WO2008047836A1 - Composition de résine thermoplastique - Google Patents

Composition de résine thermoplastique Download PDF

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Publication number
WO2008047836A1
WO2008047836A1 PCT/JP2007/070258 JP2007070258W WO2008047836A1 WO 2008047836 A1 WO2008047836 A1 WO 2008047836A1 JP 2007070258 W JP2007070258 W JP 2007070258W WO 2008047836 A1 WO2008047836 A1 WO 2008047836A1
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thermoplastic resin
resin composition
polymer
film
group
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PCT/JP2007/070258
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English (en)
Japanese (ja)
Inventor
Shigeo Otome
Kazunari Yasumura
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Nippon Shokubai Co., Ltd.
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Priority to JP2008539847A priority Critical patent/JPWO2008047836A1/ja
Publication of WO2008047836A1 publication Critical patent/WO2008047836A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters

Definitions

  • the present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition containing a thermoplastic resin having a UV-absorbing monomer unit and a specific antioxidant.
  • Acrylic resins represented by PMMA are high! /, Have excellent light transmittance and optical characteristics, and have a good balance of mechanical strength, moldability, and surface hardness. Therefore, it is widely used for transparent materials and optical related applications in automobile parts, household appliances, various industrial parts.
  • an ultraviolet absorber is generally added to an acrylic resin.
  • these UV absorbers have a low molecular weight, so they are prone to pre-out, and also due to transpiration during molding. There were various problems such as a decrease in the amount of addition, a decrease in ultraviolet absorption capacity, and contamination of the manufacturing process.
  • thermoplastic resin having both transparency and heat resistance a rataton ring-containing polymer obtained by subjecting a polymer having a hydroxyl group and an ester group in a molecular chain to a rataton cyclocondensation reaction
  • these polymers have high heat resistance, it is known that foam and silver stritas are likely to enter into a molded product having a molding temperature higher than that of a general acrylic resin! /.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-170941
  • Patent Document 2 JP 2001-151814 A
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-138106 Disclosure of the invention
  • a resin or resin composition is used by a polymer filter during production of a resin copolymerized with an ultraviolet absorbing monomer or during film formation. It is conceivable to remove foreign matter inside.
  • filtration is performed with a polymer filter, it is necessary to mold at a higher temperature. In this case, problems such as thermal stability at the time of molding may become prominent.
  • the present invention has been made in view of the above-described situation, and has desired characteristics such as transparency, mechanical strength, and moldability, and is particularly excellent in thermal stability at the time of molding, and ultraviolet rays.
  • An object is to provide a thermoplastic resin composition having an absorbing ability.
  • thermoplastic resin having an ultraviolet-absorbing monomer unit has transparency and ultraviolet-absorbing ability, and has formulated a specific antioxidant.
  • the inventors have found that all the above problems can be solved, and have completed the present invention.
  • the UV-absorbing monomer generally has a problem that it tends to be deteriorated during molding because the heat resistance is lowered when the copolymer is bulky. That is, particularly when a bulky UV-absorbing monomer is copolymerized, the thermal stability during molding tends to deteriorate.
  • an ultraviolet absorber was added, it was not incorporated into the polymer skeleton, and therefore the evaporation of the additive during molding and the resulting contamination of the manufacturing process were more likely to occur.
  • the present inventors have found that the above problem can be solved by blending a specific antioxidant with a thermoplastic resin having an ultraviolet-absorbing monomer unit.
  • the present invention is a thermoplastic resin composition containing a thermoplastic resin having an ultraviolet-absorbing monomer unit and an antioxidant, wherein the antioxidant is represented by the following general formula (1);
  • R 1 is the same or different and represents an alkyl group having 1 to 5 carbon atoms
  • R 2 is the same or different and represents an alkyl group having 1 to 8 carbon atoms
  • R 3 represents a hydrogen atom or an alkyl group having from 8 to 8 carbon atoms
  • R 4 represents a hydrogen atom or a methyl group. It is a plastic resin composition.
  • thermoplastic resin composition of the present invention contains a thermoplastic resin having an ultraviolet-absorbing monomer unit and an antioxidant represented by the above general formula (1).
  • a thermoplastic resin composition having desired properties such as mechanical strength and molding processability, excellent thermal stability during molding, and having ultraviolet absorbing ability can be obtained.
  • the antioxidant is not limited to the phenyl (meth) acrylate represented by the general formula (1), and the phenyl (meth) acrylate represented by the general formula (1) is sufficient. It is preferably contained as a main component. In addition, as long as the effect of the present invention can be exhibited, it may contain other antioxidants.
  • thermoplastic resin e.g., polystyrene resin
  • antioxidant e.g., polystyrene resin
  • another component e.g., polystyrene resin
  • thermoplastic resin (Thermoplastic resin)
  • the thermoplastic resin according to the present invention has a polymer structural unit (repeating structural unit) constructed by polymerizing an ultraviolet absorbing monomer.
  • the UV-absorbing monomer any monomer that exhibits UV-absorbing ability can be used.
  • a benzotriazole derivative, a triazine derivative, or a benzophenone derivative having a polymerizable group introduced therein is preferable.
  • UV-absorbing monomer examples include 2- [2'-hydroxy-5'-methacryloylene-2H benzotriazolene, 2- "2'-hydroxy-5'-me _ 2H Benzotriazolole, 2- [2'-Hydroxyl 3'-tert-Butyl-5'-Methacryloyloxy] phenyl] 2H Benzotriazole, UVA-5 represented by the following chemical formula UV absorption such as UVA-5 Monomer, and triazine derivatives such as UVA-2, UVA-3, and UVA-4 represented by the following chemical formula.
  • UVA-5 represented by the following chemical formula UV absorption
  • UVA-2, UVA-3, and UVA-4 represented by the following chemical formula.
  • benzotriazole-based UV-absorbing monomers and triazine derivatives are more preferred.
  • 2- [2′-Hydroxy-5′-methacryloyloxy] ethylphenyl] 2H benzotriazole is particularly preferable from the viewpoint of ultraviolet absorption ability and coloring after molding. Since these monomers have a high UV-absorbing ability even in a small amount, they exhibit a sufficiently high effect in a thermoplastic resin with a small amount of the repeating unit derived from the monomer. Therefore, since the amount of structural units other than the UV-absorbing monomer unit in the thermoplastic resin can be relatively increased, a thermoplastic resin having sufficient thermoplasticity suitable for various uses such as a film can be obtained. can do. In addition, since there are few structural units derived from the UV-absorbing monomer, coloring of products such as thermoplastic resins and films obtained from the resins can be sufficiently suppressed, and it can be suitably used for various applications. it can.
  • the content of the UV-absorbing monomer unit contained in the thermoplastic resin according to the present invention is preferably 20% by mass or less with respect to 100% by mass of the thermoplastic resin.
  • a form in which the content of the ultraviolet absorbing monomer is 15% by mass or less is also a preferred form of the present invention. More preferably, it is! ⁇ 15 mass%, More preferably, it is 2 ⁇ ; 10 mass%, Especially preferably, it is 3 ⁇ ; 10 mass%. If the content of the UV-absorbing monomer unit is less than 1% by mass, the resulting polymer may have insufficient UV-absorbing ability, which is not preferable. On the contrary, when the content ratio of the UV-absorbing monomer unit exceeds 20% by mass, the resulting polymer has low heat resistance and is economically preferable.
  • thermoplastic resin according to the present invention is not particularly limited as long as it is a thermoplastic resin having a polymer structural unit (repeating structural unit) constructed by polymerizing an ultraviolet absorbing monomer. Absent. Of these, those having a glass transition temperature of 110 ° C or higher are preferred, and those having a glass transition temperature of 120 ° C or higher are preferred.
  • the thermoplastic resin according to the present invention preferably has a weight average molecular weight of 1000 to 300,000. More preferred ⁇ (between 5000 and 250000, more preferred ⁇ (between 10000 and 20000 0, particularly preferred ⁇ is between 50000 and 200000).
  • the weight average molecular weight of the polymer (thermoplastic resin) in the resin composition can be determined, for example, by gel permeation chromatography (GPC) polystyrene conversion.
  • GPC gel permeation chromatography
  • the weight average molecular weight can be determined under the following conditions using GPC (manufactured by Tosohichi Corporation, apparatus name: GPC system).
  • Reference ⁇ j Reference column (TSKgel SuperH-RC)
  • thermoplastic resin which can be used in the present invention, acrylic resin having a UV-absorbing monomer unit, methacrylic resin, and other thermoplastic resins can be used. It is preferably at least one selected from the group consisting of acrylic resins having units and methacrylic resins. Among these, it is particularly preferable that the thermoplastic resin is a methacrylol resin. Thereby, transparency and mechanical strength can be improved.
  • the above-mentioned acrylic resin is a resin obtained by polymerizing a monomer component essentially comprising acrylic acid and / or acrylic acid ester in (meth) acrylic acid or (meth) acrylic acid ester described later. And / or a resin obtained by polymerizing a monomer component mainly composed of an acrylate ester.
  • the methacrylic resin is a resin obtained by polymerizing a monomer component which essentially contains methacrylic acid and / or methacrylic acid ester in (meth) acrylic acid and (meth) acrylic acid ester described later, A resin obtained by polymerizing a monomer component mainly composed of methacrylic acid and / or methacrylic acid ester is preferable.
  • the acrylic resin and the methacrylic resin at least one structural unit selected from the group consisting of an N-substituted maleimide-derived structural unit, a rataton ring structure, a dartaric anhydride structure, and a dartalimide structure, which will be described later, is included. It is preferable that the structure in the polymer excluding these structural units in the main chain is composed mainly of the above-mentioned (meth) acrylic acid ester as described above.
  • thermoplastic resin which is effective in the present invention, from the viewpoint of heat resistance, a rataton ring-containing polymer having a UV-absorbing monomer unit, a maleimide polymer, a dartaric anhydride polymer, a dartarimide polymer can be used.
  • a combination or the like is suitable, and these may be used alone or in combination of two or more.
  • thermoplastic resin that can be suitably used in the present invention, a force that is at least one selected from the group consisting of an acrylic resin and a methacrylic resin having an ultraviolet-absorbing monomer unit, and / or Alternatively, it is at least one selected from the group consisting of a lactone ring-containing polymer having a UV-absorbing monomer unit, a maleimide polymer, a dartaric anhydride polymer, and a dartalimide polymer.
