WO2012057079A1 - メタクリル樹脂組成物及び樹脂改質剤並びに成形体 - Google Patents
メタクリル樹脂組成物及び樹脂改質剤並びに成形体 Download PDFInfo
- Publication number
- WO2012057079A1 WO2012057079A1 PCT/JP2011/074434 JP2011074434W WO2012057079A1 WO 2012057079 A1 WO2012057079 A1 WO 2012057079A1 JP 2011074434 W JP2011074434 W JP 2011074434W WO 2012057079 A1 WO2012057079 A1 WO 2012057079A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- acrylate
- methacrylic resin
- polymer block
- resin composition
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- 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
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2233/00—Use of polymers of unsaturated acids or derivatives thereof, as reinforcement
- B29K2233/04—Polymers of esters
- B29K2233/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
-
- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Definitions
- the present invention relates to a methacrylic resin composition having excellent transparency, moldability and mechanical properties.
- Methacrylic resin is excellent in optical properties such as transparency and weather resistance, and its molded body has a beautiful appearance.
- display members such as lighting fixtures and signboards, optical members such as display parts, etc. It has been used in various applications including interior members, building members, electronic / electrical members, and medical members.
- the methacrylic resin is a brittle material, it has been difficult to use the methacrylic resin as it is for applications that require flexibility, flex resistance, impact resistance, flexibility, and the like.
- Patent Document 1 Japanese Patent Application Laid-Open No. 10-168271
- a resin composition mainly having improved impact resistance obtained by mixing a block copolymer having a highly syndiotactic polymethacrylic acid alkyl ester block with an acrylic resin. Things are being considered.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2000-154329 examines a resin composition in which an acrylic resin is blended with a block copolymer containing a methacrylic polymer block and an acrylic polymer block as an impact resistance improver. Has been.
- Patent Document 3 Japanese Patent Application Laid-Open No. 2003-277574
- a resin composition having a good balance of weather resistance, flexibility, and mechanical strength, in which an acrylic thermoplastic elastomer is mixed with a methacrylic resin is studied.
- Patent Document 4 discusses a resin composition having a wide range of compositions and excellent transparency, molding processability, and the like, in which an acrylic resin is mixed with a plurality of types of acrylic block copolymers.
- Patent Document 5 Japanese Patent Application Laid-Open No. 2006-124724
- a resin excellent in heat resistance and oil resistance obtained by dynamically crosslinking a thermoplastic resin by adding a block copolymer having an acrylic polymer block. Compositions are being considered.
- An object of the present invention is to provide a methacrylic resin having flexibility, bending resistance, impact resistance or flexibility, and excellent melt fluidity and injection moldability while maintaining the transparency inherent in the methacrylic resin. It is to provide a composition.
- the present inventors have intensively studied to achieve the above object.
- the resin composition comprising a methacrylic resin and a block copolymer having a specific polymer block and a refractive index, while maintaining the transparency inherent in the methacrylic resin, flexibility, bending resistance, It has been found that impact resistance or flexibility can be expressed.
- the methacrylic resin composition of the present invention comprises 10 to 99 parts by mass of a methacrylic resin (A) having 80% by mass or more of methyl methacrylate units, 10 to 60% by mass of a methyl methacrylate polymer block (b1), and acrylic acid. 90 to 40% by mass of the ester polymer block (b2) and 90 to 1 part by mass of a block copolymer (B) having a refractive index of 1.485 to 1.495 (provided that The total of (A) and (B) is 100 parts by mass).
- the acrylic ester polymer block (b2) contained in the block copolymer (B) is a copolymer of 50 to 90% by mass of alkyl acrylate ester and 50 to 10% by mass of (meth) acrylic acid aromatic ester.
- a block is preferred.
- As the (meth) acrylic acid aromatic ester benzyl acrylate is preferred.
- the resin modifier of this invention consists of the said block copolymer (B), It is characterized by the above-mentioned.
- the molded object of this invention can be manufactured from the said resin composition.
- the haze value in a 3 mm-thick molded product obtained from the methacrylic resin composition is preferably 2% or less.
- the resin composition of the present invention is excellent in flexibility, flex resistance, impact resistance or flexibility, melt flowability, and injection moldability while maintaining the transparency inherent in methacrylic resins.
- the methacrylic resin (A) used in the present invention is a resin mainly having methyl methacrylate units, and has 80% by mass or more of methyl methacrylate units.
- the methyl methacrylate unit contained in the methacrylic resin (A) is preferably 90% by mass or more, and more preferably 95% by mass or more.
- the methacrylic resin (A) may contain monomer units other than methyl methacrylate units.
- the monomer include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, and isoamyl methacrylate.
- the methacrylic resin (A) is a copolymer
- the form of copolymerization is not particularly limited, and may be any of random copolymerization, block copolymerization, graft copolymerization, alternating copolymerization, and the like.
- limiting in particular about the stereoregularity of the methacryl resin (A) used for this invention Any of isotactic, heterotactic, or syndiotactic may be sufficient.
- the number average molecular weight of the methacrylic resin (A) is not particularly limited, but is usually from 5,000 to 2,000,000, preferably from 10,000 to 1,000,000.
- the number average molecular weight is a polystyrene-reduced number average molecular weight determined by gel permeation chromatography (GPC) measurement.
- the said methacrylic resin (A) may be used individually by 1 type, and may mix and use 2 or more types of methacrylic resins from which molecular weight etc. differ.
- the block copolymer (B) used in the present invention has a methyl methacrylate polymer block (b1) and an acrylate polymer block (b2).
- the methyl methacrylate polymer block (b1) is a polymer block mainly composed of methyl methacrylate units, and the methyl methacrylate units are usually 50% by mass or more, preferably 60 to 100% by mass, more preferably 90%.
- the content is preferably 100 to 100% by mass, more preferably 95 to 100% by mass, particularly preferably 98 to 100% by mass, and 100% by mass is also desirable.
- the above-mentioned methyl methacrylate polymer block (b1) may contain monomer units other than methyl methacrylate units.
- the monomer capable of forming the monomer unit include methacrylic acid esters, acrylic acid esters, unsaturated carboxylic acids, olefins, conjugated dienes, aromatic vinyls, and acrylamides other than methyl methacrylate described above with respect to the methacrylic resin (A).
- the compatibility of the methyl methacrylate polymer block (b1) with the methacrylic resin (A) is increased.
- aromatic methacrylate esters such as phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and phenyl acrylate
- Acrylic acid aromatic esters such as benzyl acrylate and phenoxyethyl acrylate are preferred.
- methacrylic acid esters or acrylic acid esters other than methyl methacrylate typically methacrylic acid aromatic esters and acrylic acid aromatic esters are not excessively contained, and the amount used is a methyl methacrylate polymer. It is preferably 10% by mass or less, more preferably 5% by mass or less, of the monomer forming the block (b1). Further, the monomer composition can be adjusted so that the refractive index of the polymer consisting only of the monomer forming the methyl methacrylate polymer block (b1) is in the range of 1.485 to 1.495. preferable.
- the acrylate polymer block (b2) is a polymer block mainly composed of acrylate units, and the acrylate units are usually 50% by mass or more, preferably 60 to 100% by mass, more preferably 80%. ⁇ 100% by mass.
- acrylic ester examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, acrylic Acrylic acid alkyl esters such as amyl acid, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate; phenyl acrylate, benzyl acrylate, acrylic Examples include acrylic acid aromatic esters such as phenoxyethyl acid; 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, glycidyl acrylate, and allyl acrylate.
- acrylic acid esters acrylic acid alkyl esters, acrylic acid aromatic esters, and 2-methoxyethyl acrylate are preferred.
- the resin composition of the present invention tends to be superior in flexibility, flex resistance, impact resistance or flexibility.
- the acrylate polymer block (b2) may contain monomer units other than acrylate units.
- Monomers that can form the monomer units include methyl methacrylate and the above-mentioned methacrylates, unsaturated carboxylic acids, olefins, conjugated dienes, aromatic vinyls, acrylamides, methacrylamides, acrylonitriles, methacrylonitriles, Examples include vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride.
- methacrylic acid aromatic esters such as phenyl methacrylate, benzyl methacrylate, and phenoxyethyl methacrylate are preferable.
- an acrylic ester polymer block (b2) is the said acrylic acid alkyl ester, and (meth) acrylic-acid aromatic ester.
- a copolymer block is preferred.
- (meth) acrylic acid aromatic ester is a general term for acrylic acid aromatic ester and methacrylic acid aromatic ester.
- the (meth) acrylic acid aromatic ester copolymerized with the alkyl acrylate among the above-mentioned acrylic acid aromatic ester and methacrylic acid aromatic ester, the flexibility and flex resistance of the resin composition of the present invention, Benzyl acrylate is preferable from the viewpoint of excellent impact resistance or flexibility and excellent transparency.
- the proportion of the acrylic acid alkyl ester unit in the copolymer block is preferably 50 to 90% by mass, more preferably 60 to 80% by mass.
