WO2017188031A1 - Procédé de production d'un copolymère séquencé de maléimide - Google Patents

Procédé de production d'un copolymère séquencé de maléimide Download PDF

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Publication number
WO2017188031A1
WO2017188031A1 PCT/JP2017/015330 JP2017015330W WO2017188031A1 WO 2017188031 A1 WO2017188031 A1 WO 2017188031A1 JP 2017015330 W JP2017015330 W JP 2017015330W WO 2017188031 A1 WO2017188031 A1 WO 2017188031A1
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Prior art keywords
block copolymer
polymer
block
polymerization
monomer
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PCT/JP2017/015330
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English (en)
Japanese (ja)
Inventor
倫明 北村
慎也 井本
中西　秀高
悠 ▲高▼橋
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株式会社日本触媒
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Priority claimed from JP2017074859A external-priority patent/JP7170382B2/ja
Application filed by 株式会社日本触媒 filed Critical 株式会社日本触媒
Priority to CN201780026033.5A priority Critical patent/CN109071740B/zh
Priority to EP17789316.1A priority patent/EP3450473A4/fr
Priority to US16/095,862 priority patent/US11015011B2/en
Publication of WO2017188031A1 publication Critical patent/WO2017188031A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a method for producing a block copolymer having a polymer block containing a structural unit derived from an acrylate ester and a polymer block containing a structural unit derived from an N-substituted maleimide ring structure and a methacrylic acid ester.
  • acrylic resins have been mainly used as these optical material resins.
  • acrylic resins having a ring structure are used for optical films and the like because they have transparency and heat resistance.
  • polymers polymerized using maleimide monomers are known to be thermoplastic resins with excellent heat resistance, and to be suitably used as raw materials for optical films due to excellent transparency and retardation control. Yes. Therefore, the acrylic resin which has a maleimide ring structure obtained by superposing
  • acrylic polymers are decomposed from the polymer ends by a depolymerization reaction, and in order to impart thermal decomposition resistance, the molecular ends are sealed in the form of thioethers with a chain transfer agent using a thiol compound such as dodecyl mercaptan.
  • a thiol compound such as dodecyl mercaptan.
  • a monomer (B1) containing methacrylic acid ester and N-substituted maleimide in the presence of a thiol compound (C1) a block copolymer having excellent flexibility and strength can be obtained. It was.
  • Such a polymerization method is usually a living radical polymerization.
  • thiol compounds are not commonly used in living radical polymerizations to inhibit polymerization reactions, it is surprising that only the idea of using thiol compounds in living radical polymerizations is surprising. Furthermore, the present inventors have surprisingly found that the polymerization reaction is not hindered despite the fact that such a polymerization method is a living radical polymerization using a thiol compound. Moreover, it has also been found that in such a polymerization method, there are few unreacted maleimide monomers. This is thought to be due to the suppression of the occurrence of Michael adducts of maleimide monomers and thiol compounds. Even though the maleimide monomers and thiol compounds coexist, the generation of such Michael adducts can be suppressed. Is a surprising finding.
  • the present invention relates to a block copolymer having a polymer block (A) containing a structural unit derived from an acrylate ester and a polymer block (B) containing a structural unit derived from an N-substituted maleimide ring structure and a methacrylic ester. It relates to a manufacturing method and the like.
  • the method for producing a block copolymer of the present invention comprises a nitroxide polymer (A1) having a nitroxide structure having an organophosphorus unit at the terminal of a polymer block (A), a monomer (B1 ) In the presence of the thiol compound (C1).
  • the present invention also includes a block copolymer having a polymer block (A) containing a structural unit derived from an acrylate ester and a polymer block (B) containing a structural unit derived from an N-substituted maleimide ring structure and a methacrylic ester. included.
  • the weight average molecular weight of such a block copolymer may be, for example, 150,000 to 450,000.
  • such a block copolymer may be manufactured by the manufacturing method.
  • the present invention includes a resin composition containing the block copolymer.
  • a resin composition may contain the block copolymer and another resin as a resin component.
  • Such other resins include, for example, resins having a skeleton in common with the block copolymer (for example, resins having structural units derived from at least one monomer selected from methacrylic acid esters and N-substituted maleimides, particularly Or a resin having a structural unit derived from the monomer (B1).
  • a typical resin composition containing another resin has, for example, a structural unit derived from at least one monomer selected from the block copolymer and a methacrylic acid ester and an N-substituted maleimide as a resin component.
  • a resin composition for example, a polymer having a structural unit derived from the monomer (B1)) and having a weight average molecular weight of the whole resin component of 50,000 to 500,000.
  • the present invention also includes a film containing the block copolymer or the resin composition (for example, an optical film such as a polarizer protective film), a polarizing plate provided with the film, and an image display provided with the polarizing plate. Also includes devices.
  • a maleimide block copolymer having a structural unit derived from an acrylic monomer can be provided.
  • Such a block copolymer is excellent in flexibility and strength.
  • the terminal of such a block copolymer is sealed with a thiol compound, it is excellent in thermal decomposition resistance.
  • the maleimide monomer remaining in the polymerization solution is small, the amount of maleimide monomer that volatilizes even when the polymerization solution is heat-treated is small, and the amount of maleimide monomer attached to the production facility can be reduced.
  • a novel block copolymer having a polymer block containing a structural unit derived from an acrylate ester, and a polymer block containing a structural unit derived from an N-substituted maleimide ring structure and a methacrylic acid ester, and this A resin composition containing a block copolymer can be provided.
  • Such a block copolymer or resin composition has excellent physical properties (characteristics) such as excellent heat resistance, and is extremely useful in optical film applications and the like.
  • the present invention relates to a polymer block (A) comprising a structural unit derived from an acrylate ester (or simply referred to as “acrylate unit”, hereinafter the same in the same expression), an N-substituted maleimide ring structure and
  • This is a method for producing a block copolymer having a polymer block (B) containing a structural unit derived from a methacrylic ester (or a methacrylic ester unit).
  • a nitroxide polymer (A1) having a nitroxide structure having an organophosphorus unit at the terminal of a polymer block (A), and a monomer (B1) containing a methacrylic acid ester and an N-substituted maleimide are thiol-based.
  • a polymerization step of polymerizing in the presence of the compound (C1) is included.
  • the nitroxide polymer (A1) has a nitroxide structure having an organophosphorus unit at the end of the polymer block (A) containing an acrylate unit.
  • the nitroxide polymer (A1) may have a nitroxide structure having an organic phosphorus unit at least at one end of the polymer block (A), but preferably has both ends of the polymer block (A).
  • the acrylate unit is not particularly limited.
  • aliphatic acrylate for example, acrylic acid alkyl ester (for example, acrylic acid C such as methyl acrylate, ethyl acrylate, butyl acrylate, etc.) 1-18 alkyl), etc.
  • alicyclic acrylates for example, cycloalkyl acrylates (eg, C 3-20 cycloalkyl acrylates such as cyclopropyl acrylate, cyclobutyl acrylate), crosslinked cyclic acrylates (eg, isobornyl acrylate) and the like]
  • aromatic acrylates for example, acrylic acid aryl esters (e.g., phenyl acrylate, C 6-20 aryl such as acrylic acid o- tolyl) acrylic acid aralkyl ester (e.g., benzyl acrylate Acrylic acid C 6-10 aryl C 1-4 alkyl), acrylic acid phenoxyalkyl
  • the acrylate unit preferably includes at least an alkyl acrylate unit, more preferably includes at least a C 1-18 alkyl acrylate unit, and an n-butyl acrylate unit. It is more preferable that at least be included.
  • the content of the acrylic acid alkyl ester unit in the acrylic acid ester unit is, for example, 50 to 100 mol%, preferably 70 to 100 mol%, in terms of the monomer constituting the polymer block (A). is there.
  • the content of the acrylic acid alkyl ester unit in the acrylic acid ester unit is, for example, 50 to 100% by mass, preferably 70 to 100% by mass.
  • the polymer block (A) may have one or more units derived from monomers other than the acrylate unit.
  • the nitroxide structure having an organic phosphorus unit usually has a nitroxy free radical (NO).
  • NO nitroxy free radical
  • the nitroxide structure having an organophosphorus unit is, for example, a structure represented by the following formula (1).
  • R 1 represents a hydrogen atom or a substituent
  • R 2 represents a linking group
  • X represents an organophosphorus unit.
  • examples of the substituent include a hydrocarbon group.
  • examples of the hydrocarbon group include aliphatic groups [eg, C 1-10 alkyl groups (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, etc.
  • C 1-4 alkyl group etc. Preferably C 1-4 alkyl group etc.], alicyclic group [eg C 3-12 cycloalkyl group (eg cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group etc.), preferably C 3-7 cycloalkyl group etc.], aromatic group ⁇ eg C 6-20 aromatic group [eg C 6-20 aryl group (eg phenyl group, o-tolyl group, m-tolyl group, p-tolyl group) Group, 2,3-xylyl group, 1-naphthyl group, etc.), C 7-20 aralkyl group (eg benzyl group, etc.)] ⁇ and the like.
  • the hydrocarbon group may further have a substituent (for example, a halogen atom).
  • R 1 is preferably an aliphatic group, more preferably a C 1-10 alkyl group, and even more preferably a C 1-4 alkyl group.
  • examples of the linking group include a hydrocarbon group.
  • examples of the hydrocarbon group include aliphatic groups [eg, C 1-10 alkyl groups (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, etc.
  • a C 1-5 alkyl group an alicyclic group [eg, a C 3-12 cycloalkyl group (eg, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.), preferably a C 3 -7 cycloalkyl group etc.], aromatic group ⁇ eg C 6-20 aromatic group [eg C 6-20 aryl group (eg phenyl group, o-tolyl group, m-tolyl group, p-tolyl group] , 2,3-xylyl group, 1-naphthyl group, etc.), C 7-20 aralkyl group (eg, benzyl group, etc.)] ⁇ and the like.