  • the maleimide polymer is a polymer having a structural unit derived from N-substituted maleimide such as phenylmaleimide, cyclohexylmaleimide, methylmaleimide, etc.
  • the rataton ring-containing polymer is a molecule having a rataton ring structure.
  • a polymer having a chain (preferably in the main skeleton of the polymer or in the main chain), and the above-mentioned dartaric anhydride polymer is a polymer having a glutaric anhydride structure in the molecular chain.
  • the dartalimide polymer is a polymer having a dartalimide structure in the molecular chain.
  • acrylic resins are used for the above-mentioned latatotone ring-containing polymers, maleimide polymers, dartaric anhydride polymers, and glutarimide polymers.
  • / or methacrylic resin is preferred. That is, at least one structural unit selected from the group consisting of an ultraviolet-absorbing monomer unit and a structural unit derived from N-substituted maleimide, a rataton ring structure, a dartal anhydride structure, and a dartalimide structure.
  • An acrylic resin and / or a methacrylic resin having a main chain in the main chain is preferred.
  • the main chain has a rataton ring structure represented by the following general formula (2) among the polymers containing the outer ring.
  • a heat-resistant acrylic resin having a ring structure in the main chain is preferred.
  • the main chain has a rataton ring structure represented by the following general formula (2).
  • thermoplastic resins those composed of a polymer having a structure that substantially does not contain nitrogen atoms are preferable from the viewpoint of difficulty in coloring (yellowing) the film.
  • the thermoplastic resin that has power in the present invention has a ring structure in the main chain in terms of transparency, hue, other optical properties (optical properties), and moldability.
  • Rataton ring-containing polymers are preferred, where polymers are preferred. In other words, those having a rataton ring structure in the main chain are preferred.
  • the 6-membered ring is more preferable because of the stability of the structure. The 6-membered ring is more preferable.
  • examples of the rataton ring structure in the main chain include the structure represented by the following general formula (2): JP-A-2004-168882.
  • thermoplastic resin composition of the present invention it is preferred that the ring structure of the thermoplastic resin in the main chain is one having an open ring structure.
  • thermoplastic resin composition of this invention containing this thermoplastic resin is shape
  • molded the fault that a foam and a silver streak enter in the obtained molded article can be avoided.
  • the organic group may contain an oxygen atom.
  • an alkyl group having 120 carbon atoms such as a methylol group, an ethyl group, or a propyl group
  • an unsaturated aliphatic hydrocarbon group having 120 carbon atoms such as an ethyl group or an open phenyl group.
  • -20 such as a phenyl group or a naphthyl group; one or more hydrogen atoms of the alkyl group, the unsaturated hydrocarbon group, or the aromatic hydrocarbon group A group substituted with a hydroxyl group; a group in which one or more hydrogens of the alkyl group, the unsaturated hydrocarbon group, or the aromatic hydrocarbon group are substituted with a carboxyl group; the alkyl group or the unsaturated hydrocarbon group One or more forces of hydrogen of an aromatic hydrocarbon group; a group substituted with an ether group; one or more of the alkyl group, the unsaturated hydrocarbon group, or the hydrogen of the aromatic hydrocarbon group is an ester group; A substituted group is preferred.
  • an alkyl group having 1 to 20 carbon atoms an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, and an aromatic hydrocarbon having 2 to 20 carbon atoms It is preferable that the basic group or at least one of these groups is a group substituted with a hydroxyl group, a carboxyl group, an ether group, or an ester group.
  • the content of the ratatone ring structure of the rataton ring-containing polymer is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, still more preferably 10 to 60% by mass, and particularly preferably 10 to 50% by mass. . If the content of the rataton ring structure represented by the above formula (2) is less than 5% by mass, the heat resistance, solvent resistance and surface hardness may be insufficient, which is not preferable.
  • the Lataton ring-containing polymer may have a structure other than the structure represented by the formula (2).
  • Examples of the structure other than the latathone ring structure represented by the above formula (2) include, for example, a (meth) acrylate ester, a hydroxyl group-containing monomer, an unsaturated group, which will be described later as a method for producing a latathone ring-containing polymer.
  • a polymer structural unit (repeating unit) constructed by polymerizing at least one selected from carboxylic acids and monomers represented by the following formula (3) is preferred! /.
  • R 8 represents a hydrogen atom or a methyl group
  • X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an OAc group, a CN group, a CO—R 9 group, or 1 represents a C—O—R 10 group
  • an Ac group represents a acetyl group
  • R 9 and R 1 represent a hydrogen atom or an organic group having 20 to 20 carbon atoms
  • the content of the structure other than the rataton ring structure represented by the above formula (2) in the polymer structure containing the rataton ring is a polymer structural unit (repeated structural unit) constructed by polymerizing (meth) acrylic acid ester. ) Is preferably 10 to 95% by mass, more preferably 10 to 90% by mass, still more preferably 40 to 90% by mass, particularly preferably 50 to 90% by mass, and a hydroxyl group-containing monomer is polymerized. In the case of a polymer structural unit (repeating structural unit) constructed in this manner, it is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, still more preferably 0 to; 15% by mass, and particularly preferably 0 to; 10% by mass.
  • a polymer structural unit (repeating structural unit) constructed by polymerizing an unsaturated carboxylic acid it is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, further preferably 0 to 15% by mass. Particularly preferably, 0 to 10% by mass.
  • a polymer structural unit (repeating structural unit) constructed by polymerizing the monomer represented by the general formula (3) Preferably they are 0-30 mass%, More preferably, they are 0-20 mass%, More preferably, they are 0-; 15 mass%, Especially preferably, they are 0-; 10 mass%.
  • thermoplastic resin having a ring structure in the main chain is the same as the preferred form of the above-described rataton ring-containing polymer.
  • the method for producing the above-described ratatone ring-containing polymer is not particularly limited.
  • the polymer is obtained after obtaining a polymer (a) having a hydroxyl group and an ester group in the molecular chain by a polymerization step.
  • the obtained polymer (a) is obtained by performing a rataton cyclocondensation reaction step for introducing a rataton ring structure into the polymer by heat treatment.
  • a polymer having a hydroxyl group and an ester group in the molecular chain is obtained by conducting a polymerization reaction of the monomer component containing the monomer represented by the following formula (4).
  • R 11 and R 12 are the same or different and represent a hydrogen atom or an organic group having 20 to 20 carbon atoms;
  • Examples of the monomer represented by the above formula (4) include, for example, 2- (hydroxymethyl) methyl propylenolate, 2- (hydroxymethylol) normal butyl acrylate, 2- (hydroxymethyl) acrylic acid. Tertiary butyl etc. are mentioned. Of these, methyl 2- (hydroxymethyl) acrylate and methyl 2- (hydroxymethyl) acrylate are particularly preferred, and methyl 2- (hydroxymethyl) acrylate is particularly preferred because of its high heat resistance improvement effect. . As the monomer represented by the above formula (4), only one kind may be used, or two or more kinds may be used in combination.
  • the content ratio of the monomer represented by the above formula (4) in the monomer component used in the polymerization step is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably. Is 10 to 60% by mass, particularly preferably 10 to 50% by mass.
  • the content of the monomer represented by the above formula (4) in the monomer component used in the polymerization process is more than 90% by mass, This is not preferable because gelation may occur during cyclization of the rataton, and the molding processability of the obtained polymer may be poor.
  • the monomer component used in the polymerization step may contain a monomer other than the monomer represented by the formula (4).
  • monomers include (meth) acrylic acid esters, hydroxyl group-containing monomers, unsaturated carboxylic acids, and monomers represented by the above formula (3).
  • monomer other than the monomer represented by the above formula (4) only one type may be used, or two or more types may be used in combination.
  • the (meth) acrylic acid ester is not particularly limited as long as it is a (meth) acrylic acid ester other than the monomer represented by the formula (4).
  • methyl acrylate acrylic Acrylates such as ethyl acid, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, benzyl acrylate, etc .; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-methacrylate
  • methacrylic acid esters such as butyl, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate.
  • methyl methacrylate is preferable because it is particularly excellent in heat resistance and transparency.
  • the content ratio in the monomer component used in the polymerization process is sufficient to achieve the effect of the present invention. on exerting, preferably, 10 to 95 weight 0/0, more preferably 10 to 90 weight 0/0, more preferably 40 to 90 wt%.
  • the hydroxyl group-containing monomer is not particularly limited as long as it is a hydroxyl group-containing monomer other than the monomer represented by the formula (4).
  • ⁇ -hydroxymethylstyrene ⁇ - Examples include hydroxyethyl styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, etc., and these may be used alone or in combination of two or more.
  • the content ratio in the monomer component to be subjected to the polymerization step sufficiently exhibits the effects of the present invention.
  • Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, a-substituted acrylic acid, and ⁇ -substituted methacrylic acid. These may be used alone or in combination of two kinds. You may use the above together. Among these, acrylic acid and methacrylic acid are particularly preferable in that the effects of the present invention are sufficiently exhibited.
  • the content ratio in the monomer component to be subjected to the polymerization step is preferably 0 to 30% by mass, and more preferably, in order to sufficiently exert the effects of the present invention. Is 0 to 20% by mass, more preferably 0 to; 15% by mass, particularly preferably 0 to 10% by mass.
  • Examples of the monomer represented by the above formula (3) include styrene, butyltoluene, ⁇ -methylenstyrene, acrylonitrile, methinolevinoleketone, ethylene, propylene, vinylinacetate, and the like. May be used alone or in combination of two or more. Of these, styrene and ⁇ -methylstyrene are particularly preferable in that the effects of the present invention are sufficiently exhibited.
  • the monomer represented by the above formula (3) its content in the monomer component used in the polymerization step is preferably 0 to sufficiently exhibit the effects of the present invention. 30% by mass, more preferably 0 to 20% by mass, further preferably 0 to; 15% by mass, particularly preferably 0 to 10% by mass.
  • the preferred form of the polymerization reaction for polymerizing the monomer components to obtain a polymer having a hydroxyl group and an ester group in the molecular chain is a polymerized form using a solvent. Polymerization is particularly preferred.
  • the polymerization temperature and polymerization time vary depending on the type of monomer used, the ratio of use, etc., but preferably the polymerization temperature is 0 to; 150 ° C, and the polymerization time is 0.5 to 20 hours. More preferably, the polymerization temperature is 80 to 140 ° C, the polymerization time is! To 10 hours.