- the proportion of the (meth) acrylic acid aromatic ester unit in the copolymer block is preferably 50 to 10% by mass, more preferably 40 to 20% by mass.
- the transparency of the resin composition of the present invention tends to be more excellent.
- the monomer composition can be adjusted so that the refractive index of the polymer consisting only of the monomer forming the acrylate polymer block (b2) is in the range of 1.485 to 1.495. preferable.
- the content ratio of the methyl methacrylate polymer block (b1) is 10 to 60% by mass, preferably 20 to 55% by mass.
- the content ratio of (b1) is in the above range, flexibility, flex resistance, impact resistance, or flexibility can be easily imparted without impairing the transparency of the methacrylic resin (A).
- the above content ratio means the total content ratio of all methyl methacrylate polymer blocks (b1). .
- the content of the acrylate polymer block (b2) is 90 to 40% by mass, preferably 80 to 45% by mass.
- the content ratio of (b2) is in the above range, the resin composition of the present invention tends to have excellent impact resistance or flexibility.
- the block copolymer (B) includes a plurality of acrylate polymer blocks (b2), the above content ratio means the total content ratio of all the acrylate polymer blocks (b2). .
- the block copolymer (B) is characterized in that the refractive index is between 1.485 and 1.495.
- the refractive index is between 1.485 and 1.495.
- the refractive index of the block copolymer (B) is preferably from 1.486 to 1.494, more preferably from 1.487 to 1.494.
- the refractive index is in the above range, not only the flexibility, the bending resistance, the impact resistance or the flexibility is excellent, but the transparency of the obtained resin composition tends to be more excellent.
- the bonding form of the block copolymer is not particularly limited.
- a diblock copolymer, a triblock copolymer, and a star block copolymer are preferable, and represented by [methyl methacrylate polymer block (b1)]-[acrylate polymer block (b2)].
- the block copolymer (B) has a methyl methacrylate polymer block (b1) and an acrylate polymer block (b2), but the acrylic ester is added within a range not impairing the effects of the present invention.
- the monomer to be the polymer block (c) includes unsaturated carboxylic acid, olefin, conjugated diene, aromatic vinyl, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride. , Vinylidene chloride, vinylidene fluoride, ⁇ -caprolactone, valerolactone, and the like.
- the bonding form thereof is, for example, [methyl methacrylate polymer block (b1)]-([acrylic ester type Polymer block (b2)]-[methyl methacrylate polymer block (b2)]) n- [polymer block (c)], [polymer block (c)]-[methyl methacrylate polymer block (b1) ]-([Acrylate polymer block (b2)]-[methyl methacrylate polymer block (b1)]) n- [polymer block (c)] (n represents an integer of 1 or more) and the like. Can be mentioned.
- the molecular chain form of the block copolymer (B) is not particularly limited, and examples thereof include linear, branched, and radial forms.
- the number average molecular weight of the block copolymer (B) is not particularly limited, but is usually in the range of 10,000 to 1,000,000, preferably in the range of 20,000 to 400,000, more preferably in the range of 20,000 to 200,000, still more preferably 30,000 to 200,000. And particularly preferably in the range of 30,000 to 100,000. When the number average molecular weight of the block copolymer (B) is smaller than this, the effect of improving flexibility, flex resistance and impact resistance is small, and when it is larger than this, the melt flowability and injection moldability are lowered.
- the molecular weight distribution (Mw / Mn) of the block copolymer (B) is preferably in the range of 1.0 to 2.0. More preferably in the range of ⁇ 1.6.
- the method for producing the block copolymer (B) is not particularly limited, but preferably, a method of living polymerizing monomers constituting each polymer block is used.
- living polymerization techniques for example, an anionic polymerization is carried out in the presence of a mineral salt such as an alkali metal or alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator (Japanese Patent Publication No. 7-25859).
- a method of anionic polymerization in the presence of an organoaluminum compound see JP-A-11-335432
- a method of polymerization using an organic rare earth metal complex as a polymerization initiator special feature.
- block copolymers can be obtained with high purity, and the molecular weight distribution is narrow, that is, oligomers that cause a decrease in paintability and oil resistance of the polymer composition, and factors that reduce flexibility. Therefore, a method of anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound is preferable.
- organoaluminum compound examples include isobutyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isobutyl bis (2,6-di-t-butylphenoxy) aluminum, isobutyl bis [2,2′-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, n-octylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, n-octylbis (2,6 -Di-t-butylphenoxy) aluminum, n-octylbis [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, tris (2,6-di-t-butyl-4-methyl) And phenoxy) aluminum, tris (2,6-diphenylphenoxy) aluminum, and the like.
- isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isobutylbis (2,4-di-t-butylphenoxy) aluminum, n-octylbis (2,6-di-t -Butyl-4-methylphenoxy) aluminum and n-octylbis (2,4-di-t-butylphenoxy) aluminum are particularly preferred from the viewpoint of polymerization activity, block efficiency and the like.
- the block copolymer (B) can be suitably used as a resin modifier.
- the methacrylic resin composition of the present invention containing the methacrylic resin (A) and the block copolymer (B) is excellent in transparency even when they are mixed in an arbitrary composition ratio, and is flexible and flexible. Excellent in resistance, impact resistance or flexibility.
- the blending amount of the methacrylic resin (A) and the block copolymer (B) in the methacrylic resin composition of the present invention is 10 to 99 parts by mass of the methacrylic resin (A) and 90 to 1 part by mass of the block copolymer (B).
- the characteristics of the resin composition include the proportion of the acrylate polymer block (b1) contained in the block copolymer (B), the methacrylic resin (A) in the composition forming a matrix phase, or the dispersed phase. It can be set as appropriate depending on whether it is formed.
- the amount of the acrylate polymer block (b2) contained in the block copolymer (B) is large relative to the entire methacrylic resin composition, and the phase composed of the methacrylic resin (A) is a dispersed phase
- an acrylic soft material excellent in flexibility can be obtained.
- the composition of the acrylic soft material having such characteristics varies depending on the molecular specifications and types of the block copolymer (B) and the molecular specifications of the methacrylic resin (A).
- the content of the acid ester polymer block (b2) is usually 25 to 75% by mass, preferably 30 to 60% by mass.
- the dispersed phase can be in the form of a sphere (sphere), a rod (cylinder), a plate (lamella), or the like.
- the dispersion size is preferably in the range of 10 nm to 1 ⁇ m, more preferably in the range of 20 to 700 nm, and still more preferably in the range of 50 to 300 nm.
- the dispersion size means a diameter in the case of a spherical shape or a rod shape, and a thickness direction in the case of a plate shape.
- the content of the acrylate polymer block (b2) is 30 to 40% by mass with respect to the entire methacrylic resin composition.
- an acrylic soft resin can be produced.
- acrylic soft resins are flexible and have excellent optical properties such as transparency, a light guide using a light source such as a TV, a PC monitor, a mobile phone display unit, a mobile terminal, an optical film for advertising, an LED light source, etc. Can be used as a light guide using a light source such as a TV, a PC monitor, a mobile phone display unit, a mobile terminal, an optical film for advertising, an LED light source, etc. Can be used as
- the amount of the acrylate polymer block (b2) contained in the block copolymer (B) is small relative to the entire methacrylic resin composition, and the phase consisting of the methacrylic resin (A) is a matrix phase
- the methacrylic resin (A) forms a matrix phase
- the methacrylic resin (A) and the methyl methacrylate polymer block (b1) contained in the block copolymer (B) are compatible with each other.
- the acrylate polymer block (b2) contained in the coalescence (B) forms a dispersed phase.
- the dispersed phase of the acrylate polymer block (b2) is preferably in various forms such as a sphere, a rod (cylinder), and a plate (lamella).
- the dispersion size in this case depends on the molecular weight of the acrylate polymer block, but is preferably in the range of 5 to 100 nm, more preferably in the range of 19 to 50 nm.
- the dispersion size means a diameter in the case of a spherical shape or a rod shape, and a thickness direction in the case of a plate shape.
- the composition of the acrylic hard material having such characteristics varies depending on the molecular specifications and types of the block copolymer (B) and the molecular specifications of the methacrylic resin (A).
- the content of the acid ester polymer block (b2) is usually 3 to 40% by mass, preferably 3 to 30% by mass, more preferably 5 to 30% by mass, and further preferably 5 to 20% by mass.
- the content of the acrylate polymer block (b2) is not less than the above lower limit value, the impact resistance and the melt fluidity are excellent, and when it is not more than the upper limit value, the rigidity and the surface damage resistance are excellent. It will be a thing.
- a methacrylic resin composition in which an acrylic rubber component composed of a multilayer structure graft copolymer produced by emulsion polymerization or the like is blended with a methacrylic resin.
- the methacrylic resin composition produced by this method it is difficult to suppress foreign matter defects caused by aggregation of rubber components, and the dispersion diameter of the rubber component is generally 100 nm or more, so that it is optically transparent. It is also difficult to obtain the material.