  • the hydrocarbon group may further have a substituent (for example, a halogen atom).
  • R 2 is preferably an aliphatic group, more preferably a C 1-10 alkyl group, and further preferably a C 1-5 alkyl group.
  • the organic phosphorus unit may be a group containing phosphorus (phosphorus-containing group).
  • the phosphorus-containing group preferably includes at least a structure represented by a P ( ⁇ O) OR 3 structure (R 3 represents a hydrogen atom or a hydrocarbon group).
  • the hydrocarbon group includes, for example, an aliphatic group [for example, a C 1-10 alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert group, -Butyl group etc., preferably C 1-4 alkyl group etc.], alicyclic group (eg C 3-12 cycloalkyl group etc.), aromatic group (eg C 6-20 aromatic group etc.) Etc.
  • an aliphatic group for example, a C 1-10 alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert group, -Butyl group etc., preferably C 1-4 alkyl group etc.]
  • alicyclic group e
  • R 3 is preferably an aliphatic group, more preferably a C 1-10 alkyl group, and even more preferably a C 1-4 alkyl group.
  • organic phosphorus unit a structure represented by the following formula (2) is preferable.
  • R 3 represents a hydrogen atom or a hydrocarbon group
  • Y represents a hydrogen atom or —OR 4 (wherein R 4 represents a hydrogen atom or a hydrocarbon group).
  • examples of the hydrocarbon group include the hydrocarbon groups described above.
  • the hydrocarbon group includes, for example, an aliphatic group [for example, a C 1-10 alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert group, -Butyl group etc., preferably C 1-4 alkyl group etc.], alicyclic group (eg C 3-12 cycloalkyl group etc.), aromatic group (eg C 6-20 aromatic group etc.) Etc.
  • an aliphatic group for example, a C 1-10 alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert group, -Butyl group etc., preferably C 1-4 alkyl group etc.]
  • alicyclic group e
  • R 4 is preferably an aliphatic group, more preferably a C 1-10 alkyl group, and even more preferably a C 1-4 alkyl group.
  • R 3 is a C 1-4 alkyl group
  • Y is preferably a hydrogen atom or -OR 4
  • R 3 is a C 1-4 alkyl group
  • Y is - More preferably, it is OR 4 and R 4 is a C 1-4 alkyl group.
  • the nitroxide structure having an organic phosphorus unit is particularly preferably a structure represented by the above formula (1), wherein R 1 is a C 1-4 alkyl group and R 2 is a C 1-5 alkyl group.
  • X is a structure represented by the above formula (2)
  • R 3 is a C 1-4 alkyl group
  • Y is a hydrogen atom or —OR 4 .
  • Examples of nitroxide structures having an organophosphorus unit include, for example, structures represented by the following formula (1-1).
  • the polymer block (A) is usually a chain.
  • the nitroxide polymer (A1) may have a plurality of nitroxide structures having an organic phosphorus unit.
  • the nitroxide structure having an organophosphorus unit may be at the ends of the polymer block (A), but is preferably at both ends of the polymer block (A).
  • the nitroxide polymer (A1) preferably has a nitroxide structure having an organophosphorus unit at both ends of the chain polymer block (A).
  • the weight average molecular weight (Mw) of the nitroxide polymer (A1) as measured by GPC is not particularly limited, but is, for example, 4 to 300,000, preferably 50,000 to 250,000.
  • nitroxide polymer (A1) a commercially available product may be used, for example, Flexibloc (registered trademark) D2 (manufactured by Arkema France) or the like.
  • the monomer (B1) contains at least a methacrylic acid ester and an N-substituted maleimide.
  • the methacrylic acid ester is not particularly limited.
  • aliphatic methacrylate eg, alkyl methacrylate ester (eg, C 1-18 alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc.], etc.
  • Alicyclic methacrylates eg, methacrylic acid cycloalkyl esters (eg, C 3-20 cycloalkyl methacrylate such as cyclopropyl methacrylate, cyclobutyl methacrylate), cross-linked cyclic methacrylates (eg, isobornyl methacrylate), etc.] aromatic family methacrylate [for example, methacrylic acid aryl esters (e.g., phenyl methacrylate, methacrylic acid
  • methacrylic acid esters from the viewpoint of improving transparency, it is preferable to include at least a methacrylic acid alkyl ester, more preferably at least a C 1-18 alkyl methacrylate, and at least a methyl methacrylate. More preferably.
  • the content of the methacrylic acid alkyl ester in the methacrylic acid ester is, for example, 50 to 95% by mass, preferably 70 to 90% by mass.
  • the content of the methacrylic acid alkyl ester in the methacrylic acid ester is, for example, 50 to 95 mol%, preferably 70 to 90 mol%.
  • the N-substituted maleimide is not particularly limited.
  • N-alkylmaleimide eg, N—C 1-10 alkylmaleimide such as N-methylmaleimide, N-ethylmaleimide, etc.
  • N-cycloalkylmaleimide eg, , N-C 3-20 cycloalkyl maleimides such as cyclohexyl maleimide
  • N- aryl maleimides e.g., N- phenylmaleimide, etc. N-C 6-10 aryl maleimides, etc.
  • N- aralkyl-maleimide e.g., N- And N—C 7-10 aralkylmaleimide such as benzylmaleimide.
  • N-substituted maleimides N-cycloalkylmaleimide, N-arylmaleimide, and the like are preferable from the viewpoint of excellent optical properties, and more preferable are N-cyclohexylmaleimide, N-phenylmaleimide, and the like. is there.
  • the mass ratio of the methacrylic acid ester to the N-substituted maleimide is not particularly limited, but is, for example, 60/40 to 95/5, preferably 70/30 to 93/7, more preferably 75/25 to 90/10.
  • the monomer (B1) may contain a monomer other than methacrylic acid ester and N-substituted maleimide.
  • Other monomers include, for example, styrene monomers [eg, styrene, vinyl toluene, styrene having a substituent (eg, halogen group, alkoxy group, alkyl group, hydroxy group, etc.) (eg, ⁇ -methylstyrene, Chlorostyrene, etc.), styrene sulfonic acid or its salt, etc.], methacrylic acid, acrylic acid, vinyl compounds [eg, vinyl esters (eg, vinyl acetate), etc.], ⁇ , ⁇ -unsaturated nitriles (eg, acrylonitrile, methacrylo) Nitriles), olefins (eg, C 2-10 alkenes such as ethylene, propylene, 1-butene, isobutylene, 1-octen
  • the other monomers can be used alone or in combination of two or more.
  • the other monomer can be appropriately selected depending on the use of the block copolymer, but from the viewpoint of adjusting optical properties, it is preferable to include a styrene monomer, and more preferably to include styrene.
  • the content of methacrylic acid ester and N-substituted maleimide is, for example, 50 to 95% by mass, preferably 70 to 90% by mass.
  • the content of methacrylic acid ester and N-substituted maleimide is, for example, 50 to 95 mol%, preferably 70 to 90 mol%.
  • the content ratio of the other monomer is, for example, 1 to 20 parts by mass, preferably 100 parts by mass with respect to the total amount of methacrylic acid ester and N-substituted maleimide. Is 1 to 10 parts by mass.
  • the thiol compound (C1) only needs to be usable as a chain transfer agent. Although it does not specifically limit as thiol type compound (C1), For example, aliphatic thiol [For example, alkanethiol (for example, butanethiol, octanethiol, decanethiol, dodecanethiol (dodecyl mercaptan), hexadecanethiol, octadecanethiol, decane) C 1-20 alkanethiol such as cantrithiol), cycloalkyl mercaptan (eg, C 3-20 cycloalkyl mercaptan such as cyclohexyl mercaptan), etc.], aromatic thiol (eg, C 6-20 aryl such as thiophenol) Mercaptan etc.), mercaptocarboxylic acid esters [eg thio
  • C 1-20 alkanoic acid mercapto C 1-20 alkyl such as mercaptoethyl
  • ethylene glycol bis (mercaptoalkyl) ether eg, ethylene glycol bis (mercapto) such as 1,8-dimercapto-3,6-dioxaoctane C 1-20 alkyl
  • thiol compounds those having a hydrocarbon group having 3 or more carbon atoms are preferable.
  • the polymerization method of the nitroxide polymer (A1) and the monomer (B1) is usually living radical polymerization.
  • the block copolymer (1) can be formed by polymerizing the nitroxide polymer (A1) and the monomer (B1) via the nitroxide structure of the nitroxide polymer (A1).
  • the polymerization step (I) of the nitroxide polymer (A1) and the monomer (B1) is performed in the presence of the thiol compound (C1).
  • the block copolymer (1) has a nitroxide structure having an organophosphorus unit at the end, and this nitroxide structure is considered to repeat dissociation and bonding from the block copolymer (1).
  • the radical derived from the thiol compound (C1) is bonded to the terminal of the block copolymer (1), whereby the block copolymer of the present invention. Can be obtained.
  • the polymerization method of the nitroxide polymer (A1) and the monomer (B1) is preferably solution polymerization.
  • the polymerization temperature is not particularly limited, but is, for example, 80 to 130 ° C, and preferably 90 to 120 ° C.
  • the polymerization time in the polymerization step (I) is not particularly limited and can be appropriately selected depending on the polymerization temperature. For example, it is 0.5 to 6 hours, preferably 1 to 3 hours. In addition, it is preferable that superposition
  • the polymerization solvent examples include alcohol solvents (eg, methanol, ethanol, etc.), aromatic hydrocarbon solvents (eg, toluene, ethylbenzene, xylene, etc.), ketone solvents (eg, acetone, methyl isobutyl ketone, methyl ethyl ketone, etc.). ) And ester solvents (for example, butyl acetate and the like).
  • alcohol solvents eg, methanol, ethanol, etc.
  • aromatic hydrocarbon solvents eg, toluene, ethylbenzene, xylene, etc.
  • ketone solvents eg, acetone, methyl isobutyl ketone, methyl ethyl ketone, etc.