  • the polymerization solvent is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; Ether solvents such as tetrahydrofuran; and the like. These may be used alone, or two or more of them may be used in combination. Also used solvent If the boiling point of the polymer is too high, the final exocyclic ring-containing polymer will have a large residual volatile content, and the boiling point is preferably 50-200 ° C! /.
  • a polymerization initiator may be added as necessary.
  • the polymerization initiator is not particularly limited.
  • Organic peroxides such as diisopropylbenzene hydride peroxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl oxy-isopropyl carbonate; 2, 2 '—azobis (isobutyronitrile), 1, V —azobis ( Azo compounds such as cyclohexane carbonitryl), 2, 2'-azobis (2,4 dimethyl pararonitrile), etc., and these may be used alone or in combination of two or more. You may use together.
  • the amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the combination of the monomers used and the reaction conditions.
  • a chain transfer agent may be used for controlling the molecular weight of the polymer. Examples thereof include alkyl mercaptans such as ptyl mercaptan, octyl menolecaptan, dodecyl mercaptan, and ⁇ -styrene dimer.
  • the concentration of the produced polymer in the polymerization reaction mixture is 50% by mass or less in order to suppress gelation of the reaction solution.
  • a polymerization solvent may be appropriately added to the polymerization reaction mixture to control it to 50% by mass or less. I like it.
  • the concentration of the produced polymer in the polymerization reaction mixture is more preferably 45% by mass or less, still more preferably 40% by mass or less. Note that if the concentration of the polymer in the polymerization reaction mixture is too low, the productivity is lowered. Therefore, the concentration of the polymer in the polymerization reaction mixture is preferably 10% by mass or more, more preferably 20% by mass or more. More preferably.
  • the form of appropriately adding the polymerization solvent to the polymerization reaction mixture is not particularly limited, and the polymerization solvent may be added continuously or intermittently.
  • the concentration of the produced polymer in the polymerization reaction mixture in this way, the gelation of the reaction solution can be more sufficiently suppressed, and in particular, the heat resistance is improved by increasing the content ratio of the rataton ring. Gelation even when the ratio of hydroxyl groups to ester groups in the molecular chain is increased Can be sufficiently suppressed.
  • the polymerization solvent to be added may be the same type of solvent used during the initial charging of the polymerization reaction or a different type of solvent, but may be the same as the solvent used during the initial charging of the polymerization reaction. It is preferable to use the same type of solvent. Further, the polymerization solvent to be added may be only one type of solvent or a mixed solvent of two or more types.
  • the polymerization reaction mixture obtained at the end of the above polymerization step usually contains a solvent in addition to the obtained polymer, but the solvent is completely removed to remove the polymer in a solid state. It is preferable to introduce it into the subsequent Lataton cyclocondensation step in the state of containing the solvent which need not be taken out. In addition, if necessary, a solvent suitable for the subsequent Rataton cyclization condensation process may be added again after taking it out in a solid state.
  • the polymer obtained in the polymerization step is a polymer (a) having a hydroxyl group and an ester group in the molecular chain, and the weight average molecular weight of the polymer (a) is preferably 1000 to 300,000, more preferably «5000. —250000, more preferred ⁇ or 10000-200000, special preferred ⁇ or 50000-200000.
  • the polymer (a) obtained in the polymerization step is subjected to a heat treatment in the subsequent rataton cyclization condensation step, whereby the rataton ring structure is introduced into the polymer to form a rataton ring-containing polymer.
  • the reaction for introducing the polymer (a) heratatone ring structure the hydroxyl group and ester group present in the polymer chain of the polymer (a) are cyclized and condensed to form a rataton ring structure by heating. This is a reaction, and alcohol is produced as a by-product by the cyclization condensation. By forming a rataton ring structure in the polymer chain (in the main skeleton of the polymer), high heat resistance is imparted.
  • reaction rate of the cyclocondensation reaction leading to the rataton ring structure is insufficient, the heat resistance will not be improved sufficiently, or a condensation reaction will occur during the molding by the heat treatment during molding, and the resulting alcohol will be It is not preferable because it may exist as foam or silver streak in the molded product.
  • the rataton ring-containing polymer obtained in the rataton cyclization condensation step preferably has a rataton ring structure represented by the above formula (2).
  • the method for heat-treating the polymer (a) is not particularly limited.
  • a known method can be used, and the polymerization reaction mixture containing the solvent obtained by the polymerization step is heated as it is. It may be processed. Further, in the presence of a solvent, heat treatment may be performed using a ring-closing catalyst as necessary. In addition, the heat treatment can be performed using a vacuum furnace or a devolatilizer for removing volatile components, a heating furnace reactor, an extruder with a devolatilizer, or the like.
  • another thermoplastic resin may coexist.
  • an esterification catalyst such as ⁇ ⁇ ⁇ ⁇ -toluenesulfonic acid or a transesterification catalyst generally used as a catalyst for the cyclization condensation reaction may be used.
  • Organic carboxylic acids such as propionic acid, benzoic acid, acrylic acid, and methacrylic acid may be used as a catalyst.
  • basic compounds, organic carboxylates, carbonates and the like may be used. When a basic compound, organic carboxylate, carbonate, or the like is used, it may be as disclosed in JP-A-61-254608 and JP-A-61-261303.
  • an organic phosphorus compound is preferably used as a catalyst.
  • an organophosphorus compound when used as a catalyst, it may be as disclosed in JP-A-2001-151814.
  • an organophosphorus compound as a catalyst, it is possible to improve the cyclization condensation reaction rate and to greatly reduce the coloration of the resulting ratatone ring-containing polymer.
  • an organophosphorus compound as a catalyst, it is possible to suppress a decrease in molecular weight that can occur when a devolatilization step described later is used in combination, and to impart excellent mechanical strength.
  • the amount of the catalyst used in the cyclization condensation reaction is not particularly limited, but is preferably 0.00;! To 5 mass%, more preferably 0.01 relative to the polymer (a). -2. 5% by mass, more preferably from 0.01 to;!% By mass, particularly preferably from 0.05 to 0.5% by mass. If the amount of the catalyst used is less than 0.001% by mass, the reaction rate of the cyclization condensation reaction may not be improved sufficiently. On the other hand, if it exceeds 5% by mass, coloring may occur. This is preferable because the polymer is melt-formed by cross-linking of the polymer.
  • the addition timing of the catalyst is not particularly limited, and it may be added at the beginning of the reaction, during the reaction, or both.
  • the cyclization condensation reaction is performed in the presence of a solvent, and a devolatilization step is used in combination with the cyclization condensation reaction.
  • the devolatilization process is performed throughout the cyclization condensation reaction.
  • a form in which the devolatilization step is not used throughout the entire cyclization condensation reaction, but is used only in a part of the process.
  • the alcohol produced as a by-product in the condensation cyclization reaction is forcibly devolatilized and removed, so the equilibrium of the reaction is advantageous for the production side.
  • the devolatilization step is a process in which volatile components such as a solvent and residual monomers and alcohol produced as a by-product by a cyclization condensation reaction leading to a rataton ring structure are removed under reduced pressure heating, if necessary. Say good. If this removal treatment is insufficient, the residual volatile components in the produced resin increase, resulting in problems such as coloration due to deterioration during molding, and molding defects such as bubbles and silver streaks.
  • the apparatus to be used is not particularly limited, but in order to more effectively perform the present invention, the heat exchanger and the devolatilization tank are used.
  • reaction treatment temperature is 150 to 3
  • a range of 50 ° C is preferred.
  • a range force S of 200-300 ° C is preferred. If the reaction treatment temperature is lower than 150 ° C, the cyclization condensation reaction may be insufficient and the residual volatile matter may increase, and if it is higher than 350 ° C, coloring or decomposition may occur.
  • the pressure during the reaction treatment is in the range of 93 1 to 1.33 hPa (700 to ImmHg), preferably 798 to 66.5 hPa. A range of (600 to 50 mmHg) is more preferable. If the pressure is lower than 931 hPa, there is a problem that volatile components including alcohol are likely to remain. 1. If the pressure is lower than 33 hPa, industrial implementation becomes difficult and there are problems.
  • vents When the above extruder with a vent is used, one or a plurality of vents may be used.
  • the reaction treatment temperature is preferably in the range of 150 to 350 ° C, more preferably in the range of 200 to 300 ° C. If the temperature is lower than 150 ° C, the cyclization condensation reaction may be insufficient and residual volatile matter may increase. If the temperature is higher than 350 ° C, coloring may occur. Or decomposition may occur.
  • the pressure at the time of reaction treatment is preferably in the range of 931-1.33hPa (700 ⁇ ; ImmHg), preferably in the range of 798 ⁇ ; 13.3hPa (600 ⁇ ;! OmmHg). More preferred.
  • 931 hPa there is a problem that volatile components including alcohol are likely to remain. 1.
  • the pressure is lower than 33 hPa, there is a problem that industrial implementation becomes difficult.
  • the physical properties of the resulting latathone ring-containing polymer may be deteriorated under severe heat treatment conditions. Is preferably carried out using a vented extruder or the like under the mildest conditions possible using the above-described dealcoholization reaction catalyst.
  • the polymer ⁇ obtained in the polymerization step is preferably introduced into the cyclization condensation reactor system together with the solvent. In response, it may be passed through the reactor system such as a vented extruder once again.
  • the devolatilization step may not be used together throughout the entire cyclization condensation reaction, but may be used only in part of the process.
  • the apparatus for producing the polymer ⁇ is further heated to advance the cyclization condensation reaction to some extent in advance, and then the cyclization condensation reaction using the devolatilization step is performed at the same time to complete the reaction. It is.
  • the polymer (a) is heated at a high temperature close to 250 ° C or higher using a twin-screw extruder.
  • the heat treatment is carried out, the decomposition of the latonic ring-containing polymer may be deteriorated before the cyclization condensation reaction occurs due to the difference in heat history. Therefore, if the cyclization condensation reaction is allowed to proceed to some extent before performing the cyclization condensation reaction using the devolatilization process at the same time, the reaction conditions in the latter half can be relaxed, and the physical properties of the resulting latathone ring-containing polymer deteriorate. Can be suppressed, which is preferable.