- blend is a crosslinked rubber component, it exists in the tendency for melt fluidity to fall.
- the methacrylic resin is modified by adding a conventional acrylic block copolymer, the content of the acrylic ester polymer block contained in the acrylic block copolymer with respect to the entire resin composition Even if it is 20 mass% or less, transparency will be impaired remarkably.
- the original transparency of the methacrylic resin (A) is not impaired, and injection molding is performed. It also has excellent melt fluidity.
- the melt flow rate (MFR) is preferably 20 g / 10 min or more, more preferably 25 g / 10 min or more, under the conditions of 230 ° C. and 37.3 N in accordance with ISO 1173.
- These resin compositions having a good balance between melt fluidity and impact resistance can improve injection moldability that requires large-scale injection molding and fine shape transfer, and therefore can be used for car interior materials, car exterior materials, and home appliances. It is suitable for a body, a light guide plate, a sheet such as a solar cell, a window film, a surface pattern optical film for a flat panel display such as an LCD.
- the said methacrylic resin composition may contain another polymer other than a methacrylic resin (A) and a block copolymer (B) as needed.
- the other polymer include olefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, polynorbornene; ethylene ionomer; polystyrene, styrene-maleic anhydride copolymer, Styrenic resins such as high impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; methyl methacrylate-styrene copolymer; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, polyamide such as polyamide elastomer; polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyviny
- the methacrylic resin composition of the present invention is a rubber, softener, lubricant, plasticizer, adhesive, tackifier, antioxidant, heat stabilizer, light stabilizer within the range not impairing the effects of the present invention.
- Additives such as antistatic agents, flame retardants, foaming agents, colorants, dyeing agents; fillers such as inorganic fillers and fiber reinforcing agents may be contained.
- the rubber examples include acrylic rubber; silicone rubber; styrene TPE (thermoplastic elastomer) such as SEPS, SEBS, and SIS; olefin rubber such as IR, EPR, and EPDM.
- styrene TPE thermoplastic elastomer
- olefin rubber such as IR, EPR, and EPDM.
- the softening agent examples include mineral oil softening agents such as paraffinic oil and naphthenic oil. When a softening agent is added, the fluidity at the time of molding can be improved.
- the inorganic filler examples include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate. When an inorganic filler is added, heat resistance, weather resistance and the like can be improved, and the amount of the composition can be increased.
- the fiber reinforcing agent examples include glass fibers, inorganic fibers such as carbon fibers, and organic fibers.
- the composition can be reinforced.
- a heat stabilizer, an antioxidant and the like it is practically preferable to add a heat stabilizer, an antioxidant and the like from the viewpoint of further improving heat resistance and weather resistance.
- the method for producing the methacrylic resin composition of the present invention is not particularly limited, but from the viewpoint of enhancing the dispersibility of each component contained in the resin composition, the methacrylic resin (A) and the block copolymer (B) are melted. A method of producing by kneading is preferred.
- the methacrylic resin (A) and the block copolymer (B) may be added to a melt-kneading apparatus and kneaded in a molten state, and if necessary, these and other polymers, additives, A filler or the like may be added simultaneously and melt-kneaded, or the block copolymer (B) may be melt-kneaded with the above-mentioned other polymers, additives, fillers, etc., and then melt-kneaded with the methacrylic resin (A). May be.
- a kneading apparatus for example, a kneading apparatus such as a kneader ruder, an extruder, a mixing roll, or a Banbury mixer can be used.
- the temperature at the time of kneading may be appropriately adjusted according to the melting temperature of the methacrylic resin (A), the block copolymer (B), etc. to be used. .
- the methacrylic resin composition of the present invention can also be produced by the method described below in order to improve transparency, dispersibility and the like. That is, first, the block copolymer (B) is dissolved in a monomer mixture (A ′) containing 80% by mass or more of methyl methacrylate, and then the monomer mixture containing the block copolymer (B). This is a method for producing the resin composition of the present invention by polymerizing (A ′). When the monomer mixture (A ′) is polymerized in such a production method, the polymerization may be performed by a bulk polymerization method without using a solvent or by a solution polymerization method using a solvent.
- the solvent used in the solution polymerization method is not particularly limited as long as it is a solvent capable of dissolving the monomer mixture (A ′), the resulting methacrylic resin (A), and the block copolymer (B),
- aromatic hydrocarbons such as benzene, toluene, and ethylbenzene are listed.
- the heat history is shortened, so that not only coloring and foreign matters accompanying thermal decomposition are suppressed, but also the methacrylic resin (A) and the block Since the dispersibility with the copolymer (B) is also improved, the transparency is improved.
- the methacrylic resin composition of the present invention thus produced can be obtained in a desired form such as a pellet or powder.
- a polymer composition in the form of pellets, powder, etc. can be suitably used as a molding material.
- the methacrylic resin composition of the present invention is excellent in melt fluidity, it can be molded using a molding method or a molding apparatus generally used for thermoplastic polymers.
- a molded body can be produced by a molding method such as injection molding, extrusion molding, compression molding, blow molding, calender molding, vacuum molding, and the like, a molding method that undergoes heat melting, a solution casting method, and the like.
- a molded product having an arbitrary shape such as a mold, a pipe, a sheet, a film, a fibrous material, or a laminate including a layer made of the polymer composition
- the molded product obtained from the methacrylic resin composition of the present invention is excellent in transparency and impact resistance.
- the haze value is preferably 2%.
- it is more preferably 1.5% or less, and further preferably 1% or less.
- the impact resistance is preferably 21 kJ / m 2 or more in terms of Charpy impact strength without notch in accordance with ISO 179-1eU.
- the molded object which consists of a methacryl resin composition of this invention is excellent in a softness
- Example 1 [Production of Block Copolymer B-1] (1) A three-way cock was attached to a 1-liter three-necked flask, and the inside was deaerated and replaced with nitrogen. Then, 776 ml of toluene, 46.0 ml of 1,2-dimethoxyethane, and isobutylbis (2,6- 19.6 ml of a toluene solution containing 8.8 mmol of di-t-butyl-4-methylphenoxy) aluminum was added, and 1.8 mmol of sec-butyllithium was further added. To this, 45.3 ml of methyl methacrylate was added and reacted at room temperature for 1 hour.
- Example 2 [Production of Block Copolymer B-2] (1) In Example 1, except that the amount of n-butyl acrylate was changed to 50.5 ml and the amount of benzyl acrylate was changed to 14.2 ml, the acrylic block copolymer B- 2 was obtained. The evaluation results are shown in Table 1.
- Example 3 [Production of block copolymer B-3] (1) In Example 1, except that the amount of n-butyl acrylate was changed to 47.1 ml and the amount of benzyl acrylate was changed to 17.0 ml, the acrylic block copolymer B- 3 was obtained. The evaluation results are shown in Table 1.
- Example 4 [Production of Acrylic Block Copolymer B-4] (1) A three-way cock was attached to a 1-liter three-necked flask, and the inside was deaerated and replaced with nitrogen. Then, 776 ml of toluene, 46.0 ml of 1,2-dimethoxyethane, and isobutylbis (2,6- 21.0 ml of a toluene solution containing 9.4 mmol of di-t-butyl-4-methylphenoxy) aluminum was added, and 1.9 mmol of sec-butyllithium was further added. To this, 19.2 ml of methyl methacrylate was added and reacted at room temperature for 1 hour.
- Example 1 [Production of Acrylic Block Copolymer B-5] (1) In Example 1, except that the amount of n-butyl acrylate was changed to 67.3 ml and benzyl acrylate was not added, an acrylic block copolymer B-5 was obtained by the same method as in Example 1. It was. The evaluation results are shown in Table 1.
- Example 4 An acrylic block copolymer B-6 was obtained in the same manner as in Example 4 except that the amount of n-butyl acrylate was changed to 94.3 ml and benzyl acrylate was not added. The evaluation results are shown in Table 1.
- Example 4 [Production of System Block Copolymer B-8] (1) In Example 1, except that the amount of n-butyl acrylate was changed to 26.9 ml and the amount of benzyl acrylate was changed to 34.0 ml, an acrylic block copolymer B- 8 was obtained. The evaluation results are shown in Table 1.
- a methacrylic resin (A) which has a methyl methacrylate unit 80 mass% or more, a methyl methacrylate polymer block (b1), and an acrylate polymer block (b2), and a refractive index is 1.
- a molded product using a methacrylic resin composition (C-1 to C-4) comprising a block copolymer (B) having a molecular weight of 485 to 1.495 is obtained by using a block copolymer having a refractive index outside the range of the presently known results. It can be seen that it is excellent in transparency as compared with the case of using the coalescence (C-5 to C-7). Moreover, it turns out that it is excellent in impact resistance performance compared with a methacrylic resin simple substance (comparative example 8).
- Examples 9 and 10, Comparative Examples 9 and 10 >> [Production of Methacrylic Compositions C-10 to 13]
- the block copolymers (B) obtained in Examples 3 and 4 and Comparative Examples 1 and 2 were mixed with methacrylic resin (A) (manufactured by Kuraray Co., Ltd .: Parapet GH-S) in the proportions shown in Table 3.