  • ester solvents for example, butyl acetate and the like.
  • methanol, toluene, xylene and the like are particularly preferable.
  • These solvents may
  • a catalyst may be used in the polymerization. Although it does not specifically limit as a catalyst, for example, at least 1 sort (s) chosen from an acid, a base and these salts, a metal complex, and a metal oxide can be used. Kinds of acids, bases and salts thereof, metal complexes, and metal oxides are not particularly limited.
  • the catalyst is not reduced in transparency, It is preferable to use it in a range where no adverse effects such as coloring occur.
  • the acid examples include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and phosphorous acid, and organic acids such as p-toluenesulfonic acid, phenylsulfonic acid, carboxylic acid, and phosphoric acid ester.
  • the base is not limited, and examples thereof include metal hydroxides, amines, imines, alkali metal derivatives, alkoxides, and ammonium hydroxide salts.
  • the salt of an acid and a base is not limited, For example, they are metal organic acid salt (for example, metal carboxylate), metal inorganic acid salt (for example, metal carbonate etc.).
  • metal organic acid salt for example, metal carboxylate
  • metal inorganic acid salt for example, metal carbonate etc.
  • the metal of the metal organic acid salt or metal inorganic acid salt does not impair the properties of the finally obtained block copolymer, resin composition or resin molded article, and does not cause environmental pollution at the time of disposal.
  • alkali metals such as lithium, sodium, and potassium
  • alkaline earth metals such as magnesium, calcium, strontium, and barium
  • zinc zirconium and the like.
  • zinc is preferable.
  • the carboxylic acid constituting the metal carboxylate is not limited, and for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, octylic acid, nonanoic acid, decanoic acid, lauric acid, Myristic acid, palmitic acid, stearic acid, behenic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid.
  • zinc acetate, zinc propionate, zinc octylate, or zinc stearate is preferable.
  • a metal complex is not limited,
  • the example of the organic component is acetylacetone.
  • the metal oxide is not limited and is, for example, zinc oxide, calcium oxide, or magnesium oxide.
  • acid and base salts are preferable, metal organic acid salts are more preferable, and metal carboxylates are particularly preferable.
  • usage-amount of a catalyst is not specifically limited.
  • the mass ratio of the nitroxide polymer (A1) and the monomer (B1) is not particularly limited, but is, for example, 3/97 to 40/60, preferably 5 / 95 to 30/70, more preferably 7/93 to 25/75.
  • the amount of the thiol compound (C1) used is not particularly limited, but the total amount of the nitroxide polymer (A1) and the monomer (B1) is 100.
  • the parts are by weight, it is, for example, 1 ppm to 10000 ppm, preferably 10 ppm to 3000 ppm, more preferably 50 ppm to 1000 ppm.
  • the usage-amount of a thiol type compound (C1) is 1 ppm or more, since the heat resistance of resin is excellent, it is preferable. Moreover, if it is 10000 ppm or less, since superposition
  • additional polymerization may be performed after the polymerization step (I) of the nitroxide polymer (A1) and the monomer (B1).
  • additional polymerization is preferably performed by adding a radical polymerization initiator.
  • radical polymerization initiator examples include organic peroxides [for example, tert-amylperoxyisononanoate, t-amylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5- Trimethylhexanate, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl monocarbonate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxyacetate, 1,1-bis (tert-butylperoxy) 3 , 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, tert-butylperoxy 2-ethylhexanate, tert-butylperoxyisobutyrate, tert-hexylperoxy-2- Tilhexanate, di-tert-butyl peroxide, 2,5
  • a polymerization initiator may be used independently or may use 2 or more types together.
  • the amount of the polymerization initiator used is not particularly limited, but the monomer [monomer in additional polymerization, for example, monomer (B1), remaining monomer or unreacted monomer (and additional monomer (if necessary) (The total amount of B1))] is preferably about 0.1 to 10 parts by weight, more preferably about 0.5 to 5 parts by weight per 100 parts by weight.
  • a chain transfer agent may be added.
  • the chain transfer agent include thiol compounds (C1) exemplified above; halides such as carbon tetrachloride, carbon tetrabromide, methylene chloride, bromoform, bromotrichloroethane; ⁇ -methylstyrene dimer, ⁇ -terpinene, ⁇ -Unsaturated hydrocarbon compounds such as terpinene, dipentene and terpinolene. These may be used alone or in combination of two or more. Among them, it is preferable to use a thiol compound (C1) having a hydrocarbon group having 3 or more carbon atoms.
  • the amount of the chain transfer agent used is not particularly limited, but the monomer [monomer in additional polymerization, for example, monomer (B1), remaining monomer or unreacted monomer (and additional monomer (if necessary) (The total amount of B1))] is preferably about 0.001 to 1 part by weight, more preferably about 0.01 to 0.3 part by weight per 100 parts by weight. Moreover, it is also a preferable form to use what removed the foreign material and impurities with the filter etc. before use as a chain transfer agent.
  • the monomer (B1) to be added may be one type or two or more types.
  • the monomer (B1) to be added is preferably another monomer in the monomer (B1) described above, and more preferably includes a styrene monomer, and further preferably includes styrene.
  • the addition ratio of the monomer (B1) to be added is not particularly limited, but it is, for example, 1 to 50 parts by mass, preferably 100 parts by mass with respect to the total amount of methacrylic acid ester and N-substituted maleimide used in the polymerization step (I). 2 to 30 parts by mass.
  • the polymerization liquid after completion of the polymerization reaction may be filtered, dried, added with a solvent (for example, an aromatic hydrocarbon solvent such as toluene), heated, devolatilized, etc., if necessary.
  • a solvent for example, an aromatic hydrocarbon solvent such as toluene
  • heated, devolatilized, etc. if necessary.
  • additives for example, an ultraviolet absorber, an antioxidant, a stabilizer, a reinforcing material, a flame retardant, an antistatic agent, an organic filler, an inorganic filler, An anti-blocking agent, a resin modifier, an organic filler, an inorganic filler, a plasticizer, a lubricant, a retardation reducing agent, etc.
  • Other additives may be added to the polymerization solution after completion of the polymerization reaction.
  • the amount of other additives is not particularly limited.
  • the compounding quantity of other resin is not specifically limited.
  • Examples of the ultraviolet absorber include benzophenone compounds, salicylate compounds, benzoate compounds, triazole compounds, triazine compounds, and the like.
  • Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 4-n-octyloxy-2-hydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-n- Examples include octyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 1,4-bis (4-benzoyl-3-hydroxyphenone) -butane.
  • silicate compound examples include pt-butylphenyl silicate.
  • benzoate-based compound examples include 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate.
  • triazole compounds examples include 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazole-2- Yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2-benzotriazol-2-yl-4,6-di-tert-butylphenol, 2- [5-chloro (2H) -benzo Triazol-2-yl] -4-methyl-6-t-butylphenol, 2- (2H-benzotriazol-2-yl) -4,6-di-t-butylpheno 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetra
  • triazine compounds for example, 2-mono (hydroxyphenyl) -1,3,5-triazine compounds, 2,4-bis (hydroxyphenyl) -1,3,5-triazine compounds, 2,4, 6-tris (hydroxyphenyl) -1,3,5-triazine compound, and specifically, 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5- Triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3 5-triazine, 2,4-diphenyl- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4 Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxypheny
  • UV absorbers having a — (3-alkyloxy-2-hydroxypropyloxy) -5- ⁇ -cumylphenyl] -s-triazine skeleton (alkyloxy; long-chain alkyloxy groups such as octyloxy, nonyloxy, decyloxy, etc.) It is done.
  • an ultraviolet absorber having a 2,4,6-tris (hydroxyphenyl) -1,3,5-triazine skeleton is preferably used, and 2,4,6-tris (2-hydroxy-4-long chain alkyloxy) is used.
  • the ultraviolet absorber having is a particularly preferred triazine-based ultraviolet absorber.
  • antioxidant is not specifically limited,
  • well-known antioxidants such as a phenol type, a phosphorus type, or a sulfur type
  • phenolic antioxidants include n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, n-octadecyl-3- (3,5-di-t-butyl).
  • thioether antioxidant examples include pentaerythrityl tetrakis (3-lauryl thiopropionate), dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl. -3,3'-thiodipropionate and the like.
  • phosphoric acid antioxidants include tris (2,4-di-t-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [ d, f] [1,3,2] dioxaphosphin-6-yl] oxy] -N, N-bis [2-[[2,4,8,10-tetrakis (1,1 dimethylethyl) Dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] -ethyl] ethanamine, genyltridecyl phosphite, triphenyl phosphite, 2,2-methylenebis (4,6 -Di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphi
  • thermoplastic polymer examples include olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, and poly (4-methyl-1-pentene); halogens such as polyvinyl chloride, polyvinylidene chloride, and polyvinyl chloride.
  • Styrene polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.
  • Polyester such as cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, etc .; Polyester such as nylon 6, nylon 66, nylon 610, etc. Polyacetal; Polycarbonate; Polyphenylene oxide; Polyphenylene sulfide; Polyether ether ketone; Polysulfone; Polyethersulfone; Polyoxybenzylene; Polyamideimide; Rubber such as ABS resin and ASA resin blended with polybutadiene rubber or acrylic rubber Polymer and the like.
  • Block copolymer Using the production method described above, a block copolymer having a polymer block (A) containing a structural unit derived from an acrylate ester and a polymer block (B) containing a structural unit derived from an N-substituted maleimide ring structure and a methacrylic ester is used. A polymer can be obtained.
  • a block copolymer having a polymer block (A) containing a structural unit derived from an acrylate ester and a polymer block (B) containing a structural unit derived from an N-substituted maleimide ring structure and a methacrylic acid ester can provide.
  • Such a block copolymer is not particularly limited in its production method, but may be produced in particular by the production method.
  • Such a block copolymer may be a polyblock copolymer (for example, a di-deca block copolymer).
  • the block copolymer preferably has a polymer block (B) at least on both sides of the polymer block (A) (having (B)-(A)-(B)).
