、メタクリル樹脂組成物を溶融押出してペレットとして得る押出工程を設けてもよい。 As a method of mixing the methacrylic resin, the organic disulfide compound and the phosphine compound, conventionally known methods may be mentioned, and examples thereof include mixing by a mixer, melt kneading by a kneader, and solvent kneading. In this method, after mixing each component, you may provide the extrusion process of melt-extruding a methacryl resin composition and obtaining as a pellet.
　溶媒混練の場合、溶媒中で、メタクリル樹脂、有機ジスルフィド化合物およびホスフィン系化合物を混合し、混合後に溶媒を除去すればよい。溶媒としては、メタクリル酸メチルを５０質量％以上含有する単量体、ケトン類、アルコール類、エーテル類などが挙げられる。中でも、メタクリル酸メチルを５０質量％以上含有する単量体やケトン類が好ましく、ケトン類としてはアセトンが好ましい。溶媒は、単独で用いてもよく、２種以上を併用してもよい。 In the case of solvent kneading, a methacrylic resin, an organic disulfide compound and a phosphine compound are mixed in a solvent, and the solvent may be removed after mixing. Examples of 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.
　メタクリル樹脂、有機ジスルフィド化合物およびホスフィン系化合物の混合は、いかなる順序で行われてもよい。これら各成分を一度に混合してもよいし、メタクリル樹脂と、有機ジスルフィド化合物およびホスフィン系化合物のうちいずれか一方の化合物とを混合して混合物を得、次いで、得られた混合物と他方の化合物とを混合してもよい。 Mixing of 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.
　メタクリル樹脂としては、予め単量体成分を上述の従来公知の重合方法で重合して製造された樹脂であればよく、市販のメタクリル樹脂であってもよい。 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.
　メタクリル樹脂を製造する際に、単量体成分に、有機ジスルフィド化合物およびホスフィン系化合物のうちいずれか一方の化合物を配合して、メタクリル樹脂と該一方の化合物とを含有する重合体組成物を得、得られた重合体組成物と他方の化合物を混合する方法としては、上述したように、加熱溶融時の着色を抑制する観点から、単量体成分に、有機ジスルフィド化合物を配合してから上述の従来公知の重合方法で重合して、メタクリル樹脂と有機ジスルフィド化合物とを含有する重合体組成物を得、得られた重合体組成物とホスフィン系化合物を混合する方法が好ましい。この方法による加熱溶融時の着色の抑制は、重合方法が塊状重合である場合に、より有効である。 When producing a 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. As described above, 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.
　この方法において、重合体組成物と他方の化合物を混合した後に、未反応の単量体成分を脱揮する脱揮工程、組成物を溶融押出してペレットとして得る押出工程、脱揮しながら溶融押出する脱揮押出工程などを設けてもよい。なお、これら各工程は、混合直後に設けられてもよいし、例えば、重合体組成物を得た直後に設けられてもよい。 In this method, 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. In addition, each of these processes may be provided immediately after mixing, for example, may be provided immediately after obtaining a polymer composition.
　メタクリル樹脂を製造する際に、有機ジスルフィド化合物およびホスフィン系化合物を配合する方法としては、単量体成分に、有機ジスルフィド化合物およびホスフィン化合物を配合してから上述の従来公知の重合方法で重合する方法が挙げられる。 As a method of blending an organic disulfide compound and a phosphine compound when producing a methacrylic resin, a method of blending an organic disulfide compound and a phosphine compound into a monomer component and then polymerizing by the above-mentioned conventionally known polymerization method Is mentioned.
　この方法において、単量体成分を重合した後に、必要に応じて、未反応の単量体成分を脱揮する脱揮工程、メタクリル樹脂組成物を溶融押出してペレットとして得る押出工程、脱揮しながら溶融押出する脱揮押出工程などを設けてもよい。 In this method, after polymerizing the monomer component, if necessary, a devolatilization step for devolatilizing the unreacted monomer component, an extrusion step for melt-extrusion of the methacrylic resin composition to obtain a pellet, devolatilization A devolatilizing extrusion process for melt extrusion may be provided.
　本発明のメタクリル樹脂組成物は、熱安定性に優れているので、加熱溶融時に熱分解し難く、かつ、加熱溶融時の着色が抑制される。そのため、本発明のメタクリル樹脂組成物は、加熱溶融して成形する際に着色し難く、光学部品、看板、照明器具、銘板、自動車部品などの屋内外の各種用途に好適に用いることができ、中でも優れた透明性が要求される用途に特に好ましく用いることができる。 Since 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.