- methacrylic resin compositions C-10 to C-13 were produced by melt-kneading in a lab plast mill.
- the methacrylic resin compositions C-10 to C-13 obtained in the above (1) were subjected to thermal breathing to obtain a molded product having a thickness of 3 mm. Table 3 shows the evaluation results of this molded body.
- compositions having high content of the acrylic acid block (b) (Examples 9 and 10) have high tensile fracture elongation (that is, have toughness), and the refractive index is outside the range of this finding. It turns out that it is excellent in transparency compared with the case where a block copolymer is used (Comparative Examples 9 and 10).
- the methacrylic resin composition of the present invention has mechanical properties such as flexibility, flex resistance, impact resistance, or flexibility without impairing optical properties such as transparency and weather resistance inherent in the methacrylic resin itself. Can be improved. Moreover, it is excellent also in moldability, for example, injection moldability. Therefore, it is useful for various applications including lighting devices, display members such as signboards, optical members such as display parts, interior members, building members, electronic / electrical members, medical members, and the like.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
例えば、特許文献1(特開平10-168271号)では、アクリル系樹脂に、高シンジオタクチックなポリメタクリル酸アルキルエステルブロックを有するブロック共重合体を混合した、主として耐衝撃性が向上した樹脂組成物が検討されている。
本発明の成形体は上記樹脂組成物から製造することができる。上記メタクリル樹脂組成物から得られる厚さ3mmの成形体におけるヘイズ値は2%以下であることが好ましい。
本発明で用いられるメタクリル樹脂(A)はメタクリル酸メチル単位を主として有する樹脂であり、メタクリル酸メチル単位を80質量%以上有している。メタクリル樹脂(A)に含まれるメタクリル酸メチル単位は90質量%以上が好ましく、95質量%以上がより好ましい。
アクリル酸メチル、アクリル酸エチル、アクリル酸n-プロピル、アクリル酸イソプロピル、アクリル酸n-ブチル、アクリル酸イソブチル、アクリル酸sec-ブチル、アクリル酸tert-ブチル、アクリル酸アミル、アクリル酸イソアミル、アクリル酸n-ヘキシル、アクリル酸シクロヘキシル、アクリル酸2-エチルヘキシル、アクリル酸ペンタデシル、アクリル酸ドデシル、アクリル酸イソボルニル、アクリル酸フェニル、アクリル酸ベンジル、アクリル酸フェノキシエチル、アクリル酸2-ヒドロキシエチル、アクリル酸2-メトキシエチル、アクリル酸グリシジル、アクリル酸アリルなどのアクリル酸エステル;
アクリル酸、アクリル酸、無水マレイン酸などの不飽和カルボン酸;
エチレン、プロピレン、1-ブテン、イソブチレン、1-オクテンなどのオレフィン;
1,3-ブタジエン、イソプレン、ミルセンなどの共役ジエン;
スチレン、α-メチルスチレン、p-メチルスチレン、m-メチルスチレンなどの芳香族ビニル;
アクリルアミド、メタクリルアミド、アクリロニトリル、メタクリロニトリル、酢酸ビニル、ビニルピリジン、ビニルケトン、塩化ビニル、塩化ビニリデン、フッ化ビニリデンなどが挙げられる。これら単量体は1種単独で、あるいは2種以上混合して用いることができる。
本発明で用いられるブロック共重合体(B)は、メタクリル酸メチル重合体ブロック(b1)とアクリル酸エステル重合体ブロック(b2)とを有する。
また、メタクリル酸メチル重合体ブロック(b1)を形成する単量体のみからなる重合体の屈折率が1.485~1.495の範囲となるように、かかる単量体組成を調整することが好ましい。
ここで、(メタ)アクリル酸芳香族エステルとはアクリル酸芳香族エステルおよびメタクリル酸芳香族エステルを総称するものである。アクリル酸アルキルエステルと共重合する(メタ)アクリル酸芳香族エステルとしては、上記したアクリル酸芳香族エステルおよびメタクリル酸芳香族エステルの中でも、本発明の樹脂組成物の可撓性、耐屈曲性、耐衝撃性または柔軟性を優れたものとし、しかも透明性も優れたものとする観点からアクリル酸ベンジルが好ましい。
また、アクリル酸エステル重合体ブロック(b2)を形成する単量体のみからなる重合体の屈折率が1.485~1.495の範囲となるように、かかる単量体組成を調整することが好ましい。
[メタクリル酸メチル重合体ブロック(b1)]-[アクリル酸エステル重合体ブロック(b2)]-[メタクリル酸メチル重合体ブロック(b1)]、[アクリル酸エステル重合体ブロック(b2)]-[メタクリル酸メチル重合体ブロック(b1)]-[アクリル酸エステル重合体ブロック(b2)]などで表されるトリブロック共重合体;
[メタクリル酸メチル重合体ブロック(b1)]-([アクリル酸エステル重合体ブロック(b2)]-[メタクリル酸メチル重合体ブロック(b1)])n+1、[メタクリル酸メチル重合体ブロック(b1)]-([アクリル酸エステル重合体ブロック(b2)]-[メタクリル酸メチル重合体ブロック(b1)])n-[アクリル酸エステル重合体ブロック(b2)]、[アクリル酸エステル重合体ブロック(b2)]-([メタクリル酸メチル重合体ブロック(b1)]-[アクリル酸エステル重合体ブロック(b2)])n+1、[アクリル酸エステル重合体ブロック(b2)]-([メタクリル酸メチル重合体ブロック(b1)]-[アクリル酸エステル重合体ブロック(b2)])n-[メタクリル酸メチル重合体ブロック(b1)](nは1以上の整数を表す)などの重合体ブロックを4以上有するマルチブロック共重合体;
([メタクリル酸メチル重合体ブロック(b1)]-[アクリル酸エステル重合体ブロック(b2)])mX、([アクリル酸エステル重合体ブロック(b2)]-[メタクリル酸メチル重合体ブロック(b1)])mX、([メタクリル酸メチル重合体ブロック(b1)]-[アクリル酸エステル重合体ブロック(b2)]-[メタクリル酸メチル重合体ブロック(b1)])nX(mは平均値2を超える正数、Xはカップリング残基を表す)で表されるスター型ブロック共重合体などが挙げられる。
メタクリル樹脂(A)からなる相が分散相を形成している場合、分散相の形態としては、球状(スフェア)、棒状(シリンダー)、板状(ラメラ)等の形態をとることができる。分散サイズは10nm~1μmの範囲が好ましく、20~700nmの範囲がより好ましく、50~300nmの範囲がさらに好ましい。ここで、上記分散サイズとは、球状、棒状の場合はその直径、板状の場合は厚み方向のことを言う。
メタクリル樹脂(A)がマトリックス相を形成している場合、メタクリル樹脂(A)とブロック共重合体中(B)中に含まれるメタクリル酸メチル重合体ブロック(b1)が相溶し、ブロック共重合体(B)中に含まれるアクリル酸エステル重合体ブロック(b2)が分散相を形成していることが好ましい。この場合のアクリル酸エステル重合体ブロック(b2)の分散相の形態としては、球状(スフェア)、棒状(シリンダー)、板状(ラメラ)と種々の形態をとる事が好ましい。この場合の分散サイズは、アクリル酸エステル重合体ブロックの分子量に依存するが、5~100nmの範囲が好ましく、19~50nmの範囲がより好ましい。ここで、上記分散サイズとは、球状、棒状の場合はその直径、板状の場合は厚み方向のことを言う。
上記無機充填剤としては、炭酸カルシウム、タルク、カーボンブラック、酸化チタン、シリカ、クレー、硫酸バリウム、炭酸マグネシウムなどが挙げられる。無機充填剤を添加すると、耐熱性、耐候性等の向上が可能となり、組成物の増量が可能となる。
これら添加剤の中でも、耐熱性、耐候性をさらに良好なものとする観点からは、熱安定剤、酸化防止剤などを添加することが実用上好ましい。
具体的には、メタクリル樹脂(A)およびブロック共重合体(B)を溶融混練装置に添加して溶融状態で混練すればよいが、必要に応じてこれらと上記その他の重合体、添加剤、フィラーなどを同時に添加して溶融混練してもよいし、ブロック共重合体(B)を、上記その他の重合体、添加剤、フィラーなどと溶融混練した後に、メタクリル樹脂(A)と溶融混練してもよい。混練装置としては、例えば、ニーダールーダー、押出機、ミキシングロール、バンバリーミキサーなどの混練装置を用いることができる。混練時の温度は、使用するメタクリル樹脂(A)、ブロック共重合体(B)等の溶融温度などに応じて適宜調節すればよいが、通常110℃~300℃の範囲内の温度で混練する。
すなわち、まず、ブロック共重合体(B)を、メタクリル酸メチルを80質量%以上含有する単量体混合物(A’)に溶解させ、ついでブロック共重合体(B)を含有する単量体混合物(A’)を重合することにより本発明の樹脂組成物を作製する方法である。かかる作製方法において単量体混合物(A’)を重合する場合、重合は、溶媒を用いずに塊状重合法により行っても、溶媒を用いて溶液重合法により行ってもよい。溶液重合法に用いる溶媒としては、単量体混合物(A’)、得られるメタクリル樹脂(A)、及びブロック共重合体(B)に対して溶解能を有する溶媒であれば特に制限されず、例えば、ベンゼン、トルエン、エチルベンゼン等の芳香族炭化水素等が挙げられる。また、必要に応じて、2種類以上の溶媒を混合して使用してもよい。以上の作製方法によれば、溶融押出機での溶融混錬法と比較して、熱履歴が短くなるので熱分解に伴う着色や異物が抑制されるばかりでなく、メタクリル樹脂(A)とブロック共重合体(B)との分散性も向上するので、透明性が向上する。