  • a block copolymer has a structural unit derived from a thiol type compound (C1).
  • the block copolymer preferably has a thiol-based compound (C1) -derived structural unit at the ends, and more preferably at both ends.
  • the N-substituted maleimide ring structure possessed by the block copolymer is preferably a unit represented by the following formula (3).
  • R 4 and R 5 are each independently a hydrogen atom or a methyl group, and R 6 is a hydrogen atom or a substituent.
  • examples of the substituent include a hydrocarbon group.
  • examples of the hydrocarbon group include an aliphatic group ⁇ eg, an alkyl group [eg, a C 1-6 linear alkyl group (eg, a methyl group, an ethyl group), etc.], a C 1-6 branched alkyl group (eg, an isopropyl group).
  • C 1-6 alkyl group etc. etc.]
  • alicyclic group eg C 3-20 cycloalkyl group such as cyclopentyl group, cyclohexyl group etc.
  • aromatic group ⁇ eg C 6-20 aromatic Group [for example, C 7-20 aralkyl group (eg, benzyl group, etc.), C 6-20 aryl group (eg, phenyl group, etc.)] ⁇ .
  • the hydrocarbon group may further have a substituent such as halogen.
  • the formula (3) is preferably such that R 4 and R 5 are each independently a hydrogen atom, and R 6 is a C 3- 20 cycloalkyl group or C 6-20 aromatic group, more preferably R 4 and R 5 are each independently a hydrogen atom, and R 6 is a cyclohexyl group or a phenyl group.
  • the content ratio of the N-substituted maleimide ring structure is, for example, 5 to 90% by mass from the viewpoint that the block copolymer has excellent heat resistance, and preferably It is 10 to 70% by mass, more preferably 10 to 60% by mass, and further preferably 10 to 50% by mass.
  • the content of the N-substituted maleimide ring structure in the polymer block (B) of the block copolymer is such that the monomer constituting the polymer block (B) is from the viewpoint that the block copolymer has excellent heat resistance. In terms of conversion, for example, it is 7 to 90 mol%, preferably 10 to 75 mol%, more preferably 10 to 60 mol%.
  • the block copolymer is a triblock copolymer
  • the content ratio of the N-substituted maleimide ring structure in each polymer block (B) may be within such a range.
  • the content of other units in the polymer block (B) is, for example, 30% by weight or less (eg, 0.1 to 20% by weight), preferably Is 15% by weight or less (for example, 1 to 10% by weight).
  • the content of other units in the polymer block (B) is, for example, 30 mol% or less (for example, 0.1 to 20 mol%), preferably 15 mol%, in terms of the monomer constituting the polymer block (B). The following (for example, 1 to 10 mol%).
  • the block copolymer when used for optical applications such as an optical film, it preferably has a styrenic unit from the viewpoint of canceling out the positive birefringence of the N-substituted maleimide ring.
  • the content ratio of the styrenic unit in the polymer block (B) can be appropriately selected according to the desired optical properties and the like. For example, it is 0.1 to 15% by weight, preferably 1 to 10% by weight, more preferably 3 to 8%. % By weight.
  • the content ratio of the styrenic unit in the polymer block (B) is, for example, 0.1 to 20 mol%, preferably 1 to 12 mol%, more preferably 3 to 3 mol in terms of the monomer constituting the polymer block (B). 10 mol%.
  • the content rate of the other unit (for example, styrene-type unit etc.) in each polymer block (B) should just be the above ranges.
  • the content of the N-substituted maleimide ring structure is, for example, 1 to 50% by mass, preferably 5 to 30% by mass, from the viewpoint that the block copolymer has excellent heat resistance. More preferably, it is 10 to 20% by mass.
  • the content of the N-substituted maleimide ring structure is, for example, 2 to 80 in terms of the monomer constituting the block copolymer from the viewpoint that the block copolymer has excellent heat resistance.
  • the mol% preferably 7 to 50 mol%, more preferably 15 to 30 mol%.
  • the content ratio of the N-substituted maleimide ring structure in each polymer block (B) may be within such a range.
  • the weight average molecular weight (Mw) determined by the GPC measurement method of the block copolymer is not particularly limited, but is, for example, 0.5 to 500,000, preferably 50,000 to 500,000, more preferably 100,000 to 500,000.
  • the weight average molecular weight (Mw) in the GPC measurement method of the block copolymer may be 450,000 or less (for example, 1 to 450,000), preferably 18 to 450,000, more preferably 200 to 400,000. .
  • Mw weight average molecular weight
  • it is easy to obtain sufficient film strength.
  • it may be easy to obtain an appropriate melt viscosity, or it may be advantageous in terms of workability.
  • gelation hardly occurs during melt molding.
  • the molecular weight distribution (Mw / Mn) of the block copolymer is not particularly limited, but is, for example, 1.1 to 2.7, preferably 1.2 to 2.3, and more preferably 1.3 to 1.9. .
  • the molecular weight distribution (Mw / Mn) of the block copolymer is 1.65 or more (for example, 1.65 to 2.5), preferably 1.7 to 2.4 (for example, 1.8 to 2. 3). By setting the molecular weight distribution within this range, it is easy to obtain a film having excellent smoothness.
  • the ratio of the weight average molecular weight (Mw) of the polymer block (A) to the polymer block (B) is not particularly limited, and is, for example, 1: 0.5 to 1: 3, preferably 1: 0.8 to 1: 2.5 (for example, 1: 0.9 to 1: 2), more preferably 1: 1 to 1: 2.
  • the ratio of the number average molecular weight (Mn) of the polymer block (A) to the polymer block (B) is not particularly limited, but is preferably 1: 0.2 to 1: 2, for example. Is 1: 0.4 to 1: 1.
  • the viscosity at the time of melt-processing the block copolymer can be easily set to an appropriate range, and a molded product excellent in appearance such as smoothness can be easily obtained.
  • the block copolymer is a triblock copolymer
  • the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) between the polymer block (A) and each polymer block (B) is as described above. As long as it is within the range.
  • the weight average molecular weight (Mw) and the like may be a value measured by GPC in terms of polystyrene, for example.
  • the thermal decomposition temperature of the block copolymer depends on the type of monomer used and the content of the N-substituted maleimide ring structure, but is, for example, 270 ° C. or higher (eg, 270 ° C. to 350 ° C.), preferably 280 ° C. to 350 ° C.
  • the glass transition temperature (Tg) of the block copolymer depends on the type of monomer used, the content of the N-substituted maleimide ring structure, etc., for example, 110 ° C. or higher (eg, 110 ° C. to 200 ° C.), preferably It is 115 ° C to 160 ° C, more preferably 120 ° C to 150 ° C.
  • the present invention also includes a resin composition containing the block copolymer.
  • a resin composition containing the block copolymer.
  • Such a resin composition should just contain the said block copolymer as resin (or resin component), and may contain other resin.
  • resins can be appropriately selected according to the use and are not particularly limited.
  • Other resins include thermoplastic polymers such as olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-1-pentene); polyvinyl chloride, polyvinylidene chloride, polychlorinated Vinyl halide polymers such as vinyl; styrene polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer; polyethylene terephthalate, polybutylene terephthalate, Polyesters such as polyethylene naphthalate; cellulose acylates such as cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate; nylon 6, nylon 66, nylon 610 Polyacetal; Polycarbonate; Polyphenylene oxide
  • the rubbery polymer preferably has a graft portion having a composition compatible with the acrylic resin on the surface.
  • the average particle diameter of the rubbery polymer is, for example, 20 to 20 from the viewpoint of improving transparency when formed into a film.
  • the thickness is preferably 300 nm, more preferably 50 to 200 nm, still more preferably 70 to 150 nm.
  • thermoplastic polymers include acrylic resins.
  • acrylic resin a methacrylic resin containing a resin corresponding to the block (A) and / or the block (B) [for example, methacrylic acid ester (for example, the above exemplified methacrylic acid ester such as methyl methacrylate) as a polymerization component.
  • methacrylic acid ester for example, the above exemplified methacrylic acid ester such as methyl methacrylate
  • Resins for example, resins having a methacrylate as a polymerization component such as polymethyl methacrylate, resins having a methacrylate as a polymerization component and an aromatic vinyl compound as a polymerization component such as methyl methacrylate-styrene copolymer
  • methacryl A resin in which a ring structure is introduced into a resin a methacrylic resin having a ring structure, for example, a methacrylate such as methyl methacrylate-styrene-N-substituted maleimide copolymer, an aromatic vinyl compound, and a cyclic imide (maleimide Compounds etc.) resins having structural units derived from) etc.
  • Block copolymers not belonging to the category of the block copolymer for example, a block copolymer in which a ring structure such as a block copolymer having no N-substituted maleimide structure is not introduced into the block (B)] Is also included.
  • the other resin is a resin having a skeleton common to the block copolymer, for example, a resin corresponding to the block (B) (a structure derived from at least one monomer selected from a methacrylic acid ester and an N-substituted maleimide) Resin having a unit, for example, a methacrylic resin having a methacrylic acid ester as a polymerization component; a monomer such as a methacrylic acid ester-N-substituted maleimide copolymer, a methacrylic acid ester-styrene monomer-N-substituted maleimide copolymer ( Resin having a structural unit derived from B1), resin corresponding to block (A), block copolymer having block (A) and block (B) and having no ring structure [for example, polymerizing methyl methacrylate Polymerizes block (hard block) and acrylic ester (butyl acrylate, etc.) Min to block
  • the block copolymer of the present invention can also be used as a modifier for other resins (particularly, resins having a skeleton common to acrylic resins and block copolymers).
  • a resin composition including the block copolymer and a resin having a skeleton common to the block copolymer [for example, the block copolymer and a monomer A mixture (polymer blend) with a polymer containing (B1) as a polymerization component can be obtained efficiently.