  • the devolatilization step is started after a lapse of time from the start of the cyclization condensation reaction, that is, the hydroxyl group and ester present in the molecular chain of the polymer (a) obtained in the polymerization step. Raise the cyclization condensation reaction rate obtained by cyclization reaction of the group in advance, and then continue the cyclization condensation reaction using the devolatilization step at the same time.
  • the form to perform is mentioned.
  • a kettle-type reactor is used in advance to advance the cyclization condensation reaction to a certain reaction rate in the presence of a solvent, and then a reactor equipped with a devolatilizer, for example, a heat
  • a reactor equipped with a devolatilizer for example, a heat
  • examples include a form in which the cyclization condensation reaction is completed with a devolatilizer composed of an exchanger and a devolatilization tank or an extruder with a vent.
  • the presence of a catalyst for the cyclization condensation reaction is preferred over the ability S.
  • the hydroxyl group and the ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are subjected to a cyclization condensation reaction in advance to increase the cyclization condensation reaction rate to some extent.
  • the method of carrying out the cyclization condensation reaction using the devolatilization step at the same time is a preferred form in the present invention for obtaining a latatotone ring-containing polymer. With this form, a cyclacondensation reaction rate with a higher glass transition temperature is further increased, and a rataton ring-containing polymer having excellent heat resistance can be obtained.
  • the reactor that can be employed in the cyclization condensation reaction performed in advance before the cyclization condensation reaction simultaneously using the devolatilization step is not particularly limited, but preferably an autoclave, a kettle reactor, heat exchange And a devolatilizer comprising a devolatilizer and a devolatilizer, and a vented extruder suitable for a cyclization condensation reaction using a devolatilization step at the same time can also be used. More preferred are autoclaves and kettle reactors. However, even when using a reactor such as an extruder with a vent, adjust the temperature condition, barrel condition, screw shape, screw operating condition, etc. Thus, it is possible to carry out the cyclization condensation reaction in the same state as in an autoclave or a kettle reactor.
  • the polymerization reaction mixture obtained in the polymerization step may be used as it is. This means that once the solvent is removed, a solvent suitable for the cyclization condensation reaction may be added again.
  • Solvents that can be added again are not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; ketones such as methylethylketone and methylisobutylketone: black mouth form, DMSO ( Dimethyl sulfoxide), tetrahydrofuran or the like may be used, but the same type of solvent as that which can be used in the polymerization step is preferable.
  • Examples of the catalyst to be added in the above method (i) include esterification catalysts or transesterification catalysts such as ⁇ -toluenesulfonic acid, basic compounds, organic carboxylates, and carbonates that are generally used. In the invention, it is preferable to use the organophosphorus compound described above.
  • the addition timing of the catalyst is not particularly limited, and it may be added at the beginning of the reaction, during the reaction, or both.
  • the amount of added catalyst is not particularly limited, against the mass ⁇ this polymer (a), preferably (or 0.00;!. ⁇ 5 mass 0/0, more preferably (or 0.5 01-2 5 wt 0 / 0 , more preferably from 0.01 to !!% by mass, particularly preferably from 0.05 to 0.5% by mass.
  • the heating temperature and the heating time of the above method (i) are not particularly limited, but the heating temperature is preferably room temperature or higher, more preferably 50 ° C or higher, and the heating time is preferably 1 to 20 hours, more preferably 2 to 10 hours. If the heating temperature is low or if the heating time is short, the cyclization condensation reaction rate decreases, which is not preferable. Also, if the heating time is too long, the resin may be colored or decomposed, which is not preferable.
  • Examples of the method (ii) include a method in which the polymerization reaction mixture obtained in the polymerization step is heated as it is using a pressure-resistant kettle or the like.
  • the heating temperature is preferably 100 ° C or higher, more preferably 150 ° C or higher.
  • the heating time is preferably 1 to 20 hours, more preferably 2 to 10 hours. If the heating temperature is low, or if the heating time is short, the cyclization condensation reaction rate decreases, which is not preferable. Also, if the heating time is too long, the resin may be colored or decomposed, which is not preferable.
  • the mass reduction rate between the two is preferably 2% or less, more preferably 1.5% or less, and even more preferably 1% or less. If the mass reduction rate is higher than 2%, the cyclization condensation reaction rate does not rise to a sufficiently high level even if the cyclization condensation reaction is carried out simultaneously with the devolatilization step at the same time. There is a risk that the physical properties will deteriorate.
  • another thermoplastic resin may coexist.
  • the hydroxyl group and ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent.
  • a polymer obtained by a previously performed cyclized condensation reaction (a polymer in which at least a part of hydroxyl groups and ester groups present in the molecular chain have undergone cyclized condensation reaction) and
  • the solvent may be introduced as it is into the cyclization condensation reaction using the devolatilization step at the same time, and if necessary, the polymer (at least a part of the hydroxyl group and ester group present in the molecular chain is cyclized and condensed). It may be introduced into a cyclization condensation reaction using a devolatilization step at the same time after undergoing other treatments such as isolating the reacted polymer) and adding a solvent again.
  • the devolatilization step is not limited to be completed at the same time as the cyclization condensation reaction, but may be completed after the completion of the cyclization condensation reaction.
  • the above-mentioned Lataton ring-containing polymer has a mass reduction rate of 150% to 300 ° C in dynamic TG measurement of 1% by mass or less, more preferably 0.5% by mass or more. It is preferably 0.3% by mass or less.
  • the above-mentioned Lataton ring-containing polymer has a high cyclization condensation reaction rate, it is possible to avoid the disadvantage that bubbles and silver streaks enter the molded product after molding. Further, since the rataton ring structure is sufficiently introduced into the polymer due to the high cyclization condensation reaction rate, the obtained rataton ring-containing polymer has a sufficiently high level and heat resistance.
  • reaction conditions in the method for producing a thermoplastic resin having a ring structure in the main chain are the same as the preferred forms such as reaction conditions in the method for producing a radon ring-containing polymer.
  • the antioxidant according to the present invention has the following general formula (1): [0073] [Chemical 9]
  • R 1 is the same or different and represents an alkyl group having 1 to 5 carbon atoms
  • R 2 is the same or different and represents an alkyl group having 1 to 8 carbon atoms
  • R 3 represents a hydrogen atom or an alkyl group having from 8 to 8 carbon atoms
  • R 4 represents a hydrogen atom or a methyl group
  • phenyl (meth) acrylate is essential. It is.
  • thermoplastic resin composition containing the thermoplastic resin having the UV-absorbing monomer unit and the antioxidant the antioxidant is specified as described above, so that the heat resistance during molding can be reduced. In addition, the disadvantage that bubbles and silver streaks enter the molded product after molding can be avoided.
  • R 1 is an alkynole group having from 5 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a t-butyl group, t Pentyl group and the like. Preferred are a methyl group and an ethyl group, and more preferred is an ethyl group.
  • R 2 is an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a t-butyl group, a t-pentyl group, and a t-octyl group.
  • a methyl group or a t-pentyl group is preferable, and a t-pentyl group is more preferable.
  • R 3 is a hydrogen atom or an alkyl group having 8 to 8 carbon atoms, and examples thereof include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and an octyl group. It is done. Preferably they are a hydrogen atom or a methyl group, More preferably, it is a methyl group.
  • R 4 is a hydrogen atom or a methyl group. Preferably a hydrogen atom.
  • Antioxidants described in the present invention include, for example, 2, 4 g t amylou 6- [1 (3,5-di-t aminol 2 hydroxyphenenole) phenyl acrylate, 2 , 4 Di-t —Amiru 6— [1— (3,5 Di-tert-aminol 2-hydroxyphenol) butyl] phenyl acrylate, 2, 4 Di-t-amyl 6— [1— (3, 5 1-hydroxyl 2-hydroxyphenyl) propynole] phenyl acrylate, 2-t butynole 6- (3-t butyl-2-hydroxy-5-methylbenzyl) 4 methylphenyl acrylate, and the like.
  • One type of the above may be used, or two or more types may be used in combination.
  • 2,4-di-tert-amyl-6- [1— (3,5-di-tert-amyl-2 hydroxyphenenyl) ethyl] phenyl acrylate and / or 2- t-Butyl 6
  • One (3-t-Butyl-2 hydroxy-5 methylbenzyl) -4 Methylphenyl acrylate.
  • 2,4 di-t-amyl 6- [1- (3,5 di-t aminole 2-hydroxyphenenole) ethynole] phenyl acrylate.
  • compounds having a double bond (radically polymerizable double bond) in the molecule are used for processing to capture polymer alkyl radicals under oxygen-free conditions such as during processing. It can be used as a stabilizer, has excellent yellowing resistance, and has excellent solubility in organic solvents.
  • thermoplastic resin having an ultraviolet absorbing monomer unit is considered to generate an alkyl radical as soon as the side chain ultraviolet absorbing group is thermally cleaved.
  • the antioxidant having the structure used in the thermoplastic resin composition is particularly effective.
  • the timing of adding the antioxidant is not particularly limited as long as the physical properties of the resin composition are not impaired! /,
  • the thermoplastic resin for example, acrylic resin
  • the thermoplastic resin, the antioxidant, and other components are heated and melted simultaneously or sequentially and kneaded.
  • a method in which a thermoplastic resin or a mixture of it and other components is heated and melted, and an antioxidant or a mixture of it and other components is added thereto and kneaded.
  • a method of adding a mixture with these components and kneading is preferred.
  • the ratio of the antioxidant is less than 0.01 wt%, the thermal stability becomes FuTakashi min, foaming or silver stream during molding task may occur in. Conversely, the ratio of oxidizing prevention agent exceeds 0 mass% 5., bleed-out of excess antioxidants is Okoruko and power s.
  • thermoplastic resin composition of the present invention preferably has a glass transition temperature of 110 ° C or higher.
  • the glass transition temperature (Tg) of the thermoplastic resin composition that is suitable for the present invention is preferably 120 ° C or higher, more preferably 125 ° C or higher, still more preferably 130 ° C or higher, more preferably 135 ° C or higher. Most preferably, the temperature is 140 ° C or higher.
  • the glass transition temperature is a temperature at which a polymer molecule starts micro-Brownian motion, and there are various measurement methods.
  • AS TM- D-3418 USA
  • DSC differential scanning calorimeter
  • the glass transition temperature of the thermoplastic resin composition is such that when the thermoplastic resin composition is composed of a thermoplastic resin and an antioxidant, or when it is composed of a thermoplastic resin, an antioxidant and a deactivator.