　本発明のメタクリル樹脂組成物を成形体を製造するには、例えば、本発明のメタクリル樹脂組成物を混練機により加熱し溶融混練した後、成形機にて成形すればよい。成形方法としては、成形機として射出成形機を用い、成形型内に射出して成形する射出成形法；成形機として押出成形機を用い、ダイから押し出して成形する押出成形法；成形機としてプレス機を用い、プレス機に充填しプレスして成形するプレス成形法などが挙げられる。
　一般に、メタクリル樹脂の成形は通常２３０~２９０℃程度で行われる。２９０℃を超えるとメタクリル樹脂が分解することがあるため、成形が行えないことがある。
　本発明のメタクリル樹脂組成物は、熱安定性に優れることから、成形温度が２９０℃を超える場合にも分解することなく成形を行うことができる。さらに、本発明のメタクリル樹脂組成物は、加熱溶融時の着色が抑制されるため、透明性に優れた成形体が得られる。 In order to produce a molded product of the methacrylic resin composition of the present invention, for example, the methacrylic resin composition of the present invention may be heated and melt-kneaded with a kneader and then molded with a molding machine. As 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.
In general, the methacrylic resin is usually molded at about 230 to 290 ° C. If the temperature exceeds 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.
　以下、実施例によって本発明を具体的に説明するが、本発明はこれらの実施例に限定されない。 Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples.
　なお、メタクリル樹脂組成物の熱安定性および熱着色性の評価は以下の方法で行った。 The thermal stability and thermal colorability of the methacrylic resin composition were evaluated by the following methods.
　＜熱安定性＞
　ＴＧ−ＤＴＡ装置（エスアイアイ・ナノテクノロジー（株）製、「ＴＧ／ＤＴＡ６３００」）を用いて、窒素流量２００ｍＬ／分、昇温速度２℃／分で、４０℃から５１０℃までビーズ状またはペレット状のメタクリル樹脂組成物を昇温しながら重量変化を測定し、２９０℃と３００℃での単位時間あたりの熱分解速度（重量％／分）を算出した。熱分解速度の値が小さいほど、メタクリル樹脂組成物は熱安定性に優れることを示す。 <Thermal stability>
Using a 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.
　＜熱着色性＞
　実施例４~６、比較例４~５で得られた各ペレット状のメタクリル樹脂組成物について、以下の方法で黄色度（ＹＩ値）を測定した。
　射出成形装置（東芝機械（株）製、「ＩＳ−１３０」）を用いて、シリンダー温度２６０℃のシリンダー内にペレット状のメタクリル樹脂組成物を充填し１０分間滞留させた後に、該メタクリル樹脂組成物を射出して、厚さ３ｍｍの板状成形体を得た。このメタクリル樹脂組成物を充填し滞留させた後に射出する操作を３回繰り返し、３回目の射出で得られた板状成形体について、長辺が７０ｍｍ、短辺が２５ｍｍの板状となるように切断し、さらに端面を研磨して、評価サンプルとした。得られた評価サンプルについて、分光光度計（（株）日立製作所製、「Ｈｉｔａｃｈｉ　Ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ　Ｕ−４０００」）を用いて、長辺光路（光路長７０ｍｍ）透過時の黄色度（ＹＩ値）を測定した。ＹＩ値が小さいほど、メタクリル樹脂組成物は加熱溶融時の着色が抑制されており、また、成形体は透明性に優れることを示す。 <Thermal coloring>
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 | disconnected and grind | polished the end surface further and it was set as the evaluation sample. About the obtained evaluation sample, 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"). . As 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.
　実施例７~８、比較例６で得られた各ペレット状のメタクリル樹脂組成物について、以下の方法で黄色度（ＹＩ値）を測定した。
　射出成形装置（（株）名機製作所製、「Ｍ１４０／３７０−ＳＪ」）を用いて、シリンダー温度２６０℃のシリンダー内にペレット状のメタクリル樹脂組成物を６分間滞留させた後に、該メタクリル樹脂組成物を射出して、ＪＩＳ　Ｋ　７１６２　１Ａ型試験片と同形状であって、長辺が１７０ｍｍ、短辺が２０ｍｍ、厚さ４ｍｍのダンベル形状成形体を得た。このメタクリル樹脂組成物を充填し滞留させた後に射出する操作を１２回繰り返し、１１回目および１２回目の射出で得られた各ダンベル形状成形体につき、端面を研磨して評価サンプルとした。得られた評価サンプルについて、それぞれ、分光光度計（（株）日立製作所製、「Ｈｉｔａｃｈｉ　Ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ　Ｕ−４０００」）を用いて、長辺光路（光路長１７０ｍｍ）透過時の黄色度（ＹＩ値）を計測し、１１回目の射出で得られた評価サンプルのＹＩ値と１２回目の射出で得られた評価サンプルのＹＩ値との平均ＹＩ値を算出した。平均ＹＩ値が小さいほど、メタクリル樹脂組成物は加熱溶融時の着色が抑制されており、また、成形体は透明性に優れることを示す。 About 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. 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. About the obtained evaluation samples, 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.