  • the content of the other resin in the resin composition can be appropriately selected depending on the application and the like, for example, 1 to 99% by mass (for example, 5 to 90% by mass) ), Preferably 15 to 80% by mass (for example, 20 to 75% by mass), more preferably about 30 to 70% by mass.
  • the block copolymer of the present invention contains another resin [for example, an acrylic resin (for example, an acrylic resin having a skeleton common to the block copolymer)], the block copolymer of the present invention
  • the ratio with the other resin can be appropriately selected according to the desired physical properties.
  • the former / the latter (mass ratio) 99/1 to 1/99 (for example, 95/5 to 5/95)
  • it may be about 90/10 to 10/90 (for example, 85/15 to 15/85), more preferably about 70/30 to 30/70.
  • the physical properties (Mw, molecular weight distribution, thermal decomposition temperature, Tg, etc.) of the resin composition containing such a block copolymer are not necessarily the same as those of the block copolymer, but from the same range. You may choose.
  • the physical properties of the entire resin component satisfy the physical properties of the block copolymer (for example, Mw is 5 to 500,000, 150,000 to 450,000, etc.). It is not necessary and may be satisfied.
  • the weight average molecular weight (Mw) by the GPC measurement method of the resin composition of the present invention is not particularly limited, but is, for example, 50,000 or more (for example, 50,000 to 500,000), preferably 80,000 or more (for example, 80 to 400,000). ), More preferably about 100,000 or more (for example, about 100,000 to 300,000). With such a molecular weight, it is easy to obtain an appropriate melt viscosity, which is advantageous in terms of molding processing, and is advantageous in terms of physical properties (such as strength) of the molded product.
  • the glass transition temperature (Tg) of the resin composition of the present invention may be, for example, 110 ° C. or higher (eg, 110 ° C. to 200 ° C.), preferably 115 ° C. to 160 ° C., more preferably 120 ° C. to 150 ° C. Good.
  • Tg glass transition temperature
  • the thermal decomposition temperature of the resin composition of the present invention is, for example, 270 ° C. to 350 ° C., preferably 280 ° C. to 350 ° C., although it depends on the type of monomer used and the content of the N-substituted maleimide ring structure. May be.
  • the degree of coloration (YI) of the resin composition (or block copolymer) of the present invention varies depending on the type of resin constituting the resin composition, the presence or absence of an additive (particularly an ultraviolet absorber), and the like.
  • the resin (resin component) constituting the product is the block copolymer, or the resin having a structural unit derived from at least one monomer selected from the block copolymer and a methacrylic acid ester and an N-substituted maleimide. If it is constituted and does not contain an ultraviolet absorber, YI is preferably 4.0 or less, more preferably 3.5 or less.
  • the resin component is composed of the block copolymer, or the block copolymer and a resin having a structural unit derived from at least one monomer selected from methacrylic acid ester and N-substituted maleimide, and absorbs ultraviolet rays.
  • the coloring degree YI is preferably 20.0 or less, and more preferably 17.5 or less.
  • the degree of coloration (YI) of the resin composition can be measured with a color difference meter according to JIS-K7103 by dissolving a sample in chloroform to give a 15% solution.
  • the resin composition (or block copolymer) is a conventional additive (additives exemplified in the section of the method for producing the block copolymer, for example, an ultraviolet absorber, an antioxidant, etc.) depending on applications. May be included. You may use an additive individually or in combination of 2 or more types.
  • the ratio of the additive is not particularly limited, and can be appropriately selected depending on the type of additive, the type of resin component, the use, and the like.
  • the amount of the ultraviolet absorber used is not particularly limited, but is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the resin (resin component) constituting the resin composition. It may be a degree. If it is in such a range, it is advantageous in respect of ultraviolet absorption and difficulty in bleeding out.
  • a resin composition having excellent strength may be efficiently obtained by constituting a resin composition with a block copolymer (or a mixture of a block copolymer and another resin) and a metal alkoxide. is there.
  • metal alkoxide for example, periodic table Group 13 metal alkoxide [e.g., aluminum alkoxide (e.g., aluminum trimethoxide, aluminum triisopropoxide, aluminum C 1-10 alkoxide such as ethyl acetoacetate aluminum diisopropylate)
  • Typical metal alkoxides of Group 4 metal alkoxides eg, titanium alkoxides (titanium C 1-10 alkoxides such as titanium tetramethoxide, titanium tetraisopropoxide), zirconium alkoxides (zirconium tetramethoxide, zirconium iso transition metal alkoxides such as zirconium C 1-10 alkoxide), etc.
  • silicon alkoxide e.g., tetraethoxysilane, vinyl tri Tokishishiran like mono- to tetra-C 1-10 alkoxysilane
  • the ratio of the metal alkoxide may be, for example, about 0.0001 to 1 part by mass with respect to 100 parts by mass of the resin component (or block copolymer).
  • the resin composition which has the outstanding stability can be obtained efficiently by comprising a resin composition with a block copolymer (or a mixture of a block copolymer and another resin) and an antioxidant. There is a case.
  • Such an antioxidant may be composed of a combination of a phenolic antioxidant (particularly a hindered phenolic antioxidant), a phosphorus antioxidant, and a sulfurous antioxidant.
  • these antioxidants include the antioxidants exemplified above.
  • the ratio (mass ratio) of the total amount of the phenolic antioxidant and sulfur antioxidant and the phosphorus antioxidant is, for example, 2/3 to 8/1, preferably 1/1 to It may be about 4/1, more preferably about 1/1 to 3/1.
  • the proportion of the antioxidant is, for example, about 0.0001 to 10 parts by mass, preferably about 0.001 to 1 part by mass with respect to 100 parts by mass of the resin component (or block copolymer). It may be.
  • the block copolymer of the present invention (for example, the block copolymer obtained by the production method of the present invention) or the molded product of the resin composition (for example, a film or a sheet) is not particularly limited, but optical It is suitable for use, 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.
  • the optical film is not particularly limited as long as it has excellent optical characteristics, but preferably a retardation film, a zero retardation film (in-plane, thickness direction retardation is extremely small), a viewing angle compensation film, a light diffusion film.
  • a retardation film a zero retardation film (in-plane, thickness direction retardation is extremely small)
  • a viewing angle compensation film a light diffusion film.
  • examples thereof include a film, a reflection film, an antireflection film, an antiglare film, a brightness enhancement film, and a conductive film for a touch panel.
  • the optical sheet include a diffusion plate, a light guide, a retardation plate, a zero retardation plate, and a prism sheet.
  • molding method is not specifically limited, You may follow a conventionally well-known method.
  • a film is formed by forming a block copolymer or a resin composition by a known film formation method [for example, solution casting method (solution casting method), melt extrusion method, calendar method, compression molding method, etc.] Can be obtained.
  • a solution casting method solution casting method
  • melt extrusion method calendar method
  • compression molding method etc.
  • a solution casting method melt extrusion method, or the like is preferable.
  • a solvent for example, thermoplastic polymers
  • other additives for example, ultraviolet absorbers, antioxidants, stabilizers, reinforcing materials, flame retardants
  • Antistatic agents organic fillers, inorganic fillers, anti-blocking agents, resin modifiers, organic fillers, inorganic fillers, plasticizers, lubricants, retardation reducing agents, etc.
  • block copolymers can be mixed with block copolymers. Good.
  • the blending amount of the ultraviolet absorber in the film is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass in the film. If the blending amount is too small, the contribution to improving the weather resistance is low, and if it is too large, the mechanical strength may be lowered or yellowing may be caused.
  • the apparatus for performing the solution casting method is, for example, a drum type casting machine, a band type casting machine, or a spin coater.
  • the solvent used in the solution casting method is not limited as long as the block copolymer is dissolved.
  • the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as cyclohexane and decalin; esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • alcohols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve
  • ethers such as tetrahydrofuran and dioxane
  • halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride
  • dimethylformamide dimethyl sulfoxide is there.
  • the melt extrusion method is, for example, a T-die method or an inflation method.
  • the molding temperature during melt extrusion is preferably 150 to 350 ° C, more preferably 200 to 300 ° C.
  • a belt-like film can be formed by attaching a T-die to the tip of a known extruder.
  • the formed belt-like film may be wound up on a roll to form a film roll.
  • melt extrusion method from the formation of an acrylic resin by mixing materials to the formation of a film using the resin can be performed continuously.
  • a band-shaped optical film may be obtained by forming an easy-adhesion layer on the band-shaped film.
  • the film may be a biaxially stretched film from the viewpoint of increasing mechanical strength.
  • the biaxially stretched film may be a simultaneous biaxially stretched film or a sequential biaxially stretched film.
  • the direction of the slow axis of the stretched film may be the film flow direction, the width direction, or an arbitrary direction.
  • the thickness of the film is not particularly limited and can be appropriately adjusted depending on the use and the like. For example, it is 1 to 400 ⁇ m, preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m, and still more preferably 20 to 60 ⁇ m. For example, when used for applications such as protective films, antireflection films, polarizing films, etc. used in image display devices such as liquid crystal display devices and organic EL display devices, it is preferably 1 to 250 ⁇ m, more preferably 10 to 100 ⁇ m, and further The thickness is preferably 20 to 80 ⁇ m.
  • the haze of the film is preferably 1% or less (for example, 0 to 1%), more preferably 0.5% or less (for example, 0 to 0.5%). Haze is measured based on JIS K7136.
  • the b value of the film is preferably 2% or less (for example, 0.1 to 2%), more preferably 1.5% or less (for example, 0.1 to 1.5%), and even more preferably 1% or less ( For example, 0.1 to 1%), most preferably 0.5% or less (for example, 0.1 to 0.5%).
  • the Tg of the film is, for example, 110 ° C. or higher (eg, 110 ° C. to 200 ° C.), preferably 115 ° C. to 160 ° C.
  • the film of the present invention can be used as a polarizer protective film used for a polarizing plate provided in an image display device such as a liquid crystal display device (LCD), and can usually be used as a polarizer protective film as it is.