  • the glass transition temperature when the thermoplastic resin composition is measured is preferably within the above range.
  • the thermoplastic resin composition contains components other than these, the thermoplastic resin and the antioxidant constituting the thermoplastic resin composition are mixed in a content mass ratio that will be included in the thermoplastic resin composition.
  • a glass transition when measuring a mixture in which the thermoplastic resin, antioxidant, and deactivator constituting the thermoplastic resin composition are mixed at a content mass ratio to be included in the thermoplastic resin composition The temperature is preferably within the above range.
  • thermoplastic resin composition according to the present invention preferably has a 5% weight loss temperature in thermogravimetric analysis (TG) of 280 ° C or higher, more preferably 290 ° C or higher, and still more preferably. 300 ° C or higher.
  • TG thermogravimetric analysis
  • the 5% weight loss temperature in thermogravimetric analysis (TG) is an indicator of thermal stability, and if it is below 280 ° C, sufficient thermal stability may not be exhibited.
  • thermoplastic resin composition according to the present invention has a total amount of residual volatile components contained therein of preferably 5000 ppm or less, more preferably 2000 ppm or less. If the total amount of residual volatiles exceeds 5000 ppm, it may cause coloration, volatilization, or formation defects such as silver streaks due to alteration during formation.
  • thermoplastic resin composition according to the present invention may contain a thermoplastic resin other than the thermoplastic resin having an ultraviolet-absorbing monomer unit.
  • thermoplastic resins are not particularly limited in type, but thermoplastic methacrylic resins that are thermodynamically compatible are preferred in terms of improving transparency and mechanical strength.
  • the content ratio of the thermoplastic resin having an ultraviolet-absorbing monomer unit and the other thermoplastic resin in the thermoplastic resin composition according to the present invention is preferably 60 to 99 :; , more preferably 70 to 97: 3 to 30 weight 0/0, more preferably 80 to 95: 5 to 20 mass 0/0.
  • Thermoplastic resin having UV-absorbing monomer unit in thermoplastic resin composition If the content is less than 60% by mass, the effects of the present invention may not be fully exhibited.
  • thermoplastic resins examples include olefin polymers such as polyethylene, polypropylene, ethylene monopropylene copolymer, poly (4-methyl-1 pentene); cycloolefin polymers (cycloolefin resin); Halogen-containing polymers such as chlorinated butyl resin; Acrylic polymers such as polymethyl methacrylate; Polystyrene (PSt), Styrene-methyl methacrylate copolymer, Styrene acrylonitrile copolymer, Acrylonitrile-butadiene-styrene block copolymer Styrene polymers such as coalescence; Polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; Polyamides such as nylon 6, nylon 66, nylon 610; Polyacetal: Polycarbonate (PC); Polyphenylene oxide; Polyphenylene sulfide; Polyether ether ketone; Polysulfone; Polyethers
  • the rubbery polymer preferably has a graft portion having a composition compatible with the Lataton ring polymer of the present invention on the surface, and the average particle size of the rubbery polymer is transparent when formed into an extruded film.
  • the thickness is preferably 300 nm or less, more preferably 150 nm or less.
  • Amorphous resins for optical films such as cycloolefin resin, triacetyl cellulose (TAC), polycarbonate (PC), polystyrene (PSt), etc. are difficult to copolymerize, but the amorphous resin for optical films absorbs ultraviolet rays.
  • thermoplastic resin composition of the present invention can be obtained by adding a copolymer which is a thermoplastic resin having a monomer unit.
  • a copolymer of a UV-absorbing monomer and (meth) acrylic acid ester in the present invention.
  • a more preferred form is a form in which a copolymer of 2- [2′-hydroxy-1 5′-methacryloyloxy] ethylphenyl) 2H-benzotriazole and (meth) acrylic acid ester is added.
  • thermoplastic resins that are thermodynamically compatible with the thermoplastic resin having the UV-absorbing monomer unit, in particular, the Lataton ring-containing polymer, include cyanide bulle monomer units and Copolymers containing aromatic bule monomer units, specifically attarilontrinore Styrene copolymer and polyvinylidene chloride Bulle resin, a methacrylic acid ester may be used a polymer containing the 50 weight 0/0 or more. Among them, acrylonitrile styrene copolymer is preferable because of its good compatibility with a wide range of copolymer compositions.
  • thermoplastic resin having an ultraviolet-absorbing monomer unit and other thermoplastic resins are thermodynamically compatible with each other because the glass transition point of the thermoplastic resin composition obtained by mixing them is determined. Confirmation can be made by measuring. Specifically, only one glass transition point measured by a differential scanning calorimeter is observed for a mixture of a thermoplastic methacrylic resin and another thermoplastic resin. I can say that.
  • an acrylonitrile styrene-based copolymer is used as the other thermoplastic resin
  • its production method can use an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a Balta polymerization method, or the like. From the viewpoint of transparency and optical performance of the obtained optical film, it is preferably obtained by a solution polymerization method or a Barta polymerization method.
  • thermoplastic resin composition according to the present invention, a trace amount of unreacted reactive groups remain even after the catalyst is added and the cyclization condensation reaction is sufficiently performed. Since phenomena such as thickening may occur, it is preferable to add a deactivator for the cyclization condensation catalyst.
  • a deactivator for the cyclization condensation catalyst.
  • an acid catalyst or a basic catalyst is used in the cyclization condensation reaction. In this case, the deactivator deactivates the catalyst by a neutralization reaction. If the catalyst is a basic substance, an acidic substance may be used as the deactivator.
  • the quenching agent is not particularly limited as long as it does not substantially generate a substance or the like that hinders the physical properties of the resin composition during heat processing.
  • a metal carboxylic acid when used as the quenching agent, for example, a metal carboxylic acid is used. Examples thereof include salts, metal complexes, and metal oxides. Among these, metal carboxylates and metal carboxylates that are preferred are metal oxides.
  • the metal is not particularly limited as long as it does not inhibit the physical properties of the resin composition and does not cause environmental pollution at the time of disposal.
  • an alkali metal such as lithium, sodium, or potassium
  • alkaline earth metals such as magnesium, calcium, strontium and nord; zinc; zirconium
  • the carboxylic acid constituting the metal carboxylate is not particularly limited.
  • formic acid acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, Decanoic acid, lauric acid
  • myris examples include chic acid, palmitic acid, stearic acid, behenic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citrate, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, etc. Can be mentioned. Although it does not specifically limit as an organic component in a metal complex, Acetyl acetone etc.
  • the metal oxide examples include zinc oxide, calcium oxide, magnesium oxide, etc. Among them, zinc oxide is preferable.
  • an acidic substance for example, an organic phosphoric acid compound or a carboxylic acid group-containing compound can be used.
  • the quenching agent may be used alone or in combination of two or more. The quenching agent may be added in any form such as solid, powder, dispersion, suspension, aqueous solution and the like.
  • the blending amount of the deactivator is not particularly limited as long as it is appropriately adjusted according to the catalyst used for the cyclization condensation, but is preferably 10 to the thermoplastic resin; ! OOOOppm, more preferred ⁇ is 50-5000ppm, and more preferred ⁇ is 100-3000ppm. If the amount of the deactivator is less than 10 ppm, the deactivator has insufficient action, and foaming or thickening due to cross-linking between polymers may occur during molding. On the other hand, if the amount of the deactivator exceeds 10 OOOppm, the deactivator will be used more than necessary, and the physical properties of the resin composition may be hindered, such as a decrease in molecular weight.
  • the timing of adding the deactivator is after the catalyst is added and the cyclization condensation reaction is sufficiently performed in the production of the thermoplastic resin, and before the obtained resin composition is thermally processed.
  • a method of adding a deactivator at a predetermined stage during the production of a thermoplastic resin or a method of adding a thermoplastic resin after producing the thermoplastic resin.
  • the thermoplastic resin, the deactivator, and other components are simultaneously or sequentially heated and melted and kneaded; the thermoplastic resin or the other component and the other components are mixed.
  • Examples thereof include a method in which the mixture is heated and melted, and a quencher or a mixture of it and other components is added thereto and kneaded.
  • a deactivator after producing a thermoplastic resin. More preferably, a thermoplastic resin or a mixture of it and other components is heated and melted, and the deactivator or A method of kneading by adding a mixture of the above and other components is preferable.
  • thermoplastic resin it is preferable to provide a devolatilization step after kneading the thermoplastic resin and the quenching agent. Yes.
  • the devolatilization step include the devolatilization step described above as the devolatilization step performed in the production of the rataton ring-containing polymer.
  • thermoplastic resin composition useful in the present invention contains other additives! /, And may /!
  • additives include, for example, antioxidants such as hindered phenols, phosphorus, and io; stabilizers such as light stabilizers, weather stabilizers, and heat stabilizers; glass fibers, carbon fibers, and the like.
  • Reinforcing materials near infrared absorbers; flame retardants such as tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide; antistatic agents such as anionic, cationic, and nonionic surfactants; inorganic pigments; Colorants such as organic pigments and dyes; Organic fillers and inorganic fillers; Resin modifiers; Organic fillers and inorganic fillers; Plasticizers; Lubricants; Antistatic agents;
  • the content of other additives in the thermoplastic resin molded body is preferably 0 to 5% by mass, more preferably 0 to 2% by mass, and still more preferably 0 to 0.5% by mass.
  • the thermoplastic resin composition according to the present invention has a thickness of 90-; the light transmittance at 500 nm at 100 m is preferably 80% or more, more preferably 85% or more, and still more preferably 95% or less. Above. Further, the thickness is 90 to; the light spring transmittance power at 380 nm in lOO ⁇ m is less than 0%, more preferably less than 20%, and still more preferably less than 10%. By making the light transmittance within such a range, it can be used with a force S that is suitable for various uses, particularly optical applications such as optical materials. As the optical material, if the thermoplastic resin composition that is more preferably colorless is colored, it will significantly lower the product value as an optical material.
  • the light transmittance of this wavelength is 80% or more, that is, an absorption of less than 20% means that a thermoplastic resin that absorbs less visible light. It means that the composition becomes nearly colorless.