　（実施例１）
　メタクリル酸メチル９６重量部、アクリル酸メチル４重量部、連鎖動剤としてオクチルメルカプタン０．３質量部、重合開始剤としてラウロイルパーオキサイド０．２重量部、ジーｔｅｒｔ−ドデシルジスルフィド（以下、ＤＤＳという）０．０００５重量部、トリフェニルホスフィン（以下、ＴＰＰという）０．０５重量部を混合し、懸濁重合してメタクリル樹脂組成物を得た。さらに、得られたメタクリル樹脂組成物を８０℃で１日間減圧乾燥して、ビーズ状のメタクリル樹脂組成物を得た。得られたビーズ状のメタクリル樹脂組成物について、ＤＤＳおよびＴＰＰの配合量、ならびに熱安定性を評価した結果を表１に示す。 (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.
　（実施例２）
　実施例１において、ＴＰＰに替えてトリ−ｎ−ブチルホスフィン（以下、ＴＢＰという）を０．０５重量部混合したこと以外は、実施例１と同様にして、ビーズ状のメタクリル樹脂組成物を得た。得られたビーズ状のメタクリル樹脂組成物について、ＤＤＳおよびＴＢＰの配合量、ならびに熱安定性を評価した結果を表１に示す。 (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.
　（実施例３）
　実施例１において、ＴＰＰに替えてトリ−ｎ−オクチルホスフィン（以下、ＴＯＰという）を０．０５重量部混合したこと以外は、実施例１と同様にして、ビーズ状のメタクリル樹脂組成物を得た。得られたビーズ状のメタクリル樹脂組成物について、ＤＤＳおよびＴＯＰの配合量、ならびに熱安定性を評価した結果を表１に示す。 (Example 3)
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-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.
　（比較例１）
　実施例１において、ＤＤＳおよびＴＰＰを混合しなかったこと以外は、実施例１と同様にして、ビーズ状のメタクリル樹脂組成物を得た。得られたビーズ状のメタクリル樹脂組成物について、熱安定性を評価した結果を表１に示す。 (Comparative Example 1)
In 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.
　（比較例２）
　実施例１において、ＴＰＰを混合しなかったこと以外は、実施例１と同様にして、ビーズ状のメタクリル樹脂組成物を得た。得られたビーズ状のメタクリル樹脂組成物について、ＤＤＳの配合量、ならびに熱安定性を評価した結果を表１に示す。 (Comparative 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.
　（比較例３）
　実施例１において、ＴＰＰに替えて亜リン酸トリフェニル（以下、ＴＰＯＰという）を０．０５重量部混合したこと以外は、実施例１と同様にして、ビーズ状のメタクリル樹脂組成物を得た。得られたビーズ状のメタクリル樹脂組成物について、ＤＤＳおよびＴＰＯＰの配合量、ならびに熱安定性を評価した結果を表１に示す。 (Comparative Example 3)
In Example 1, 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.
　（実施例４）
　メタクリル酸メチル９６重量部、アクリル酸メチル４重量部、連鎖移動剤としてオクチルメルカプタン０．３質量部、エチレングリコールジメタクリレート０．１重量部、重合開始剤として１，１−ジ（ｔ−ブチルパーオキシ）シクロヘキサン０．０１重量部、ＤＤＳ０．０００５重量部、およびＴＰＰ０．００５重量部を混合し、塊状重合してメタクリル樹脂組成物を得た。次いで、得られたメタクリル樹脂組成物を脱揮押出機に供給し、ペレット状のメタクリル樹脂組成物を得た。得られたペレット状のメタクリル樹脂組成物について、ＤＤＳおよびＴＰＰの配合量、ならびに熱着色性および熱安定性を評価した結果を表２に示す。 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.
　（実施例５）
　実施例４におけるＴＰＰの混合量を、０．００５重量部から０．０５重量部に変更したこと以外は、実施例４と同様にして、ペレット状のメタクリル樹脂組成物を得た。得られたペレット状のメタクリル樹脂組成物について、ＤＤＳおよびＴＰＰの配合量、ならびに熱着色性および熱安定性を評価した結果を表２に示す。 (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.