  • LCD liquid crystal display device
  • the present invention also includes a polarizing plate provided with the film of the present invention. That is, the film of the present invention can be used as a polarizer protective film for a polarizing plate.
  • the manufacturing method of a polarizing plate is not specifically limited, You may follow a conventionally well-known method.
  • a polarizing plate can be obtained by bonding the film of the present invention to at least one surface of a polarizer using a conventional method.
  • the side of the film of the present invention bonded to the polarizer is subjected to alkali saponification treatment, and after applying a completely saponified polyvinyl alcohol aqueous solution to at least one surface of the polarizer, the film of the present invention and the polarizer are bonded together. Therefore, it can be suitably implemented.
  • the polarizer is an element that passes only polarized waves in a certain direction.
  • the polarizer used in the present invention is not particularly limited, and conventionally known polarizers can be used, and examples thereof include a polyvinyl alcohol film.
  • a polyvinyl alcohol-type film what dye
  • the polyvinyl alcohol film is formed, for example, by forming a polyvinyl alcohol aqueous solution and uniaxially stretching it to dye or dyeing it and then uniaxially stretching it, and then preferably performing a durability treatment using a boron compound. Etc. can be used suitably.
  • the film thickness of the polarizer is preferably 1 to 30 ⁇ m, and more preferably 1 to 20 ⁇ m.
  • the present invention also includes an image display device provided with the polarizing plate of the present invention described above.
  • the manufacturing method of the image display device is not particularly limited, and may be a conventionally known method.
  • a liquid crystal display device (LCD) or the like is preferable.
  • the liquid crystal display device usually comprises a liquid crystal cell and polarizing plates disposed on both sides thereof, and it is preferable to dispose the film of the present invention in contact with the liquid crystal cell. Moreover, it is preferable to further laminate
  • the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (D) of the block polymer, polymer and composition were determined by gel permeation chromatography (GPC) in terms of polystyrene.
  • GPC gel permeation chromatography
  • the glass transition temperature (Tg) was determined according to JIS K7121. Specifically, it is obtained by using a differential scanning calorimeter (manufactured by Rigaku, DSC-8230) to raise a temperature of about 10 mg from room temperature to 200 ° C. (temperature increase rate 20 ° C./min) in a nitrogen gas atmosphere. The DSC curve was evaluated by the starting point method. ⁇ -alumina was used as a reference.
  • the thermal decomposition temperature was analyzed by the following method (dynamic TG method).
  • Measuring apparatus differential type differential thermal balance (ThermoPlus2TG-8120 dynamic TG, manufactured by Rigaku Corporation) Measurement conditions: Sample amount 10 mg Temperature increase rate: 10 ° C / min Atmosphere: Nitrogen flow 200 mL / min Method: Step-like isothermal control method (controlled to a mass reduction rate value of 0.005% / s or less in the range from 150 ° C to 500 ° C)
  • N-phenylmaleimide (PMI) contained in the block copolymer is 7.45-7.50 ppm corresponding to the ortho-position and para-position protons of the benzene ring of PMI, as determined by 1 H-NMR measurement.
  • the peak intensity was obtained as an index.
  • a nuclear magnetic resonance spectrometer manufactured by BRUKER, AV300M
  • deuterated chloroform manufactured by Wako Pure Chemical Industries
  • MIT MIT folding resistance
  • the number of folding times of the film was measured according to JIS P8115. Specifically, two types of test films having a length of 90 mm and a width of 15 mm were used after being allowed to stand in a state of 23 ° C. and 50% RH for 1 hour or longer, and then used in an MIT folding fatigue tester (Toyo Seiki, DA The molds were tested under the conditions of a folding angle of 135 °, a bending speed of 175 cpm, and a load of 200 g, and the average values of the number of times until the films of the five samples broke were obtained.
  • ⁇ Thickness of film> The thickness of the film was measured using a Digimatic micrometer (manufactured by Mitutoyo Corporation). Samples for measuring and evaluating the physical properties of the film, including the physical properties indicating the evaluation methods, were obtained from the center in the width direction of the film.
  • ⁇ Haze of film> The haze of the film was measured by immersing 1,2,3,4-tetrahydronaphthalene (tetralin) in a quartz cell using NDH-1001DP manufactured by Nippon Denshoku Industries Co., Ltd. Calculated as internal haze value.
  • Example 1 Synthesis of block copolymer (A-1) by nitroxide polymerization
  • a reactor equipped with a stirrer, a temperature sensor, a condenser tube, and a nitrogen inlet tube has a nitroxide structure having phosphonate ester units at both ends.
  • Polybutyl butyl 60% toluene solution (Flexibloc D2®, Arkema France) 41 parts, 15 parts phenylmaleimide (PMI), 60 parts methyl methacrylate (MMA), 0.075 parts n -Dodecyl mercaptan (DM) and 50 parts of toluene as a polymerization solvent were charged, and the temperature was raised to 105 ° C while introducing nitrogen.
  • a block polymer copolymer (A-1) having a polymer block (B) was obtained.
  • A-1 had a weight average molecular weight of 341,000, a number average molecular weight of 169,000, and a glass transition temperature of 132 ° C.
  • the evaluation of foamability of A-1 was ⁇ .
  • Example 2 Synthesis of block copolymer (A-2) by nitroxide polymerization
  • a reactor equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introduction tube has a nitroxide structure having phosphonate ester units at both ends.
  • Polybutyl butyl 60% toluene solution (Flexibloc D2®, Arkema France) 41 parts, 15 parts phenylmaleimide (PMI), 56 parts methyl methacrylate (MMA), 0.08 parts n -Dodecyl mercaptan (DM) and 50 parts of toluene as a polymerization solvent were charged, and the mixture was heated to 105 ° C while refluxing nitrogen, and refluxed.
  • Example 3 Synthesis of Block Copolymer by Nitroxide Polymerization and Synthesis of Resin Composition (B-1) Containing Copolymer by Additional Polymerization of Unreacted Monomer 16 parts Flexibloc D2®, 18 parts PMI Solution polymerization was allowed to proceed for 1 hour under reflux in the same manner as in Example 1 except that 72 parts of MMA, 0.05 part of DM, and 101 parts of toluene as the polymerization solvent were used. At this time, the reaction rate calculated from the amount of monomers in the polymerization solution was 23% for MMA and 29% for PMI. A part of the polymerization solution was taken out and the block copolymer was isolated in the same manner as in Example 1.
  • the PMI content in the block copolymer determined by 1 H-NMR was 19% by mass.
  • the weight average molecular weight (Mw) was 392,000
  • the number average molecular weight (Mn) was 17,000
  • the molecular weight distribution (Mw / Mn) was 2.3. there were.
  • t-amylperoxyisononanoate manufactured by Arkema Yoshitomi Corp., Luperox (registered trademark) 570
  • t-amylperoxyisonononanoate is added simultaneously for additional polymerization of unreacted monomers (Arkema Yoshitomi, Lupelox (registered trademark) 570)
  • a solution consisting of 0.115 parts and 3.5 parts of toluene was added dropwise over 2 hours. After completion of dropping, a polymerization reaction is performed for 5 hours while maintaining a temperature of 105 ° C.
  • the polymer block (A) made of polybutyl acrylate has polymer blocks (B) made of PMI and MMA at both ends.
  • a polymer solution containing a block polymer copolymer and a copolymer composed of PMI and MMA was obtained.
  • the reaction rates calculated from the residual monomer amount after completion of the polymerization reaction were MMA 98% and PMI 98%.
  • the obtained polymer solution was diluted with MEK so that the polymer solid content concentration was 30% by mass, then barrel temperature was 270 ° C., rotation speed was 200 rpm, degree of vacuum was 13.3 to 400 hPa (10 to 300 mmHg), and the number of vents was 2.
  • a resin composition (B-1) comprising a block polymer copolymer having (B) and a copolymer comprising PMI and MMA was obtained.
  • B-1 had a weight average molecular weight of 181,000, a number average molecular weight of 57,000, a glass transition temperature of 134 ° C., and a thermal decomposition temperature of 320 ° C. Further, the evaluation of foamability of B-1 was ⁇ .
  • Comparative Example 1 Synthesis of Block Copolymer (A-3) by Nitroxide Polymerization
  • a reaction apparatus equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction pipe, 58 parts of Flexibloc D2 (registered trademark) and 65 parts of methacrylic acid were added.
  • Methyl acid (MMA), 0.05 part of DM, and 40 parts of toluene as a polymerization solvent were charged, and the temperature was raised to 105 ° C. while passing nitrogen through this. Thereafter, solution polymerization was allowed to proceed for 3 hours under reflux at about 105 to 110 ° C.
  • the reaction rate of MMA calculated from the amount of monomer in the polymerization solution at this time was 20%.
  • A-3 has a polymerization average molecular weight of 181,000, a number average molecular weight of 113,000, a glass transition temperature of 107 ° C., and a thermal decomposition temperature of 267 ° C., confirming a gradual weight loss and isothermal at 290 ° C. Degradation behavior was shown. Further, the evaluation of foamability of A-3 was evaluated as x.
  • Comparative Example 2 Synthesis of PMI, MMA, St Copolymer (C-1) 17 parts of phenylmaleimide (PMI), 83 parts of a reactor equipped with a stirrer, temperature sensor, cooling pipe and nitrogen introduction pipe Methyl methacrylate (MMA), 0.1 part of n-dodecyl mercaptan (DM), and 110 parts of toluene as a polymerization solvent were charged, and the temperature was raised to 105 ° C. while passing nitrogen.
  • PMI phenylmaleimide
  • MMA Methyl methacrylate
  • DM n-dodecyl mercaptan
  • toluene as a polymerization solvent
  • C-1 a copolymer composed of PMI, MMA and St.
  • the reaction rates calculated from the residual monomer amount after completion of the polymerization reaction were MMA 97%, PMI 99%, and St 99%.
  • the solvent was removed from the solution and monomers at 240 ° C. under vacuum to obtain a copolymer (C-1) composed of PMI, MMA, and St.