  • the light transmittance at 500 nm is less than 80%, visible light is absorbed, coloring of the thermoplastic resin composition becomes remarkable, transparency is lowered, and there is a possibility that it cannot be used for the intended purpose.
  • it may not be suitably used as an optical material.
  • the thermoplastic resin composition of the present invention is also suitably used as an optical material having an ultraviolet cut function. Ultraviolet rays are high in energy and cause deterioration of various materials.
  • thermoplastic resin composition has a light transmittance at 380 nm of less than 30%, thereby suppressing the transmission of light at 380 nm, which is a wavelength in the ultraviolet region, to less than 30% and suppressing the transmission of ultraviolet light. Can do.
  • the thermoplastic resin composition can be suitably used as a film or sheet having an ultraviolet cutting function having a transparent appearance that is preferably in the above range.
  • the above light transmittance is measured in accordance with JIS K7361-1: 1997, but it is difficult to mold! /
  • the resin is dissolved in an appropriate solvent and 100 11 m using a quartz cell. It is also possible to substitute a measurement at a concentration equivalent to the thickness of the film and an optical path length. For example, when measuring using a quartz cell having an optical path length of 1 cm, first, a solvent is put in the quartz cell and measured as a blank, and then a 1% by mass solution of the resin to be measured is prepared, and the solution is placed in the quartz cell. It is possible to substitute by calculating the transmittance using the difference from the blank as the transmitted light intensity by injecting the liquid so that no bubbles enter.
  • the solvent needs to completely dissolve the resin to be measured, and a solvent with the smallest possible absorption at 380 nm and 500 nm should be selected.
  • the thermoplastic resin composition is in the form of pellets
  • the light transmittance can be measured by using the pellets as a 1 mass% black mouth form solution.
  • the light transmittance measured with a black mouth form solution of about 0.3 to; mass% can be used.
  • the thermoplastic resin composition according to the present invention has a light transmittance at 500 nm at a thickness of 100 m, preferably 80% or more, more preferably 85% or more, and still more preferably 95% or more. is there. If the light transmittance at 500 nm is less than 80%, the transparency is lowered and it may not be used for the intended purpose.
  • the light transmittance at 380 ⁇ m at a thickness of 100 m is preferably less than 30%, more preferably less than 20%, and even more preferably less than 10%. If the light transmittance at 380 nm is 30% or more, the ultraviolet rays cannot be sufficiently applied, and yellowing may occur.
  • the upper limit of light transmittance at 380 nm or 500 nm is 100% at which substantially all light is transmitted. (Use and molding of thermoplastic resin composition)
  • thermoplastic resin composition of the present invention not only has excellent transparency and heat resistance, but also has properties such as low colorability, mechanical strength, and moldability, and also has an ultraviolet absorbing ability, so that it can be used as a film or sheet. It is useful, for example, as an extruded film or extruded sheet. That is, the present invention is also a finalem or sheet formed from the above thermoplastic resin composition.
  • a preferred embodiment of the thermoplastic resin composition of the present invention is an extruded film or an extruded sheet made of the thermoplastic resin composition.
  • the present invention is also a method for producing the film or sheet of the present invention, wherein the film or sheet production method is also a film or sheet production method in which a forming step is performed after a filtration treatment step using a polymer filter.
  • thermoplastic resin compositions In the normal molding process of thermoplastic resin compositions, it is inevitable that foreign substances are mixed in the thermoplastic resin composition and the molding process. It is desirable to do. For example, it is desirable to reduce the number of defects generated in industrially produced molded products by removing foreign substances and to improve the appearance of molded products. In particular, for molded products used for optical applications, it is preferable to perform the molding step after the filtration treatment step using a filter that greatly affects the optical performance due to the presence of foreign substances.
  • thermoplastic resin composition when extruding a thermoplastic resin composition, it is usually a solid (in the form of pellets) at room temperature, so it is necessary to melt the molding material in a filtration process and pass it through a polymer filter. . Therefore, in addition to receiving the thermal history in the molding process, the thermal history is also received in the preceding filtration process. In the conventional technology, there has been a problem that the thermal deterioration is caused by such a thermal history.
  • the thermoplastic resin composition that can be used in the present invention can be made to have superior heat resistance than conventional molding processes. Even when receiving a larger amount of heat history, the effect of suppressing the deterioration of the resin (molded product) due to the heat history applied to the resin can be exhibited. As a result, thermal deterioration of a molded product such as a film or a sheet formed from the thermoplastic resin composition is suppressed, and it becomes possible to more effectively exhibit effects such as high appearance and optical performance. The problem can be solved. This is one technical significance of the present invention.
  • Preferred embodiments of the film or sheet of the present invention and the preferred method for producing the film or sheet of the present invention are an extruded film or an extruded sheet described later.
  • Preferred embodiments of the present invention are the same as the preferred embodiments of the method for producing an extruded film or extruded sheet.
  • Examples of the molding step include extrusion molding of the thermoplastic resin composition of the present invention.
  • the film or sheet of the present invention is preferably used as an optical film or an optical sheet.
  • the film or sheet that is effective in the present invention is preferably an extruded film or an extruded sheet obtained by extruding the thermoplastic composition.
  • the thickness of the extruded film is preferably 1 m or more and less than 350 m, more preferably 10 mm or more and less than 350 m.
  • the film thickness is less than 1 m, it is not preferable because the strength is poor, and breakage or the like is likely to occur when stretching.
  • the thickness of the extruded sheet is preferably 350 111 to 10111 111, more preferably 350 m to 5 mm.
  • a sheet-like optical thermoplastic resin molded article having a thickness of more than 10 mm is not preferable because the sheet thickness is difficult to be uniform.
  • the total light transmittance is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more, and particularly preferably 92%. That's it.
  • the extruded film or extruded sheet preferably has a tensile strength measured in accordance with ASTM-D-882-61T (American Society for Testing and Materials) of at least lOMPa and less than lOOMPa. More preferably, it is 30 MPa or more and less than lOOMPa. If it is less than lOMPa, it is not preferable because sufficient mechanical strength may not be exhibited. If it exceeds lOOMPa, workability may be deteriorated.
  • the above extruded film or extruded sheet is measured according to ASTM-D-882-61T. It is preferable that the obtained elongation is 1% or more.
  • the upper limit is not particularly limited, but is usually preferably 100% or less. If it is less than 1%, the toughness may be lacking.
  • the extruded film or extruded sheet of the present invention preferably has a tensile modulus measured based on ASTM-D-882-61T of 0.5 GPa or more, more preferably IGPa or more, and further preferably 2 GPa or more. It is.
  • the upper limit is not particularly limited, but is usually preferably 20 GPa or less. If it is less than 5 GPa, it is not preferable because sufficient mechanical strength may not be exhibited.
  • thermoplastic resin composition of the present invention As an example of a preferred application, a method for producing an extruded film or an extruded sheet from the thermoplastic resin composition of the present invention will be described in detail below.
  • thermoplastic resin composition of the present invention is not particularly limited.
  • a thermoplastic resin having an ultraviolet-absorbing monomer unit and other thermoplastic resins or other thermoplastic resins may be used.
  • Additives and the like can be mixed by a conventionally known mixing method to produce an extruded film or sheet from a thermoplastic resin composition in advance.
  • a method for producing this thermoplastic resin composition for example, a method of pre-blending with a mixer such as an omni mixer and then extruding and kneading the obtained mixture can be employed.
  • the kneader used for extrusion kneading is not particularly limited.
  • an extruder such as a single screw extruder or a twin screw extruder or a pressure kneader, for example, a conventionally known kneader is used. be able to.
  • a method of extrusion kneading for example, a melt extrusion method can be preferably used.
  • melt extrusion method examples include a T-die method and an inflation method, and the molding temperature of the extruded film or extruded sheet is preferably 150 to 350 ° C, more preferably. (200 to 350 ° C, more preferable (200 to 300 ° C, more preferable (25 0 to 300 ° C, more preferable ⁇ 255 to 300 C. Special preference ⁇ or 260-300 o C.
  • extrusion film molding or extrusion sheet molding is performed by the above T-die method, that is, when extrusion molding is performed, a T-die is attached to the tip of a known single-screw extruder or twin-screw extruder, A film extruded into a film can be obtained as a roll-shaped film.
  • steps such as sequential biaxial stretching and simultaneous biaxial stretching by adding a process of stretching the film in a direction perpendicular to the extrusion direction.
  • the extruder used in the production of the extruded film or extruded sheet of the present invention can be applied to either a single-screw extruder or a multi-screw extruder in order to obtain a sufficient plasticization and kneading state.
  • L / D (L represents the cylinder length of the extruder, D represents the cylinder inner diameter) 1S 10 to 100 is preferable 20 to 50 is more preferable 25 to 40 is most preferable. If L / D is less than 10, it is difficult to obtain a sufficient plasticization or kneading state. If it exceeds 100, excessive shearing heat generation is applied to the resin, and the resin may be decomposed.
  • the set temperature of the cylinder is preferably 200 ° C or higher and 300 ° C or lower, and more preferably 250 ° C or higher and 300 ° C or lower. Below 200 ° C, the melt viscosity of the resin becomes high, so higher power than necessary and L / D necessary for plasticization are required, which hinders productivity. If it exceeds 300 ° C, the resin may decompose.
  • the shape of the extruder is not particularly specified.
  • the extruder has one or more open vent portions, and decomposed gas generated under reduced pressure is generated. Suction force The increase in residual volatile matter can be suppressed.
  • the degree of pressure reduction is preferably in the range of 931-1.3 hPa (700 to 1 mmHg). More preferably, it is in the range of 798—13.3 hPa (600 to 10 mmHg).
  • the pressure is higher than 931 hPa, residual volatile components in the molten resin, monomer components generated by resin decomposition, and the like are likely to remain.
  • it is lower than 1.3 hPa there is a problem that industrial implementation becomes difficult.
  • the extruded film or extruded sheet is used for optical applications such as an optical film, it is not particularly limited, but in order to prevent adverse effects on the appearance after molding, the foreign matter in the resin is removed with a polymer filter. After forming, it is preferable to mold.
  • the resin composition deteriorates when resin melted at high temperature passes through the polymer filter, and when it is continuously molded, decomposed gas components and colored deterioration products flow out. Holes, flow patterns, and flow streaks are sometimes observed as defects in Rumya sheets. Therefore, in order to reduce the melt viscosity of the resin and shorten the residence time in the polymer filter as much as possible, the molding temperature is not particularly limited, but preferably 255. C ⁇ 300. C, particularly preferably 260. C ⁇ 300. C.