　（実施例６）
　メタクリル酸メチル９６重量部、アクリル酸メチル４重量部、連鎖移動剤としてオクチルメルカプタン０．３質量部、エチレングリコールジメタクリレート０．１重量部、重合開始剤として１，１−ジ（ｔ−ブチルパーオキシ）シクロヘキサン０．０１重量部、ＤＤＳ０．０００５重量部を混合し、塊状重合して重合体組成物を得た。次いで、得られた重合体組成物１００重量部とＴＰＰ０．０５重量部とを混合して、脱揮押出機に供給し、ペレット状のメタクリル樹脂組成物を得た。得られたペレット状のメタクリル樹脂組成物について、ＤＤＳおよびＴＰＰの配合量、ならびに熱着色性および熱安定性を評価した結果を表２に示す。 (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. Next, 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.
　（比較例４）
　実施例４において、ＤＤＳおよびＴＰＰを混合しなかったこと以外は、実施例４と同様にして、ペレット状のメタクリル樹脂組成物を得た。得られたペレット状のメタクリル樹脂組成物について、熱着色性および熱安定性を評価した結果を表２に示す。 (Comparative Example 4)
In 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.
　（比較例５）
　実施例４において、ＴＰＰを混合しなかったこと以外は、実施例４と同様にして、ペレット状のメタクリル樹脂組成物を得た。得られたペレット状のメタクリル樹脂組成物について、ＤＤＳの配合量、ならびに熱着色性および熱安定性を評価した結果を表２に示す。 (Comparative Example 5)
In Example 4, 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.
　（実施例７）
　メタクリル酸メチル８８重量部、アクリル酸メチル７重量部、連鎖移動剤としてオクチルメルカプタン０．３質量部、重合開始剤としてｔｅｒｔ−アミルパーオキシ−２−エチルヘキサノエート０．０１重量部、ＤＤＳ０．０００５重量部を混合し、塊状重合して重合体組成物を得た。次いで、得られた重合体組成物９５重量部とＴＰＰ０．００５重量部とを混合して、脱揮押出機に供給し、ペレット状のメタクリル樹脂組成物を得た。得られたペレット状のメタクリル樹脂組成物について、ＤＤＳおよびＴＰＰの配合量、ならびに熱着色性および熱安定性を評価した結果を表３に示す。 (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.
　（実施例８）
　実施例７において、ＴＰＰに替えてトリフェニルホスフィンオキシド（以下、ＴＰＰＯという）を０．００５重量部混合したこと以外は、実施例７と同様にして、ペレット状のメタクリル樹脂組成物を得た。得られたペレット状のメタクリル樹脂組成物について、ＤＤＳおよびＴＰＰＯの配合量、ならびに熱着色性および熱安定性を評価した結果を表３に示す。 (Example 8)
In Example 7, 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. Table 3 shows the results of evaluating the blended amounts of DDS and TPPO, and the thermal colorability and thermal stability of the obtained pellet-shaped methacrylic resin composition.
　（比較例６）
　実施例７において、ＴＰＰを混合しなかったこと以外は、実施例７と同様にして、ペレット状のメタクリル樹脂組成物を得た。得られたペレット状のメタクリル樹脂組成物について、ＤＤＳの配合量、ならびに熱着色性および熱安定性を評価した結果を表３に示す。 (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.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　本発明によれば、熱安定性に優れ、かつ、加熱溶融時の着色が抑制されたメタクリル樹脂組成物が提供される。
　本発明のメタクリル樹脂組成物は、熱安定性に優れ、かつ、加熱溶融時の着色が抑制される。そのため、加熱溶融した本発明のメタクリル樹脂組成物を成形してなる成形体は透明性に優れる。 ADVANTAGE OF THE INVENTION According to this invention, 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.