ペレット、粉末などの形態の重合体組成物は、成形材料として好適に使用できる。
本発明のメタクリル樹脂組成物から得られる成形体は透明性、耐衝撃性に優れ、例えば厚さ3mmの成形体(典型的にはシート状の成形体)においては、ヘイズ値が好ましくは2%以下、より好ましくは1.5%以下、さらに好ましくは1%以下である。耐衝撃性は、ISO179-1eUに準拠したノッチ無しのシャルピー衝撃強度で21kJ/m2以上であるのが好ましい。
そのため、食品包装シート、キャップライナーなどの食品包装材用途;日用雑貨用途;スキー靴等のスポーツ用品用途;ゴルフボールの外皮、コア材などの運動用具または玩具用途;デスクマットなどの文具用途;バンパーガードなどの自動車内外装用途;土木シート、防水シート、窓枠シーリング材、建築物用シーリング材などの土木建築用途;掃除機用コーナーバンパー、冷蔵庫用ドアシールなどの家電機器用途;AV機器用途;OA事務機器用途;靴底、トップリフト等の履き物・衣料用品用途;テキスタイル用途;医療用機器用途などとして種々の用途に用いることができる。
実施例及び比較例において用いた測定機器および測定方法を以下に記す。
装置:東ソー社製ゲルパーミエーションクロマトグラフ(HLC-8020)
カラム:東ソー社製TSKgel GMHXL、G4000HXLおよびG5000HXLを直列に連結
溶離液:テトラヒドロフラン
溶離液流量:1.0ml/分
カラム温度:40℃
検出方法:示差屈折率(RI)計
検量線:標準ポリスチレンを用いて作成
装置:日本電子株式会社製核磁気共鳴装置「JNM-LA400」
重溶媒:重水素化クロロホルム
(3)ブロック共重合体の屈折率の測定
装置:カルニュー光学工業株式会社「KPR-200」
測定波長:587.6nm(d線)
ISO14782に準拠して、厚さ3mmのシートのヘイズを測定した。
(5)メタクリル樹脂組成物の耐衝撃性の評価
ISO179-1eUに準拠して、ノッチなしのシャルピー衝撃強度を測定した。
(6)弾性率の評価
ISO178に準拠して測定した
引張破断伸度、引張弾性率ともに引張り試験通則 ISO 527-1 (JISK7161)に準拠して測定した。
(8)メタクリル樹脂組成物の溶融混練
東洋精機株式会社製 ラボプラストミル/R60型ミキサーを用いて 230℃、70rpm、3分間の条件で混練した。
(9)メルトフローレート
ISO1173に準拠して、230℃、37.3Nの条件でメルトフローレート(MFR)を測定した。
東邦マシナリー株式会社製 油圧成形機を用いて、230℃にてプレス成形した。
(11)メタクリル樹脂の射出成形
株式会社日本製鋼所製 75SAV型射出成形機を用いて、シリンダー温度200℃、金型温度60℃の条件で、物性試験片を得た。
(1) 1リットルの三口フラスコに三方コックを付けて内部を脱気し、窒素で置換した後、室温にてトルエン776ml 、1,2-ジメトキシエタン46.0ml、およびイソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウム8.8mmolを含有するトルエン溶液19.6mlを加え、さらにsec-ブチルリチウム1.8mmolを加えた。これにメタクリル酸メチル45.3mlを加え、室温で1時間反応させた。引き続き、重合液の内部温度を-15℃に冷却し、アクリル酸n-ブチル53.9mlとアクリル酸ベンジル11.3mlとの混合液を1時間かけて滴下した。続いてメタクリル酸メチル18.8mlを加えて反応液を室温に昇温し、5時間攪拌した。この反応液を大量のメタノール中に注ぎ、析出した沈殿物を回収し、アクリル系ブロック共重合体B-1を得た。
(2) 上記(1)で得られた沈殿物についてGPC測定および1H-NMRによりMn(数平均分子量)、Mw/Mn(分子量分布)、メタクリル酸メチル重合体(PMMA)ブロックとアクリル酸n-ブチルとアクリル酸ベンジルからなる共重合体ブロック(PnBA-co-PBzA)の質量比などを求めた。
(3) 上記(1)で得られたアクリル系ブロック共重合体B-1を、真空乾燥機にて80℃で12時間乾燥させた後、熱プレスにて厚さ3mmの成形体とし、屈折率測定を行った。評価結果を表1に示す。
(1) 実施例1において、アクリル酸n-ブチルの量を50.5ml、アクリル酸ベンジルの量を14.2mlに変更する以外は 、実施例1と同じ方法によってアクリル系ブロック共重合体B-2を得た。評価結果を表1に示す。
(1) 実施例1において、アクリル酸n-ブチルの量を47.1ml、アクリル酸ベンジルの量を17.0mlに変更する以外は 、実施例1と同じ方法によってアクリル系ブロック共重合体B-3を得た。評価結果を表1に示す。
(1) 1リットルの三口フラスコに三方コックを付けて内部を脱気し、窒素で置換した後、室温にてトルエン776ml 、1,2-ジメトキシエタン46.0ml、およびイソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウム9.4mmolを含有するトルエン溶液21.0mlを加え、さらにsec-ブチルリチウム1.9mmolを加えた。これにメタクリル酸メチル19.2mlを加え、室温で1時間反応させた。引き続き、重合液の内部温度を-15℃に冷却し、アクリル酸n-ブチル66.0mlとアクリル酸ベンジル23.8mlとの混合液を1時間かけて滴下した。続いてメタクリル酸メチル19.2mlを加えて反応液を室温に昇温し、5時間攪拌した。この反応液を大量のメタノール中に注ぎ、析出した沈殿物を回収し、アクリル系ブロック共重合体B-4を得た。評価結果を表1に示す。
(1) 実施例1において、アクリル酸n-ブチルの量を67.3mlに変更、アクリル酸ベンジルを添加しないこと以外は 、実施例1と同じ方法によってアクリル系ブロック共重合体B-5を得た。評価結果を表1に示す。
実施例4において、アクリル酸n-ブチルの量を94.3mlに変更、アクリル酸ベンジルを添加しないこと以外は 、実施例4と同じ方法によってアクリル系ブロック共重合体B-6を得た。評価結果を表1に示す。
(1) 実施例1において、アクリル酸n-ブチルの量を60.6ml、アクリル酸ベンジルの量を5.7mlに変更する以外は 、実施例1と同じ方法によってアクリル系ブロック共重合体B-7を得た。評価結果を表1に示す。
(1) 実施例1において、アクリル酸n-ブチルの量を26.9ml、アクリル酸ベンジルの量を34.0mlに変更する以外は 、実施例1と同じ方法によってアクリル系ブロック共重合体B-8を得た。評価結果を表1に示す。
(1) 1リットルの三口フラスコに三方コックを付けて内部を脱気し、窒素で置換した後、室温にてトルエン776ml、1,2-ジメトキシエタン46.0ml、およびイソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウム8.8mmolを含有するトルエン溶液19.6mlを加え、さらにsec-ブチルリチウム1.8mmolを加えた。これにメタクリル酸メチル31.7mlとメタクリル酸ベンジル12.2mlとの混合液を加え、室温で1時間反応させた。引き続き、重合液の内部温度を-15℃に冷却し、アクリル酸n-ブチル67.3mlを1時間かけて滴下した。続いてメタクリル酸メチル13.2mlとメタクリル酸ベンジル5.1mlとを加えて反応液を室温に昇温し、5時間攪拌した。この反応液を大量のメタノール中に注ぎ、析出した沈殿物を回収し、アクリル系ブロック共重合体B-9を得た。評価結果を表1に示す。
(1) 実施例1~3および比較例1、3、4および参考例1で得られたブロック共重合体(B)を表2記載の割合でメタクリル樹脂(A)(株式会社クラレ製:パラペットGH-F)と混合し、ラボプラストミルにて溶融混練してメタクリル樹脂組成物Cを製造した。
(2) 上記(1)で得られたメタクリル樹脂組成物Cを熱ブレスあるいは射出成形し、厚さ3mmあるいは4mmの成形体を得た。この成形体の評価結果を表2に示す。
メタクリル樹脂(A)(株式会社クラレ製:パラペットGH-F、メタクリル樹脂組成物C-9と称する)を熱ブレスし、厚さ3mmあるいは4mmの成形体を得た。この成形体の評価結果を表2に示す。
(1) 実施例3、4および比較例1、2で得られたブロック共重合体(B)を表3記載の割合でメタクリル樹脂(A)(株式会社クラレ製:パラペットGH-S)と混合し、ラボプラストミルにて溶融混練してメタクリル樹脂組成物C-10~C-13を製造した。
(2) 上記(1)で得られたメタクリル樹脂組成物C-10~C-13を熱ブレスし、厚さ3mmの成形体を得た。この成形体の評価結果を表3に示す。
Claims (10)
- メタクリル酸メチル単位を80質量%以上有するメタクリル樹脂(A)10~99質量部、およびメタクリル酸メチル重合体ブロック(b1)10~60質量%とアクリル酸エステル重合体ブロック(b2)90~40質量%とを有し、屈折率が1.485~1.495であるブロック共重合体(B)90~1質量部を含む(ただし、(A)と(B)との合計が100質量部)メタクリル樹脂組成物。
- アクリル酸エステル重合体ブロック(b2)が、アクリル酸アルキルエステル50~90質量%と(メタ)アクリル酸芳香族エステル50~10質量%との共重合体ブロックである請求項1に記載のメタクリル樹脂組成物。
- (メタ)アクリル酸芳香族エステルがアクリル酸ベンジルである請求項2に記載のメタクリル樹脂組成物。
- 上記メタクリル樹脂組成物から得られる厚さ3mmの成形体のヘイズ値が2%以下である請求項1に記載のメタクリル樹脂組成物。
- アクリル酸エステル重合体ブロック(b2)がメタクリル樹脂組成物全体に対し5~20質量%であり、MFRが20g/10分以上である請求項4に記載のメタクリル樹脂組成物。
- メタクリル酸メチル重合体ブロック(a)10~60質量%と、アクリル酸エステル重合体ブロック(b)90~40質量%とを有し、屈折率が1.485~1.495であるブロック共重合体(B)からなる樹脂改質剤。
- アクリル酸エステル重合体ブロック(b)が、アクリル酸アルキルエステル50~90質量%と(メタ)アクリル酸芳香族エステル50~10質量%からなる請求項6に記載の樹脂改質剤。
- (メタ)アクリル酸芳香族エステルがアクリル酸ベンジルである請求項6に記載の樹脂改質剤。
- 請求項1に記載のメタクリル樹脂組成物からなる成形体。
- 射出成形体である請求項9に記載の成形体。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180052239.8A CN103180382B (zh) | 2010-10-29 | 2011-10-24 | 甲基丙烯酸树脂组合物和树脂改性剂以及成形体 |
JP2012540844A JP5855009B2 (ja) | 2010-10-29 | 2011-10-24 | メタクリル樹脂組成物及び樹脂改質剤並びに成形体 |
KR1020137012956A KR101790382B1 (ko) | 2010-10-29 | 2011-10-24 | 메타크릴 수지 조성물 및 수지 개질제 그리고 성형체 |