  • C-1 had a weight average molecular weight of 21 million, a number average molecular weight of 72,000, and a glass transition temperature of 135 ° C.
  • the evaluation of foaming property of C-1 was ⁇ .
  • the reaction rates calculated from the amount of residual monomer after completion of the polymerization reaction were MMA 96% and PMI 95%. Thereafter, the solvent was removed from the solution and monomers at 240 ° C. under vacuum to obtain a copolymer (C-2) composed of PMI and MMA.
  • C-2 had a weight average molecular weight of 180,000, a number average molecular weight of 42,000, and a glass transition temperature of 155 ° C. In addition, the evaluation of foamability of C-2 was ⁇ .
  • Example 4 Synthesis of block copolymer (A-4) by nitroxide polymerization
  • a reactor equipped with a stirrer, a temperature sensor, a condenser tube, and a nitrogen inlet tube has a nitroxide structure having phosphonate ester units at both ends.
  • the reaction rates calculated from the amount of residual monomer in the polymerization solution at this time were MMA 38%, PMI 48%, styrene 65%, and acrylonitrile 70%.
  • the PMI content in the block copolymer determined by 1 H-NMR was 22% by mass.
  • 100 parts of methyl ethyl ketone (MEK) was added for dilution, and then slowly added to a large amount of hexane with stirring. At this time, the precipitated white solid was taken out, dried at 2.6 kPa and 80 ° C.
  • a block polymer copolymer (A-4) having a polymer block (B) composed of AN was obtained.
  • (A-4) had a weight average molecular weight of 251,000, a number average molecular weight of 132,000, and a glass transition temperature of 132 ° C.
  • the evaluation of foamability of (A-4) was ⁇ .
  • Example 1 to 4 and Comparative Examples 1 to 3 are shown in Table 1. From a comparison between Examples 1 and 2 and Comparative Example 1, it was confirmed that the block copolymer had an N-substituted maleimide ring structure, and thus heat resistance was excellent.
  • Example 5 The resin composition (B-1) was press-molded at 250 ° C. to obtain a 120 ⁇ m film. Next, the film was stretched 2 ⁇ 2 times at 160 ° C. (Tg + 23 ° C.) to obtain a biaxially stretched film. Table 2 shows the Tg, thickness, haze, and folding resistance of the stretched film thus obtained.
  • Examples 6-7, Comparative Example 4 The copolymers obtained in Examples 1 and 2 and Comparative Examples 1 to 3 were mixed at 270 ° C. for 5 minutes using a lab plast mill at the blending ratio shown in Table 2, and the resin compositions (B-2 to 4) were mixed. Obtained. The obtained resin composition was processed in the same manner as in Example 5 to obtain a biaxially stretched film. Table 2 shows the Tg, thickness, haze, and folding resistance of the stretched film thus obtained.
  • Comparative Examples 5-6 Using the copolymers (C-1) to (C-2) synthesized in Comparative Examples 2 to 3, press films and biaxially stretched films were obtained in the same manner as in Example 5. Table 2 shows the Tg, thickness, haze, and folding resistance of the obtained stretched film. In Comparative Example 6, the film after press molding was brittle and broke during biaxial stretching.
  • the film formed by the block copolymer obtained by the production method of the present invention or the resin composition containing the block copolymer is excellent in heat resistance, transparency, flexibility and strength. It was confirmed to be excellent.
  • Example 8 Synthesis of Block Copolymer (A-5) by Nitroxide Polymerization 16 parts Flexibloc D2®, 18 parts PMI, 72 parts MMA, 0.1 parts DM, and 101 as polymerization solvent Except for the part of toluene, the solution polymerization was allowed to proceed for 1 hour under reflux in the same manner as in Example 3. The reaction rates calculated from the amount of monomers in the polymerization solution at this time were MMA 23% and PMI 29%. A part of the polymerization solution was taken out and the block copolymer (A-5) was isolated in the same manner as in Example 1. The PMI content in the block copolymer determined by 1 H-NMR was 19% by mass.
  • a block polymer copolymer (A-5) having a polymer block (B) was obtained.
  • (A-5) had a weight average molecular weight of 262,000, a number average molecular weight of 134,000, a glass transition temperature of 135 ° C., and a thermal decomposition temperature of 319 ° C.
  • the sample residue which measured the thermal decomposition temperature was melt
  • Comparative Example 7 Synthesis of Block Copolymer (A-6) by Nitroxide Polymerization Solution polymerization for 1 hour was allowed to proceed under reflux in the same manner as in Example 8 except that DM was not used during the polymerization. At this time, the reaction rate calculated from the amount of monomers in the polymerization solution was MMA 26% and PMI 31%. A part of the polymerization solution was taken out and the block copolymer (A-6) was isolated in the same manner as in Example 1. The PMI content in the block copolymer determined by 1 H-NMR was 19% by mass.
  • (A-6) had a weight average molecular weight of 492,000, a number average molecular weight of 231,000, a glass transition temperature of 135 ° C., and a thermal decomposition temperature of 298 ° C. Moreover, when the sample residue which measured the thermal decomposition temperature was melt
  • Example 9 Synthesis of Block Copolymer by Nitroxide Polymerization and Synthesis of Resin Composition (B-5) Containing Copolymer by Additional Polymerization of Unreacted Monomer 16 parts Flexibloc D2®, 18 parts PMI Solution polymerization was allowed to proceed for 1 hour under reflux in the same manner as in Example 1 except that 72 parts of MMA, 0.1 part of DM, and 101 parts of toluene as the polymerization solvent were used. The reaction rate calculated from the amount of monomers in the polymerization solution at this time was 22% for MMA and 26% for PMI. A part of the polymerization solution was taken out and the block copolymer was isolated in the same manner as in Example 1.
  • the PMI content in the block copolymer determined by 1 H-NMR was 19% by mass.
  • the weight average molecular weight (Mw) was 271,000
  • the number average molecular weight (Mn) was 120,000
  • the molecular weight distribution (Mw / Mn) was 2.2. there were.
  • 0.058 parts of t-amyl peroxyisononanoate manufactured by Arkema Yoshitomi Corp., Luperox (registered trademark) 570
  • t-amyl peroxyisononanoate manufactured by Arkema Yoshitomi Corp., Luperox (registered trademark) 570
  • a solution comprising 0.115 parts of Eate (manufactured by Arkema Yoshitomi, Luperox (registered trademark) 570) and 3.5 parts of toluene was added dropwise over 2 hours. After completion of dropping, a polymerization reaction is performed for 5 hours while maintaining a temperature of 105 ° C. to 110 ° C., and the polymer block (A) made of polybutyl acrylate has polymer blocks (B) made of PMI and MMA at both ends. A polymer solution containing a block polymer copolymer and a copolymer composed of PMI and MMA was obtained. The reaction rates calculated from the residual monomer amount after completion of the polymerization reaction were MMA 98% and PMI 97%.
  • the obtained polymer solution was diluted with MEK so that the polymer solid content concentration was 30% by mass, then barrel temperature was 270 ° C., rotation speed was 200 rpm, degree of vacuum was 13.3 to 400 hPa (10 to 300 mmHg), and the number of vents was 2.
  • a resin composition (B-5) containing a block polymer copolymer having (B) and a copolymer composed of PMI and MMA was obtained.
  • B-5 had a weight average molecular weight of 152,000, a number average molecular weight of 50,000, a glass transition temperature of 134 ° C., and a thermal decomposition temperature of 326 ° C.
  • the reaction rates calculated from the residual monomer amount after completion of the polymerization reaction were MMA 97% and PMI 99%. Thereafter, the solvent was removed from the solution and monomers at 240 ° C. under vacuum to obtain a copolymer (C-3) composed of PMI and MMA.
  • C-3 had a weight average molecular weight of 21 million, a number average molecular weight of 68,000, and a glass transition temperature of 134 ° C.
  • Example 10 Synthesis of Block Copolymer by Nitroxide Polymerization and Synthesis of Resin Composition (B-6) Containing Copolymer by Additional Polymerization of Unreacted Monomer 16 parts of Flexibloc D2®, 22.5 parts Cyclohexyl maleimide (CMI), 65 parts of MMA, 0.1 part of DM, and 95 parts of toluene as a polymerization solvent were allowed to proceed for 1 hour under reflux in the same manner as in Example 1. The reaction rate calculated from the amount of monomers in the polymerization solution at this time was 30% for MMA and 14% for CMI. A part of the polymerization solution was taken out and the block copolymer was isolated in the same manner as in Example 1.
  • CMI Cyclohexyl maleimide
  • the CMI content in the block copolymer determined by 1 H-NMR was 21% by mass.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mw / Mn molecular weight distribution
  • t-amylperoxyisononanoate manufactured by Arkema Yoshitomi Corp., Luperox (registered trademark) 570
  • t-amylperoxyisonononanoate is added simultaneously for additional polymerization of unreacted monomers (Arkema Yoshitomi, Lupelox (registered trademark) 570)
  • a solution consisting of 0.115 parts and 3.5 parts of toluene was added dropwise over 2 hours. After completion of dropping, a polymerization reaction is carried out for 5 hours while maintaining a temperature of 105 ° C.
  • polymer blocks (B) made of CMI and MMA are present at both ends of the polymer block (A) made of polybutyl acrylate.
  • a polymer solution containing a block polymer copolymer and a copolymer composed of CMI and MMA was obtained.
  • the reaction rates calculated from the residual monomer amount after completion of the polymerization reaction were MMA 98% and CMI 98%.
  • the resulting polymer solution was diluted by adding 100 parts of MEK, and then slowly added to a large amount of hexane with stirring. At this time, the precipitated white solid is taken out, dried at 2.6 kPa and 200 ° C.
  • a resin composition (B-6) containing a block polymer copolymer having a polymer block (B) and a copolymer comprising CMI and MMA was obtained.