Claims (13)

  1. 　メタクリル樹脂と、有機ジスルフィド化合物と、以下の式（Ｉ）で表されるホスフィン化合物および以下の式（ＩＩ）で表されるホスフィンオキシド化合物からなる群より選択される少なくとも１種の化合物と、を含有するメタクリル樹脂組成物。
    Figure JPOXMLDOC01-appb-I000001
    （式（Ｉ）中、Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、水素原子、炭素数１~１２のアルキル基、炭素数５~１２のシクロアルキル基、炭素数６~１２のアルキルシクロアルキル基、炭素数６~１２のアリール基を表し、それぞれの炭素原子に結合した任意の水素原子はヘテロ原子を含む置換基で置換されていてもよい。）
    Figure JPOXMLDOC01-appb-I000002
    （式（ＩＩ）中、Ｒ４、Ｒ５およびＲ６は、それぞれ独立して、水素原子、炭素数１~１２のアルキル基、炭素数５~１２のシクロアルキル基、炭素数６~１２のアルキルシクロアルキル基、炭素数６~１２のアリール基を表し、それぞれの炭素原子に結合した任意の水素原子はヘテロ原子を含む置換基で置換されていてもよい。）     A methacrylic resin, an organic disulfide compound, and at least one compound selected from the group consisting of a phosphine compound represented by the following formula (I) and a phosphine oxide compound represented by the following formula (II): A methacrylic resin composition to be contained.
    Figure JPOXMLDOC01-appb-I000001
    (In the formula (I), 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.)
    Figure JPOXMLDOC01-appb-I000002
    (In the formula (II), 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.)
  2. 　式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６が、同一の置換基である請求項１に記載のメタクリル樹脂組成物。 The methacrylic resin composition according to claim 1, wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same substituent.
  3. 　式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６が、フェニル基である請求項１に記載のメタクリル樹脂組成物。 The methacrylic resin composition according to claim 1, wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are phenyl groups.
  4. 　有機ジスルフィド化合物が、ジアルキルジスルフィド化合物である請求項１に記載のメタクリル樹脂組成物。 The methacrylic resin composition according to claim 1, wherein the organic disulfide compound is a dialkyl disulfide compound.
  5. 　有機ジスルフィド化合物が、ジ−ｔｅｒｔ−ドデシルジスルフィドである請求項１に記載のメタクリル樹脂組成物。 The methacrylic resin composition according to claim 1, wherein the organic disulfide compound is di-tert-dodecyl disulfide.
  6. 　メタクリル樹脂と、有機ジスルフィド化合物と、式（Ｉ）で表されるホスフィン化合物および式（ＩＩ）で表されるホスフィンオキシド化合物からなる群より選択される少なくとも１種の化合物と、を混合する工程を含む、請求項１に記載のメタクリル樹脂組成物の製造方法。 Mixing a methacrylic resin, an organic disulfide compound, and at least one compound selected from the group consisting of a phosphine compound represented by formula (I) and a phosphine oxide compound represented by formula (II) The manufacturing method of the methacrylic resin composition of Claim 1 containing.
  7. 　前記混合が溶媒中で行われる請求項６に記載の方法。 The method according to claim 6, wherein the mixing is performed in a solvent.
  8. 　前記混合後、前記溶媒が除去される請求項７に記載の方法。 The method according to claim 7, wherein the solvent is removed after the mixing.
  9. 　前記溶媒が、メタクリル酸メチルを５０質量％以上含有する単量体、ケトン類、アルコール類およびエーテル類からなる群より選択される少なくとも１種の溶媒である請求項７に記載の方法。 The method according to claim 7, wherein the solvent is at least one solvent selected from the group consisting of a monomer containing 50% by mass or more of methyl methacrylate, ketones, alcohols and ethers.
  10. 　前記溶媒が、メタクリル酸メチルを５０質量％以上含有する単量体、アセトンまたはこれらの混合溶媒である請求項７に記載の方法。 The method according to claim 7, wherein the solvent is a monomer containing 50% by mass or more of methyl methacrylate, acetone, or a mixed solvent thereof.
  11. 　メタクリル樹脂および有機ジスルフィド化合物を含有する重合体組成物と、式（Ｉ）で表されるホスフィン化合物および式（ＩＩ）で表されるホスフィンオキシド化合物からなる群より選択される少なくとも１種の化合物とを混合する工程を含む、請求項１に記載のメタクリル樹脂組成物の製造方法。 A polymer composition containing a methacrylic resin and an organic disulfide compound, and at least one compound selected from the group consisting of a phosphine compound represented by formula (I) and a phosphine oxide compound represented by formula (II); The manufacturing method of the methacryl resin composition of Claim 1 including the process of mixing.
  12. 　前記重合体組成物が、単量体成分からメタクリル樹脂を製造する際に、単量体成分に有機ジスルフィド化合物を配合して得られた組成物である、請求項１１に記載の方法。 The method according to claim 11, wherein the polymer composition is a composition obtained by blending an organic disulfide compound with a monomer component when producing a methacrylic resin from the monomer component.
  13. 　請求項１に記載のメタクリル樹脂組成物を成形してなる成形体。 A molded body formed by molding the methacrylic resin composition according to claim 1.
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