EP11836213.6A EP2634214B1 (en) | 2010-10-29 | 2011-10-24 | Methacrylic resin composition, resin modifier, and molded body |
US13/881,310 US9527994B2 (en) | 2010-10-29 | 2011-10-24 | Methacrylic resin composition, resin modifier, and molded article |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010244502 | 2010-10-29 | ||
JP2010-244502 | 2010-10-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012057079A1 true WO2012057079A1 (ja) | 2012-05-03 |
Family
ID=45993787
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/074434 WO2012057079A1 (ja) | 2010-10-29 | 2011-10-24 | メタクリル樹脂組成物及び樹脂改質剤並びに成形体 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9527994B2 (ja) |
EP (1) | EP2634214B1 (ja) |
JP (3) | JP5855009B2 (ja) |
KR (1) | KR101790382B1 (ja) |
CN (1) | CN103180382B (ja) |
TW (2) | TWI550013B (ja) |
WO (1) | WO2012057079A1 (ja) |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013171275A2 (en) | 2012-05-16 | 2013-11-21 | Novopolymers N.V. | Polymer sheet |
WO2014073216A1 (ja) | 2012-11-09 | 2014-05-15 | 株式会社クラレ | メタクリル樹脂組成物 |
WO2015076398A1 (ja) * | 2013-11-25 | 2015-05-28 | 株式会社クラレ | アクリル系樹脂フィルム |
CN104797638A (zh) * | 2012-11-09 | 2015-07-22 | 株式会社可乐丽 | 甲基丙烯酸类树脂组合物 |
WO2015107954A1 (ja) | 2014-01-14 | 2015-07-23 | 株式会社クラレ | 共重合体および成形体 |
JP2015157876A (ja) * | 2014-02-21 | 2015-09-03 | 株式会社クラレ | メタクリル樹脂組成物からなる板状成形体 |
JP2015172118A (ja) * | 2014-03-11 | 2015-10-01 | 三菱化学株式会社 | ヨウ素末端ポリマー及びその製造方法、並びにブロックコポリマー及びその製造方法 |
WO2015182750A1 (ja) * | 2014-05-30 | 2015-12-03 | 株式会社クラレ | メタクリル樹脂組成物 |
WO2016002750A1 (ja) * | 2014-06-30 | 2016-01-07 | 株式会社クラレ | メタクリル樹脂またはメタクリル樹脂組成物 |
JP2016008225A (ja) * | 2014-06-23 | 2016-01-18 | 株式会社クラレ | メタクリル系樹脂組成物、成形体、樹脂フィルム、偏光子保護フィルム、および位相差フィルム |
JP2016020415A (ja) * | 2014-07-14 | 2016-02-04 | 三菱レイヨン株式会社 | アクリル系エラストマー樹脂用加工助剤、アクリル系エラストマー樹脂組成物及び成形体 |
JP2016037575A (ja) * | 2014-08-08 | 2016-03-22 | 株式会社クラレ | 硬化型シーリング剤 |
JP2016071218A (ja) * | 2014-09-30 | 2016-05-09 | 株式会社カネカ | 光学フィルム |
WO2016080124A1 (ja) * | 2014-11-19 | 2016-05-26 | 株式会社クラレ | アクリル系フィルム |
WO2016139950A1 (ja) * | 2015-03-05 | 2016-09-09 | 株式会社クラレ | 樹脂組成物、フィルムおよびそれらの製造方法、成形体、並びに物品 |
WO2016190138A1 (ja) * | 2015-05-22 | 2016-12-01 | 株式会社クラレ | アクリル系ブロック共重合体とそれからなる樹脂組成物および成形体並びに光学部材 |
US10385201B2 (en) | 2015-04-03 | 2019-08-20 | Kuraray Co., Ltd. | Resin composite, method of producing the resin, molded product, film, and article |
JP2020166067A (ja) * | 2019-03-28 | 2020-10-08 | フクビ化学工業株式会社 | 周面発光型導光棒 |
WO2021015226A1 (ja) * | 2019-07-25 | 2021-01-28 | 株式会社クラレ | メタクリル系溶融押出成形体 |
CN114096608A (zh) * | 2019-06-27 | 2022-02-25 | 株式会社可乐丽 | 甲基丙烯酸类树脂组合物及其成型品、膜的制造方法 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9527994B2 (en) | 2010-10-29 | 2016-12-27 | Kuraray Co., Ltd. | Methacrylic resin composition, resin modifier, and molded article |
TWI655216B (zh) * | 2014-08-06 | 2019-04-01 | Kuraray Co., Ltd. | (甲基)丙烯酸樹脂組成物之製造方法 |
JP6912461B2 (ja) * | 2016-05-18 | 2021-08-04 | 株式会社クラレ | 多層フィルム |
EP3584280A4 (en) * | 2017-02-16 | 2020-12-30 | Kuraray Co., Ltd. | RESIN COMPOSITION COMPRISING AN ACRYLIC BLOCK COPOLYMER AND A LIGHT SCATTERING AGENT |
WO2019054412A1 (ja) * | 2017-09-15 | 2019-03-21 | 住友化学株式会社 | 硬化性組成物 |
JP6726811B2 (ja) * | 2018-06-12 | 2020-07-22 | 株式会社クラレ | アクリル系ブロック共重合体ペレットの製造方法 |
EP3783040A4 (en) * | 2018-08-31 | 2021-07-07 | Denka Company Limited | COPOLYMER OF CHLOROPRENE MONOMER AND UNSATURATED NITRILE COMPOUND, COMPOSITION WITH COPOLYMER, VULCANIZATION MOLDED BODY AND USE OF THE VULCANIZED MOLDED BODY |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01261447A (ja) * | 1988-04-11 | 1989-10-18 | Mitsubishi Rayon Co Ltd | メタクリル樹脂組成物 |
JPH0693060A (ja) | 1992-09-09 | 1994-04-05 | Mitsubishi Petrochem Co Ltd | メタクリル系ブロック共重合体およびその製造方法 |
JPH0725859B2 (ja) | 1989-07-10 | 1995-03-22 | エルフ アトケム ソシエテ アノニム | アクリル系三元共重合体と、その製造方法と、そのエラストマー製品製造への応用 |
JPH10168271A (ja) | 1996-12-16 | 1998-06-23 | Kuraray Co Ltd | 重合体組成物 |
JPH11335432A (ja) | 1998-03-23 | 1999-12-07 | Kuraray Co Ltd | アクリル系ブロック共重合体の製造方法 |
JP2000154329A (ja) | 1998-09-16 | 2000-06-06 | Kanegafuchi Chem Ind Co Ltd | 熱可塑性樹脂組成物 |
JP2002241568A (ja) * | 2001-02-19 | 2002-08-28 | Kanegafuchi Chem Ind Co Ltd | 熱可塑性樹脂組成物、およびフィルムまたはシート |
JP2003277574A (ja) | 2002-03-27 | 2003-10-02 | Kuraray Co Ltd | アクリル系重合体組成物 |
JP2006124724A (ja) | 2002-02-13 | 2006-05-18 | Kaneka Corp | ブロック共重合体 |
JP2007512413A (ja) | 2003-11-26 | 2007-05-17 | アーケマ・インコーポレイテッド | 精密ラジカル法アクリル共重合体増粘剤 |
WO2009054553A2 (en) * | 2008-12-25 | 2009-04-30 | Kuraray Co., Ltd. | Optical component comprising acrylic block copolymer |
WO2010055798A1 (ja) | 2008-11-11 | 2010-05-20 | 株式会社クラレ | 熱可塑性重合体組成物およびそれからなるシート状成形体 |
JP2011153243A (ja) * | 2010-01-28 | 2011-08-11 | Toray Ind Inc | 太陽電池封止材用シート |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2265310C (en) | 1998-03-23 | 2007-12-18 | Kuraray Co., Ltd. | Preparation process of acrylic acid ester polymer |