  • B-6 had a weight average molecular weight of 1270, a number average molecular weight of 41,000, a glass transition temperature of 133 ° C., and a thermal decomposition temperature of 322 ° C.
  • Table 3 shows the results of Examples 8 to 10 and Comparative Example 7.
  • Example 11 Resin composition containing copolymer by synthesis of block polymer by nitroxide polymerization and additional polymerization of unreacted monomer (B-7) 1 hour under reflux as in Example 1 except that 13 parts Flexibloc D2®, 17 parts PMI, 71 parts MMA, 0.10 parts DM, and 93 parts toluene as polymerization solvent. The solution polymerization proceeded. The reaction rate calculated from the amount of monomers in the polymerization solution at this time was 33% for MMA and 34% for PMI. A part of the polymerization solution was taken out, and the block copolymer was isolated in the same manner as in Example 1. The PMI content in the block copolymer determined by 1 H-NMR was 18% by mass.
  • the weight average molecular weight (Mw) was 284,000
  • the number average molecular weight (Mn) was 1270
  • the molecular weight distribution (Mw / Mn) was 2.2. there were.
  • 0.035 parts of t-amylperoxyisononanoate manufactured by Arkema Yoshitomi Corp., Luperox (registered trademark) 570
  • St styrene
  • a polymer solution containing a block polymer copolymer having a polymer block (B) made of PMI and MMA at both ends of a polymer block (A) made of butyl acrylate and a copolymer made of PMI, MMA and St is obtained. It was. The reaction rates calculated from the amount of monomers in the polymer solution at this time were 95% for MMA, 99% for PMI, and 96% for St. To the resulting polymer solution was added a solution prepared by dissolving 0.66 parts of an ultraviolet absorber (“ADEKA STAB (registered trademark) LA-F70” manufactured by ADEKA) in 1.23 parts of toluene, and the solid content concentration of the polymer was 30.
  • ADEKA STAB registered trademark
  • B-7 had a weight average molecular weight of 17,000, a number average molecular weight of 62,000, a glass transition temperature of 134 ° C., and a thermal decomposition temperature of 320 ° C. In addition, when the foamability evaluation of B-7 was carried out, the result was ⁇ .
  • Example 12 Resin composition (B-8) comprising a copolymer by synthesis of a block polymer by nitroxide polymerization and additional polymerization of unreacted monomers
  • Example 11 except that 0.005 part of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04) was used instead of 0.009 part of ethyl acetoacetate aluminum diisopropylate, A polymer solution containing a block polymer copolymer having a polymer block (B) made of PMI and MMA at both ends of a polymer block (A) made of polybutyl acrylate and a copolymer made of PMI, MMA and St Obtained.
  • tetraethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04
  • the reaction rates calculated from the amount of monomers in the polymer solution at this time were 95% for MMA, 99% for PMI, and 96% for St.
  • ADEKA STAB registered trademark
  • LA-F70 ultraviolet absorber
  • a resin composition (B-8) containing a block polymer copolymer having a copolymer of PMI, MMA and St was obtained.
  • B-8 had a weight average molecular weight of 169,000, a number average molecular weight of 63,000, a glass transition temperature of 134 ° C., and a thermal decomposition temperature of 319 ° C. Further, the evaluation of foamability of B-8 was ⁇ . Further, when the molecular weight of the block copolymer obtained before the additional polymerization was determined, the weight average molecular weight (Mw) was 288,000, the number average molecular weight (Mn) was 1290,000, and the molecular weight distribution (Mw / Mn) ) Was 2.2.
  • Example 13 Resin composition (B-9) containing a copolymer by synthesis of a block polymer by nitroxide polymerization and addition polymerization of unreacted monomers
  • Example 11 in place of 0.009 part of ethyl acetoacetate aluminum diisopropylate, 0.05 part of Irganox 1010 (manufactured by BASF Japan), 0.05 part of ADK STAB AO-412S, 0
  • the polymer block (B) made of PMI and MMA was used on both ends of the polymer block (A) made of polybutyl acrylate in the same manner except that 0.05 part of ADK STAB 2112 (both made by ADEKA) was used.
  • a polymer solution containing a block polymer copolymer having a copolymer made of PMI, MMA and St was obtained.
  • the reaction rates calculated from the amount of monomers in the polymer solution at this time were 95% for MMA, 99% for PMI, and 96% for St.
  • To the obtained polymer solution was added a solution prepared by dissolving 0.66 parts of an ultraviolet absorber (“ADEKA STAB (registered trademark) LA-F70” manufactured by ADEKA) in 1.23 parts of toluene, and the solid content concentration of the polymer was 30.
  • ADEKA STAB registered trademark
  • LA-F70 ultraviolet absorber
  • Example 11 After diluting with toluene to a mass percent, devolatilization was carried out in the same manner as in Example 11, and polymer blocks (B) consisting of PMI and MMA were added to both ends of the polymer block (A) consisting of polybutyl acrylate.
  • B-9 had a weight average molecular weight of 168,000, a number average molecular weight of 62,000, a glass transition temperature of 134 ° C., and a thermal decomposition temperature of 324 ° C. Further, the evaluation of foamability of B-9 was ⁇ .
  • the weight average molecular weight (Mw) was 284,000
  • the number average molecular weight (Mn) was 1270
  • the molecular weight distribution (Mw / Mn ) was 2.2.
  • Example 14 Resin composition containing a copolymer by synthesis of a block polymer by nitroxide polymerization and additional polymerization of unreacted monomers (B-10) 1 hour under reflux as in Example 1 except that 13 parts Flexibloc D2®, 17 parts PMI, 71 parts MMA, 0.10 parts DM, and 93 parts toluene as polymerization solvent.
  • the solution polymerization proceeded.
  • the reaction rate calculated from the amount of monomers in the polymerization solution at this time was 33% for MMA and 34% for PMI.
  • a part of the polymerization solution was taken out, and the block copolymer was isolated in the same manner as in Example 1.
  • the PMI content in the block copolymer determined by 1 H-NMR was 18% by mass.
  • the weight average molecular weight (Mw) was 285,000
  • the number average molecular weight (Mn) was 120,000
  • the molecular weight distribution (Mw / Mn) was 2.2. there were.
  • 0.035 parts of t-amylperoxyisononanoate manufactured by Arkema Yoshitomi Corp., Luperox (registered trademark) 570
  • St styrene
  • reaction rates calculated from the amount of monomers in the polymer solution at this time were 95% for MMA, 99% for PMI, and 96% for St.
  • the barrel temperature is 270 ° C.
  • the rotation speed is 200 rpm
  • the degree of vacuum is 13.3 to 400 hPa (10 to 300 mmHg)
  • the number of vents is 3.
  • a resin composition (B-10) comprising a block polymer copolymer having a polymer block (B) composed of PMI and MMA at both ends of (A) and a copolymer composed of PMI, MMA and St is obtained. It was. B-10 had a weight average molecular weight of 169,000, a number average molecular weight of 64,000, a glass transition temperature of 134 ° C., and a thermal decomposition temperature of 323 ° C. Further, the evaluation of foamability of B-10 was ⁇ .
  • Table 4 shows the results of Examples 11 to 14.
  • Comparative Example 9 30 parts of the block copolymer (A-6) obtained in Comparative Example 7 and 70 parts of the polymer (C-1) obtained in Comparative Example 2 were mixed at 270 ° C. for 5 minutes using a lab plast mill to obtain a resin composition. A product (B-11) was obtained. The resin composition (B-11) had a Tg of 133 ° C.
  • Resin compositions (B-7), (B-8), (B-9), (B-10) and (B-11) were each press-molded at 250 ° C. to obtain 120 ⁇ m films. Next, the film was stretched 2 ⁇ 2 times at Tg + 23 ° C. to obtain a biaxially stretched film. The Tg, thickness, haze, and folding resistance of the stretched film thus obtained were measured. In addition, the resin compositions (B-7), (B-8), (B-9), (B-10) and (B-11) were respectively converted into manual heating press machines (IMC-180C, manufactured by Imoto Seisakusho). ) At 250 ° C. to obtain a 160 ⁇ m film.
  • IMC-180C manual heating press machines
  • the internal haze of the film was measured by filling the quartz cell with 1,2,3,4-tetrahydronaphthalene (tetralin) using NDH-1001DP manufactured by Nippon Denshoku Industries Co., Ltd. Converted to value. Next, the internal haze value (100 ⁇ m conversion value) after heating at 250 ° C. for 20 minutes was determined by a manual heating press, and the internal haze change rate (%) before and after heating was determined. The results are shown in the table below.
  • a maleimide block copolymer having a structural unit derived from an acrylic monomer and excellent in flexibility and strength can be efficiently produced.

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Abstract

La présente invention concerne un procédé de production d'un copolymère séquencé de maléimide ayant une unité structurale dérivée d'un monomère acrylique. Le procédé consiste à produire un copolymère séquencé ayant un séquence polymère (A) contenant une unité structurale dérivée de l'ester d'acide acrylique, et une séquence polymère (B) contenant une structure cyclique maléimide N-substituée et une unité structurale dérivée de l'ester d'acide méthacrylique, et comprenant une étape de polymérisation pour polymériser, au niveau d'une borne de la séquence polymère (A), un polymère nitroxyde (A1) ayant une structure nitroxyde comprenant une unité organophosphorée, et un monomère (B1) contenant un ester d'acide méthacrylique et un maléimide N-substitué en présence d'un composé thiol (C1).
PCT/JP2017/015330 2016-04-28 2017-04-14 Procédé de production d'un copolymère séquencé de maléimide WO2017188031A1 (fr)

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WO2021117723A1 (fr) * 2019-12-13 2021-06-17 東洋インキＳｃホールディングス株式会社 Copolymère séquencé, composition de résine, conducteur extensible, dispositif électronique et film adhésif sensible à la pression
WO2021251295A1 (fr) * 2020-06-08 2021-12-16 日産化学株式会社 Composition pour la formation de film de couche supérieure et procédé de production d'un motif à phases séparées

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