  • the polymer filter is not particularly limited, but a polymer filter in which a disk type filter is arranged in a housing is preferably used, and a polymer filter in which a large number of leaf disk filters are arranged in the housing. Is more preferable.
  • the filter material in the leaf disk type filter may be a type in which a metal fiber non-woven fabric is sintered, a type in which metal powder is sintered, a type in which several metal meshes are laminated, or a hybrid type in which they are combined! ! /, But the most preferred type is sintered metal fiber nonwoven!
  • the filtration accuracy is not particularly limited, but is 15 111 or less, more preferably 10 m or less, and most preferably 5 m or less. Moreover, it is preferable to exceed 1 m. If it is l ⁇ m or less, the filtration residence time becomes longer, which is not preferable from the viewpoint of thermal degradation of the resin and productivity. On the other hand, if it exceeds 15 in, foreign matter is likely to be mixed, which is not preferable.
  • the filtration area with respect to the resin treatment amount per hour of the polymer filter is not particularly limited, and is appropriately set according to the treatment amount, for example, 0.001 to 0.15 m 2 / (kg / h).
  • the polymer filter provided with the leaf disk type filter is provided with a center pole passing through the center of the disk type filter.
  • the shape of the center pole is not particularly limited, but it is an internal flow type having a plurality of resin flow ports and a resin flow path in the center pole, and a disc type filter inner peripheral surface (for example, a cross section having a plurality of vertices or faces)
  • a disc type filter inner peripheral surface for example, a cross section having a plurality of vertices or faces
  • an external flow type with a resin flow path on the outer surface of the center pole that touches the inner surface of the leaf disk type filter is used. /.
  • the residence time during filtration with the polymer filter is not particularly limited, but is preferably 20 minutes or less, more preferably 10 minutes or less, and most preferably 5 minutes or less.
  • the filter inlet pressure and the filter outlet pressure during filtration are, for example, in the range of 3 to 15 MPa and 0.3 to 10 MPa, respectively, and the pressure loss (pressure difference between the filter inlet pressure and the outlet pressure) is IMPa to 15 MPa. It is preferable to be within the range. If the pressure loss is IMPa or less, the flow path through which the polymer passes through the filter tends to be biased and the quality is likely to deteriorate immediately. Conversely, 15 If it exceeds MPa, the filter may be easily damaged.
  • the resin temperature of the heat-resistant acrylic resin introduced into the filter is a force that is appropriately set according to the viscosity. Usually, it is in the range of 250 to 300 ° C, preferably in the range of 255 to 300 ° C, most preferably 260 to 300. It is in the range of ° C.
  • the process of obtaining a final molded body with less foreign matter and color by filtration with the polymer filter is not particularly limited, but (1) The filtration process is performed in a clean environment at the time of polymer production, and the process continues in a clean environment. (2) A process in which a polymer having foreign matter and colored substances is once filtered in a clean environment and then molded in a clean environment. (3) A polymer having foreign matter and colored substances in a clean environment. The process of forming at the same time as the filtration process is raised, and the polymer filter process may be performed a plurality of times for each process. In addition, it is more preferable to stabilize the resin pressure in the filter by installing a gear pump between the extruder and the filter regardless of single-screw extruder, twin-screw extruder, or multi-screw extruder.
  • thermoplastic resin having an ultraviolet-absorbing monomer unit and, if necessary, an ultraviolet absorber.
  • a thermoplastic resin composition After kneading with an extruder to produce a thermoplastic resin composition, it is preferably formed into an extruded film or an extruded sheet as it is.
  • the thermal history is reduced, so that the resin composition can be prevented from thermal degradation, and foreign substances from the environment can be prevented. Can be reduced.
  • a gear pump and a polymer filter are installed between the extruder and the T die.
  • the extruded film of the present invention may be an unstretched film or a stretched film.
  • a uniaxially stretched film or a biaxially stretched film may be used.
  • a biaxially stretched film it may be simultaneously biaxially stretched or sequentially biaxially stretched.
  • the film of the present invention (for example, an optical film) can suppress an increase in retardation even when stretched by mixing other thermoplastic resin compositions, and can maintain optical isotropy. it can.
  • the stretching temperature is not particularly limited. Specifically, the stretching temperature is preferably near the glass transition temperature of the thermoplastic resin composition of the extruded film raw material.
  • the draw ratio defined by the area ratio is preferably 1 .;! To 25 times, more preferably 1.3 to 10 times. 1. If it is less than 1 time, it is not preferable because it does not lead to improvement of toughness accompanying stretching. If it is larger than 25 times, the effect of increasing the draw ratio is not recognized.
  • the stretching speed (one direction) is preferably in the range of 10 to 20000% / min, more preferably in the range of 100 to 10,000% / min. If it is slower than 10% / min, it takes time to obtain a sufficient stretch ratio, and this is not preferable because the production cost increases. If it is faster than 20000% / min, the stretched extruded film may be broken, which is not preferable.
  • heat treatment annealing or the like can be performed after the stretching treatment.
  • the extruded film or extruded sheet of the present invention includes an antifouling layer such as an antistatic layer, an adhesive layer, an adhesive layer, an easy adhesion layer, an antiglare (non-glare) layer, or a photocatalyst layer, depending on the purpose.
  • an antifouling layer such as an antistatic layer, an adhesive layer, an adhesive layer, an easy adhesion layer, an antiglare (non-glare) layer, or a photocatalyst layer, depending on the purpose.
  • Various functional coating layers such as an antireflection layer, a hard coat layer, an ultraviolet ray shielding layer, a heat ray shielding layer, an electromagnetic wave shielding layer, and a gas barrier property are laminated and applied to the extruded film or extruded sheet of the present invention. It may be a laminate in which members each coated with a single functional coating layer are laminated via an adhesive or an adhesive. Note that the stacking order of the layers is not particularly limited, and the stacking
  • the extruded film or extruded sheet of the present invention is not particularly limited, but is suitably used for optical applications, and examples thereof include an optical protective film, an optical film, and an optical sheet.
  • the optical protective film is not particularly limited as long as it is a film that protects optical components.
  • various optical disk (VD, CD, DVD, MD, LD, etc.) substrates examples thereof include a protective film and a polarizer protective film used for a polarizing plate for a liquid crystal display device.
  • the optical film is not particularly limited as long as it has excellent optical properties.
  • the retardation film, the viewing angle compensation film, the light diffusion film, the reflection film, the antireflection film, the antiglare film, the brightness enhancement film For example, conductive films for touch panels.
  • the optical sheet include a diffusion plate, a light guide, a retardation plate, and a prism sheet.
  • thermoplastic resin composition of the present invention since a specific antioxidant is blended in the thermoplastic resin having an ultraviolet-absorbing monomer unit, it has ultraviolet-absorbing ability and transparency. In addition to providing desired properties such as mechanical strength and molding processability, it is possible to provide a molded product having excellent thermal stability during molding.
  • the weight average molecular weight of the polymer in the resin composition was determined under the following conditions using GPC (manufactured by Tosohichi Corporation, apparatus name: GPC system).
  • Reference ⁇ j Reference column (TSKgel SuperH-RC)
  • the thermal analysis of the resin composition was carried out using a differential scanning calorimeter (manufactured by Rigaku Corporation, apparatus name: DSC-8230) under the conditions of about 10 mg sample, heating rate 10 ° C / min, nitrogen flow 50cc / min. make use of went.
  • the glass transition temperature (Tg) was determined by the midpoint method according to ASTM-D-3418.
  • the light transmittance of the resin composition is as follows. Dissolve the resin composition in black mouth form and put it in 0.3% by mass in a quartz cell with an optical path length of lcm. Spectrophotometer (Shimadzu Corporation, apparatus name: UV-310 0) It measured using.
  • MMA methyl methacrylate
  • MHMA hydroxymethyl methyl acrylate
  • 2 — [2′-hydroxy 5′-methacryloyloxy] ethyl phenyl) 2H benzotriazole manufactured by Otsuka Chemical Co., Ltd., trade name: RUVA-93, UV-absorbing monomer
  • 50 parts of toluene, 0.025 part Phosphorus antioxidant (Asahi Denka Kogyo Co., Ltd., trade name: Adekas Tab 2112)
  • n Dodecino Remenorekabutane 0.025 part was charged, and the temperature was raised to 105 ° C through nitrogen.
  • tamyl peroxy isononanoate manufactured by Watofina Yoshitomi Co., Ltd., trade name: Lupasol 570
  • 0.1 part of tamil pero was added.
  • the polymer solution obtained by the above cyclization condensation reaction was subjected to a barrel temperature of 240 ° C, a rotation speed of 100 rpm, a vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent number of 1, a forevene.
  • the antioxidant 2,4G t amylou 6- [1-(3,5 di-t-amino tert-hydroxyphenol 2-ethyl) ethyl] phenyl acrylate (Sumitomo Chemical Co., Ltd., product) Name: Sumilizer GS) 40 parts and quenching agent zinc octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: Nitsuka octitas zinc 3.6%) Antioxidant dissolved in 29 parts toluene 200 parts The active agent mixed solution is injected at a rate of 0.02 kg / hour after the first vent using a high-pressure pump, and at the same time, ion-exchanged water is added using a high-pressure pump after the third vent to 0.01 kg.
  • a yellow transparent resin composition pellet was obtained.
  • the glass transition temperature of the obtained pellet is 126 ° C
  • the light transmittance at 380 nm is 13%
  • the light transmittance at 500 nm is 98% or more
  • the weight average molecular weight of the polymer in the resin composition is It was 135000.
  • Antioxidant is 2-t-butyl 6- (3-t-butyl 2-hydroxy-5-methyl benzyl) methyl phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GM)
  • a yellow transparent resin composition pellet was obtained in the same manner as in Example 1 except that the amount was changed to 40 parts.
  • the glass transition temperature of the obtained pellet is 127 ° C
  • the light transmittance at 380 nm is 14%
  • the light transmittance at 500 nm is 98% or more
  • the weight average molecular weight of the polymer in the resin composition was 130,000.
  • a yellow transparent resin composition pellet was obtained in the same manner as in Example 1 except that the antioxidant was used. When the foamability of the obtained pellets was evaluated, many fine bubbles were observed.