JP2002509948A (ja) * | 1998-03-30 | 2002-04-02 | カーネギー・メロン・ユニヴァーシティー | 水を媒体とする重合系への原子転移ラジカル重合の応用 |
US6121371A (en) | 1998-07-31 | 2000-09-19 | Carnegie Mellon University | Application of atom transfer radical polymerization to water-borne polymerization systems |
US6989190B2 (en) * | 2000-10-17 | 2006-01-24 | General Electric Company | Transparent polycarbonate polyester composition and process |
US20030139530A1 (en) * | 2001-12-14 | 2003-07-24 | Starita Joseph M. | Melt blended high density polyethylene compositions with enhanced properties and method for producing the same |
TWI314934B (en) | 2002-02-13 | 2009-09-21 | Kaneka Corporatio | Polymer composition |
JP2006503950A (ja) * | 2002-10-21 | 2006-02-02 | アルケマ | 非晶質マトリックスとブロックコポリマーとを含む延性があり且つ透明な熱可塑性組成物 |
US8163844B2 (en) | 2006-09-15 | 2012-04-24 | Kuraray Co., Ltd. | Methacrylic resin composition, resin modifier, and molded article |
FR2912967B1 (fr) | 2007-02-23 | 2009-12-18 | Arkema France | Dispositif projecteur a base d'un copolymere a blocs |
JP5416438B2 (ja) * | 2008-03-11 | 2014-02-12 | 株式会社クラレ | メタクリル系樹脂組成物からなる導光体 |
KR100886348B1 (ko) * | 2008-04-14 | 2009-03-03 | 제일모직주식회사 | 상용성이 개선된 난연 내스크래치 열가소성 수지 조성물 |
JP2010013613A (ja) | 2008-06-04 | 2010-01-21 | Toray Ind Inc | アクリル系ブロック共重合体、熱可塑性共重合体組成物およびそれからなる成形品 |
US9527994B2 (en) | 2010-10-29 | 2016-12-27 | Kuraray Co., Ltd. | Methacrylic resin composition, resin modifier, and molded article |
-
2011
- 2011-10-24 US US13/881,310 patent/US9527994B2/en active Active
- 2011-10-24 CN CN201180052239.8A patent/CN103180382B/zh active Active
- 2011-10-24 WO PCT/JP2011/074434 patent/WO2012057079A1/ja active Application Filing
- 2011-10-24 EP EP11836213.6A patent/EP2634214B1/en not_active Not-in-force
- 2011-10-24 JP JP2012540844A patent/JP5855009B2/ja active Active
- 2011-10-24 KR KR1020137012956A patent/KR101790382B1/ko active IP Right Grant
- 2011-10-27 TW TW104126030A patent/TWI550013B/zh active
- 2011-10-27 TW TW100139003A patent/TWI523908B/zh active
-
2015
- 2015-06-29 JP JP2015129817A patent/JP6173384B2/ja active Active
- 2015-06-29 JP JP2015129816A patent/JP5980381B2/ja active Active
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01261447A (ja) * | 1988-04-11 | 1989-10-18 | Mitsubishi Rayon Co Ltd | メタクリル樹脂組成物 |
JPH0725859B2 (ja) | 1989-07-10 | 1995-03-22 | エルフ アトケム ソシエテ アノニム | アクリル系三元共重合体と、その製造方法と、そのエラストマー製品製造への応用 |
JPH0693060A (ja) | 1992-09-09 | 1994-04-05 | Mitsubishi Petrochem Co Ltd | メタクリル系ブロック共重合体およびその製造方法 |
JPH10168271A (ja) | 1996-12-16 | 1998-06-23 | Kuraray Co Ltd | 重合体組成物 |
JPH11335432A (ja) | 1998-03-23 | 1999-12-07 | Kuraray Co Ltd | アクリル系ブロック共重合体の製造方法 |
JP2000154329A (ja) | 1998-09-16 | 2000-06-06 | Kanegafuchi Chem Ind Co Ltd | 熱可塑性樹脂組成物 |
JP2002241568A (ja) * | 2001-02-19 | 2002-08-28 | Kanegafuchi Chem Ind Co Ltd | 熱可塑性樹脂組成物、およびフィルムまたはシート |
JP2006124724A (ja) | 2002-02-13 | 2006-05-18 | Kaneka Corp | ブロック共重合体 |
JP2003277574A (ja) | 2002-03-27 | 2003-10-02 | Kuraray Co Ltd | アクリル系重合体組成物 |
JP2007512413A (ja) | 2003-11-26 | 2007-05-17 | アーケマ・インコーポレイテッド | 精密ラジカル法アクリル共重合体増粘剤 |
WO2010055798A1 (ja) | 2008-11-11 | 2010-05-20 | 株式会社クラレ | 熱可塑性重合体組成物およびそれからなるシート状成形体 |
WO2009054553A2 (en) * | 2008-12-25 | 2009-04-30 | Kuraray Co., Ltd. | Optical component comprising acrylic block copolymer |
JP2011153243A (ja) * | 2010-01-28 | 2011-08-11 | Toray Ind Inc | 太陽電池封止材用シート |
Non-Patent Citations (1)
Title |
---|
MACROMOL. CHEM. PHYS., vol. 201, 2000, pages 1108 - 1114 |
Cited By (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013171275A2 (en) | 2012-05-16 | 2013-11-21 | Novopolymers N.V. | Polymer sheet |
WO2013171272A2 (en) | 2012-05-16 | 2013-11-21 | Novopolymers N.V. | Multilayer encapsulant film for photovoltaic modules |
US9796844B2 (en) | 2012-11-09 | 2017-10-24 | Kuraray Co., Ltd. | Methacrylic resin composition |
CN104781339A (zh) * | 2012-11-09 | 2015-07-15 | 株式会社可乐丽 | 甲基丙烯酸类树脂组合物 |
CN104781339B (zh) * | 2012-11-09 | 2016-10-12 | 株式会社可乐丽 | 甲基丙烯酸类树脂组合物 |
KR20150082535A (ko) | 2012-11-09 | 2015-07-15 | 가부시키가이샤 구라레 | 메타크릴 수지 조성물 |
CN104797638A (zh) * | 2012-11-09 | 2015-07-22 | 株式会社可乐丽 | 甲基丙烯酸类树脂组合物 |
JPWO2014073216A1 (ja) * | 2012-11-09 | 2016-09-08 | 株式会社クラレ | メタクリル樹脂組成物 |
WO2014073216A1 (ja) | 2012-11-09 | 2014-05-15 | 株式会社クラレ | メタクリル樹脂組成物 |
EP2918636A1 (en) | 2012-11-09 | 2015-09-16 | Kuraray Co., Ltd. | Methacrylic resin composition |
EP2918636A4 (en) * | 2012-11-09 | 2016-05-25 | Kuraray Co | METHACRYLIC RESIN COMPOSITION |
US10619043B2 (en) | 2012-11-09 | 2020-04-14 | Kuraray Co., Ltd. | Methacrylic resin composition |
JPWO2015076398A1 (ja) * | 2013-11-25 | 2017-03-16 | 株式会社クラレ | アクリル系樹脂フィルム |
WO2015076398A1 (ja) * | 2013-11-25 | 2015-05-28 | 株式会社クラレ | アクリル系樹脂フィルム |
US10550234B2 (en) | 2013-11-25 | 2020-02-04 | Kuraray Co., Ltd. | Acrylic resin film |
KR20160090793A (ko) * | 2013-11-25 | 2016-08-01 | 주식회사 쿠라레 | 아크릴계 수지 필름 |