  • pentaerythritol tetrakis [3- (3,5-di-butynole 4-hydroxyphenyl) propionate] is a compound represented by the following formula.
  • pentaerythritol tetrakis [3- (3,5-di-butynole 4-hydroxyphenyl) propionate] is a compound represented by the following formula.
  • the antioxidant is a mixture of a phosphorus processing stabilizer and a phenolic antioxidant, ie octadecyl-3- (3 ', 5'-ditert--4'-hydroxyphenyl) propionate, Mixture of squirrel (2,4 di-tert-butylphenyl) phosphite and 5,7 di-tert-butyl-3- (3,4 dimethylphenyl) 3H benzofuran 2-one (Ciba Specialties manufactured by Chemikanoles Co., Ltd., trade name: A yellow transparent resin composition pellet was obtained in the same manner as in Example 1 except that IRGANOX HP 2921) was used. When the foamability of the obtained pellets was evaluated, many fine bubbles were seen and foamed.
  • the b value of the optical film was measured using a color difference meter (manufactured by Nippon Denshoku Co., Ltd., trade name: ND-1001DP).
  • the b value represents the b value of Hunter's Lab color system and was measured by a method based on JIS Z8730.
  • the film light transmittance was measured using a spectrophotometer (manufactured by Shimadzu Corporation, apparatus name: UV-3100) V and the transmittance at 380 nm.
  • Film defects refer to substances that impair the appearance of the film, and include foreign substances such as dust mixed in from the environment, polymer gels, carbides, bubbles, and scratches on the film surface that are generated and mixed in the process.
  • Solution polymerization was performed in the same manner as in Example 1 except that 39 parts of MMA monomer, 7.5 parts of MHMA, and 3.5 parts of RUVA-93 were added to the reactor.
  • 0.05 part of 2-ethylhexyl phosphate was changed to 0.05 part of stearyl phosphate (trade name: Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.).
  • a cyclization condensation reaction was carried out in the same manner as in Example 1.
  • the devolatilization operation was performed in the same manner as in Example 1 except that the antioxidant GS was changed to 80 parts to obtain a yellow transparent resin composition pellet. It was.
  • the polymer had a weight average molecular weight of 1470,000. When the foamability was evaluated, it was good with almost no foaming.
  • the temperature of the pellet (3A) was adjusted to around 60 ° C by blowing dehumidified air heated in a hopper.
  • a nitrogen introduction pipe was provided at the bottom of the hopper, and nitrogen gas was introduced into the extruder.
  • the ventroca was melted and kneaded with a Noliaflight type screw while suctioning at 13 hPa (10 mmHg).
  • the pellet (3A) is passed through a leaf disk filter with a filtration area of 0.75 m 2 and filtration accuracy of 5 ⁇ m using a gear pump, and on a cooling roll at 90 ° C from a 700 mm wide T-die. A film was formed on the film.
  • the cylinder, gear pump, filter, and T-die temperature were set to 260 ° C, the extrusion rate per unit time was 33 kg / hr, and molding was continued for 3 hours.
  • the film thickness of the obtained optical finem was 90 m, the film light transmittance at 380 nm was 0.3%, the b value was 0.8, the glass transition temperature was 125 ° C, and the film defects were 4 / m 2. It was.
  • Example 3 The procedure up to solution polymerization and cyclization condensation reaction is the same as in Example 3, and the same procedure as in Example 3 is performed except that the antioxidant is changed to the Sumizer GM in the devolatilization operation. Got. When foaming property was evaluated, it was good with almost no foaming. [0134] Also, AS resin and melt extrusion were performed in the same manner as in Example 3 to produce pellets (4A).
  • the pellet (4A) obtained above was further film-formed continuously for 3 hours through a leaf disk type filter in the same manner as in Example 3.
  • the resulting film thickness is 90 m of the optical film, the film light transmittance of 380nm is 0. 3%, b value 1.0, glass transition temperature 125 ° C, full Ilm disadvantage filed at 19 / m 2 It was.
  • the pellet (5B) obtained above was further film-formed continuously for 3 hours through a leaf disk filter in the same manner as in Example 3.
  • the resulting film thickness is 90 m of the optical film, the film light transmittance of 380 nm 0. 3%, b value 1.2 and the glass transition temperature 123 ° C, the full Ilm drawbacks have 50 / m 2 or more There were a lot of bubbles in the shape of streaks.
  • Solution polymerization was carried out in the same manner as in Example 1 except that the monomer MMA charged in the reaction kettle was 40.5 parts, MHMA 6 parts, and RUVA-93 3.5 parts.
  • the devolatilization operation was carried out in the same manner as in Example 1 except that the antioxidant GS was 80 parts, and a yellow transparent resin composition pellet was obtained.
  • the weight average molecular weight of the polymer was 150,000, and when the foamability was evaluated, it was good with almost no foaming.
  • melt extrusion was performed from a T-die installed at the exit of the extruder, and the film thickness was 90 m and the film light transmittance at 380 nm was 0.4%.
  • the b value was 0.6
  • the glass transition temperature was 122 ° C
  • the film defects were 50 pieces / m 2 or more.
  • an antioxidant / deactivator mixed solution in which 80 parts of an antioxidant (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer GS) dissolved in 200 parts of toluene was added after the first vent.
  • the high-pressure pump was used to inject at a charging rate of 0.02 kg / hour, and at the same time, ion exchange water was injected at a charging rate of 0.01 kg / hour using the high-pressure pump after the third vent.
  • the resulting pellet has a glass transition temperature of 109 ° C and a light transmittance of 13% at 380 nm.
  • the light transmittance at 500 nm was 98% or more, and the weight average molecular weight of the polymer in the resin composition was 147000.
  • the foaming property was evaluated, the foaming was slightly good but good.
  • a yellow transparent resin composition pellet was obtained in the same manner as in Example 6 except that the antioxidant was changed to Irganox 1010 (trade name, manufactured by Chinoku Specialty Chemicals Co., Ltd.). When the foamability of the obtained pellets was evaluated, relatively large bubbles were observed, and the result was foaming.
  • the resulting polymer solution was treated with a barrel temperature of 230 ° C, a rotation speed of lOOrpm, a degree of vacuum of 13.3 to 400h? & (10 to 300111111 ⁇ 3 ⁇ 4), a number of reactants and a number of forevents of 4 (upstream).
  • a barrel temperature of 230 ° C a rotation speed of lOOrpm, a degree of vacuum of 13.3 to 400h? & (10 to 300111111 ⁇ 3 ⁇ 4), a number of reactants and a number of forevents of 4 (upstream).
  • Okg / hour in terms of resin amount Introduced at a rate and devolatilized.
  • ion exchange water was injected at a rate of 0.01 kg / hour using a high-pressure pump after the third vent.
  • the pellet (7A) is passed through a leaf disk type filter with a filtration area of 0.75 m 2 and filtration accuracy of 5 m using a gear pump, and placed on a 90 ° C cooling roll from a 700 mm wide T-die.
  • a film was formed.
  • the temperature of the cylinder, gear pump, finoleta, and T-die was set to 265 ° C, and the extrusion rate per unit time was 33 kg / hr.
  • the film thickness of the resulting optical film is 90 ⁇ 111, 380 nm Finolem light fountain transmittance (0-3%, b straight (11.5, glass transition temperature (13 13 ° C, film defect is 4 Pieces / m 2 .
  • a film was formed through a polymer filter in the same manner as in Example 7 except that the antioxidant used for dry blending with the pellet (7A) was 0.33 part of Irganox 1010.
  • the film thickness of the obtained optical film was 90 m, the film light transmittance at 380 nm was 0.3%, the b value was 1.6, and the glass transition temperature was 131 ° C. Film defects were 50 / m 2 or more, and there were many bubbles.
  • thermoplastic resin composition containing the thermoplastic resin having the ultraviolet-absorbing monomer unit of the present invention and a specific antioxidant has ultraviolet-absorbing ability, heat resistance and transparency. It can be seen that the molded product has desired properties such as mechanical strength and moldability, and is excellent in thermal stability especially during high-temperature molding, and gives no molded product.
  • thermoplastic resin composition of the present invention has the ability to absorb ultraviolet rays, has desired properties such as heat resistance, transparency, mechanical strength, and moldability, and is particularly good in thermal stability during molding. Excellent, no bubbles! / Since it can give molded products, it can be used in a wide range of transparent materials and optical-related applications that require light resistance. It makes a great contribution to the required application.

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Abstract

L'invention concerne une composition de résine thermoplastique ayant des propriétés souhaitées, notamment transparence, résistance mécanique et maniabilité au moulage, ladite composition présentant notamment une excellente stabilité thermique au moulage et ayant une capacité d'absorption UV. La composition de résine thermoplastique comprend une résine thermoplastique comprenant une unité monomère absorbant les UV et un antioxydant, ledit antioxydant comprenant essentiellement un phényl(méth)acrylate représenté par la formule générale (1). (1) dans laquelle les R1 représentent indépendamment un groupement alkyle ayant de 1 à 5 atomes de carbone ; les R2 représentent indépendamment un groupement alkyle ayant de 1 à 8 atomes de carbone ; R3 représente un atome d'hydrogène ou un groupement alkyle ayant de 1 à 8 atomes de carbone ; et R4 représente un atome d'hydrogène ou un groupement méthyle.
PCT/JP2007/070258 2006-10-18 2007-10-17 Composition de résine thermoplastique WO2008047836A1 (fr)

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WO2009134488A1 (fr) * 2008-04-30 2009-11-05 3M Innovative Properties Company Monomères d’ortho-benzylphénol mono(méth)acrylate appropriés pour des films optiques microstructurés
WO2010103030A3 (fr) * 2009-03-13 2010-11-25 Basf Se Mélanges stabilisés de polyester et de polyamide
JP2011016916A (ja) * 2009-07-08 2011-01-27 Kuraray Co Ltd 光学部材用メタクリル系樹脂組成物およびそれを用いた光学部材
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JP2011185958A (ja) * 2010-03-04 2011-09-22 Konica Minolta Opto Inc 光学フィルム、及びそれを用いた偏光板、液晶表示装置
JP2013075983A (ja) * 2011-09-30 2013-04-25 Nippon Shokubai Co Ltd アクリル樹脂組成物の製造方法およびアクリル樹脂組成物

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