KR102167202B1 (ko) * | 2013-11-25 | 2020-10-19 | 주식회사 쿠라레 | 아크릴계 수지 필름 |
US10287380B2 (en) | 2014-01-14 | 2019-05-14 | Kuraray Co., Ltd. | Copolymer, and molded article |
WO2015107954A1 (ja) | 2014-01-14 | 2015-07-23 | 株式会社クラレ | 共重合体および成形体 |
KR20160108338A (ko) | 2014-01-14 | 2016-09-19 | 주식회사 쿠라레 | 공중합체 및 성형체 |
JP2015157876A (ja) * | 2014-02-21 | 2015-09-03 | 株式会社クラレ | メタクリル樹脂組成物からなる板状成形体 |
JP2015172118A (ja) * | 2014-03-11 | 2015-10-01 | 三菱化学株式会社 | ヨウ素末端ポリマー及びその製造方法、並びにブロックコポリマー及びその製造方法 |
WO2015182750A1 (ja) * | 2014-05-30 | 2015-12-03 | 株式会社クラレ | メタクリル樹脂組成物 |
JPWO2015182750A1 (ja) * | 2014-05-30 | 2017-04-20 | 株式会社クラレ | メタクリル樹脂組成物 |
JP2016008225A (ja) * | 2014-06-23 | 2016-01-18 | 株式会社クラレ | メタクリル系樹脂組成物、成形体、樹脂フィルム、偏光子保護フィルム、および位相差フィルム |
KR20170024583A (ko) * | 2014-06-30 | 2017-03-07 | 주식회사 쿠라레 | 메타크릴 수지 또는 메타크릴 수지 조성물 |
WO2016002750A1 (ja) * | 2014-06-30 | 2016-01-07 | 株式会社クラレ | メタクリル樹脂またはメタクリル樹脂組成物 |
JPWO2016002750A1 (ja) * | 2014-06-30 | 2017-04-27 | 株式会社クラレ | メタクリル樹脂またはメタクリル樹脂組成物 |
US10526430B2 (en) | 2014-06-30 | 2020-01-07 | Kuraray Co., Ltd. | Methacrylic resin or methacrylic resin composition |
KR102394025B1 (ko) | 2014-06-30 | 2022-05-03 | 주식회사 쿠라레 | 메타크릴 수지 또는 메타크릴 수지 조성물 |
JP2016020415A (ja) * | 2014-07-14 | 2016-02-04 | 三菱レイヨン株式会社 | アクリル系エラストマー樹脂用加工助剤、アクリル系エラストマー樹脂組成物及び成形体 |
JP2016037575A (ja) * | 2014-08-08 | 2016-03-22 | 株式会社クラレ | 硬化型シーリング剤 |
JP2016071218A (ja) * | 2014-09-30 | 2016-05-09 | 株式会社カネカ | 光学フィルム |
JPWO2016080124A1 (ja) * | 2014-11-19 | 2017-08-31 | 株式会社クラレ | アクリル系フィルム |
WO2016080124A1 (ja) * | 2014-11-19 | 2016-05-26 | 株式会社クラレ | アクリル系フィルム |
JPWO2016139950A1 (ja) * | 2015-03-05 | 2017-12-14 | 株式会社クラレ | 樹脂組成物、フィルムおよびそれらの製造方法、成形体、並びに物品 |
US10329394B2 (en) | 2015-03-05 | 2019-06-25 | Kuraray Co., Ltd. | Resin composite, film, methods of producing the resin composite and the film, molded product, and article |
WO2016139950A1 (ja) * | 2015-03-05 | 2016-09-09 | 株式会社クラレ | 樹脂組成物、フィルムおよびそれらの製造方法、成形体、並びに物品 |
US10385201B2 (en) | 2015-04-03 | 2019-08-20 | Kuraray Co., Ltd. | Resin composite, method of producing the resin, molded product, film, and article |
KR20180011155A (ko) | 2015-05-22 | 2018-01-31 | 주식회사 쿠라레 | 아크릴계 블록 공중합체와 그것으로 이루어지는 수지 조성물 및 성형체 그리고 광학 부재 |
US10563001B2 (en) | 2015-05-22 | 2020-02-18 | Kuraray Co., Ltd. | Acrylic block copolymer, resin composition and shaped article including the same, and optical component |
JPWO2016190138A1 (ja) * | 2015-05-22 | 2018-03-08 | 株式会社クラレ | アクリル系ブロック共重合体とそれからなる樹脂組成物および成形体並びに光学部材 |
WO2016190138A1 (ja) * | 2015-05-22 | 2016-12-01 | 株式会社クラレ | アクリル系ブロック共重合体とそれからなる樹脂組成物および成形体並びに光学部材 |
JP2020166067A (ja) * | 2019-03-28 | 2020-10-08 | フクビ化学工業株式会社 | 周面発光型導光棒 |
JP7175823B2 (ja) | 2019-03-28 | 2022-11-21 | フクビ化学工業株式会社 | 周面発光型導光棒 |
CN114096608A (zh) * | 2019-06-27 | 2022-02-25 | 株式会社可乐丽 | 甲基丙烯酸类树脂组合物及其成型品、膜的制造方法 |
EP3992243A1 (en) * | 2019-06-27 | 2022-05-04 | Kuraray Co., Ltd. | Methacrylic resin composition, molded article of same, and method for producing film |
EP3992243A4 (en) * | 2019-06-27 | 2023-06-14 | Kuraray Co., Ltd. | METHACRYLIC RESIN COMPOSITION, MOLDED ARTICLE THEREOF, AND FILM PRODUCTION METHOD |
CN114096608B (zh) * | 2019-06-27 | 2023-10-10 | 株式会社可乐丽 | 甲基丙烯酸类树脂组合物及其成型品、膜的制造方法 |
WO2021015226A1 (ja) * | 2019-07-25 | 2021-01-28 | 株式会社クラレ | メタクリル系溶融押出成形体 |
Also Published As
Publication number | Publication date |
---|---|
TWI523908B (zh) | 2016-03-01 |
EP2634214A4 (en) | 2015-11-18 |
CN103180382B (zh) | 2015-04-01 |
TWI550013B (zh) | 2016-09-21 |
JP2015166474A (ja) | 2015-09-24 |
TW201224045A (en) | 2012-06-16 |
US20130217827A1 (en) | 2013-08-22 |
US9527994B2 (en) | 2016-12-27 |
EP2634214A1 (en) | 2013-09-04 |
JPWO2012057079A1 (ja) | 2014-05-12 |
JP5855009B2 (ja) | 2016-02-09 |
KR20130130725A (ko) | 2013-12-02 |
JP6173384B2 (ja) | 2017-08-02 |
CN103180382A (zh) | 2013-06-26 |
JP5980381B2 (ja) | 2016-08-31 |
TW201542667A (zh) | 2015-11-16 |
EP2634214B1 (en) | 2018-07-18 |
JP2015166475A (ja) | 2015-09-24 |
KR101790382B1 (ko) | 2017-10-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6173384B2 (ja) | メタクリル樹脂組成物及び樹脂改質剤並びに成形体 | |
JP3828447B2 (ja) | アクリル系重合体組成物 | |
JP5649974B2 (ja) | 熱可塑性重合体組成物およびそれからなるシート状成形体 | |
TWI703166B (zh) | 由丙烯酸系嵌段共聚物所構成之樹脂組成物及成形體以及光學構件 | |
TWI609912B (zh) | (甲基)丙烯酸樹脂組成物之製造方法、光學構件之製造方法及偏光板之製造方法 | |
WO2022230482A1 (ja) | 熱可塑性エラストマー組成物、成形品、積層構造体及び該積層構造体の製造方法 | |
JP2015209504A (ja) | 透明塩化ビニル系樹脂組成物およびその成形品 | |
JP4340493B2 (ja) | アクリル系ブロック共重合体組成物 | |
WO2018143211A1 (ja) | 成形体およびその製造方法 | |
JP6796969B2 (ja) | 熱可塑性重合体組成物及び成形体 | |
JP2013125134A (ja) | 反射材 | |
JP2020169294A (ja) | 塩化ビニル系樹脂組成物及び成形品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11836213 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2012540844 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13881310 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137012956 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011836213 Country of ref document: EP |