Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
• • 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
  • C08F220/42—Nitriles
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/36—Amides or imides
  • C08F222/40—Imides, e.g. cyclic imides
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
  • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L35/06—Copolymers with vinyl aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
  • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
• • 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
  • B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
  • B29K2079/08—PI, i.e. polyimides or derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
  • B29L2031/3005—Body finishings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
  • B29L2031/3055—Cars
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/50—Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C

Definitions

• the present invention relates to a maleimide-based copolymer, a maleimide-based copolymer composition, a resin composition, and an injection-molded article.
• ABS resin Acrylonitrile-butadiene-styrene copolymer resin
• ABS resin containing a maleimide-based copolymer is also used as a heat-resistant material in applications that require heat resistance, such as automobile interior materials (for example, Patent Document 1 and Patent Document 2).
• ABS resin containing a maleimide-based copolymer has a drawback of low chemical resistance, and in order to overcome this, a maleimide-based copolymer in which a vinyl cyanide monomer is copolymerized has been proposed (for example,).
• Patent Document 3 Patent Document 4).
• Japanese Unexamined Patent Publication No. 57-98536 Japanese Unexamined Patent Publication No. 57-125242
• Japanese Unexamined Patent Publication No. 2004-339280 Japanese Unexamined Patent Publication No. 2007-9228
• the currently proposed maleimide-based copolymer copolymerized with a vinyl cyanide monomer has been required to have high heat resistance while improving fluidity during molding. Further, the maleimide-based copolymer containing the vinyl cyanide monomer tends to be colored yellow, which has been a problem especially when the molded product is used for white applications.
• a maleimide-based copolymer and a maleimide-based copolymer using the same can be obtained as a resin composition having excellent fluidity and low yellowness (YI) while maintaining a balance between heat resistance and impact resistance.
• An object of the present invention is to provide a polymer composition, a resin composition, and an injection molded product.
• the present invention has the following gist.
• the maleimide-based copolymer has an aromatic vinyl monomer unit of 40 to 60% by mass and a cyanide vinyl monomer unit of 5 to 20% by mass as the monomer unit constituting the maleimide-based copolymer.
• a maleimide-based copolymer composition containing 0 to 20 parts by mass of a copolymer containing an aromatic vinyl monomer unit.
• a maleimide-based copolymer capable of obtaining a resin composition having excellent fluidity and low yellowness (YI) while maintaining a balance between heat resistance and impact resistance, and a maleimide-based copolymer using the same.
• Copolymer compositions, resin compositions and injection molded products are provided.
• the maleimide-based copolymer of the present invention is obtained by copolymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and a maleimide monomer.
• the aromatic vinyl monomer that can be used for the maleimide-based copolymer is used to improve the hue of the maleimide-based copolymer, and is used, for example, styrene, o-methylstyrene, m-methylstyrene, p. -There are methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, ⁇ -methylstyrene, ⁇ -methyl-p-methylstyrene and the like. Among these, styrene, which has a high effect of improving hue, is preferable.
• the aromatic vinyl monomer may be used alone or in combination of two or more.
• the amount of the aromatic vinyl monomer unit contained in 100% by mass of the maleimide-based copolymer is preferably 40 to 60% by mass, more preferably 45 to 55% by mass. Specifically, for example, it is 40, 45, 46, 47, 48, 49, 50, 55, 60% by mass, and may be within the range between any two of the numerical values exemplified here. If the amount of the aromatic vinyl monomer unit is less than 40% by mass, the yellowness (YI) of the maleimide-based copolymer may increase, and if it exceeds 60% by mass, the heat resistance of the maleimide-based copolymer becomes high. May decrease.
• YI yellowness
• the vinyl cyanide monomer that can be used for the maleimide-based copolymer is used to improve the fluidity and chemical resistance of the maleimide-based copolymer, and is used, for example, acrylonitrile, methacrylonitrile, and etacrylo. There are nitriles, fumaronitrile, etc. Among these, acrylonitrile, which has a high effect of improving chemical resistance, is preferable.
• the vinyl cyanide monomer may be used alone or in combination of two or more.
• the amount of the vinyl cyanide monomer unit contained in 100% by mass of the maleimide-based copolymer is preferably 5 to 20% by mass, more preferably 7 to 15% by mass. Specifically, for example, it is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20% by mass, and is within the range between any two of the numerical values exemplified here. You may. If the amount of vinyl cyanide monomer unit is less than 5% by mass, the effect of improving chemical resistance may not be obtained, and if it exceeds 20% by mass, the yellowness (YI) of the maleimide-based copolymer will increase. It may be expensive.
• Maleimide monomers that can be used for maleimide-based copolymers are used to improve the heat resistance of maleimide-based copolymers, and are, for example, N-methylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide.
• N-alkylmaleimide, N-phenylmaleimide, N-chlorphenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, N-tribromophenylmaleimide and the like are preferable.
• the maleimide monomer may be used alone or in combination of two or more.
• the maleimide-based copolymer contains a maleimide monomer unit
• a raw material made of a maleimide monomer may be copolymerized with another monomer.
• a copolymer obtained by copolymerizing a raw material composed of an unsaturated dicarboxylic acid monomer unit with another monomer may be imidized with ammonia or a primary amine.
• the amount of the maleimide monomer unit contained in 100% by mass of the maleimide-based copolymer is preferably 30 to 50% by mass, more preferably 37 to 45% by mass. Specifically, for example, it is 30, 35, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50% by mass, and is within the range between any two of the numerical values exemplified here. May be. If the amount of the maleimide monomer unit is less than 30% by mass, the effect of improving the heat resistance may not be obtained, and if it exceeds 50% by mass, the impact strength of the maleimide-based copolymer may decrease.
• the maleimide-based copolymer may be copolymerized with a copolymerizable monomer other than the aromatic vinyl monomer, the cyanated vinyl monomer and the maleimide monomer as long as the effect of the present invention is not impaired. good.
• the monomers copolymerizable with the maleimide-based copolymer are unsaturated dicarboxylic acid anhydride monomers such as maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, and aconitic acid anhydride, and methylacrylic acid.
• Acrylic acid ester monomer such as ester, ethylacrylic acid ester, butylacrylic acid ester, methacrylic acid ester monomer such as methylmethacrylic acid ester, ethylacrylic acid ester, vinylcarboxylic acid single amount such as acrylic acid and methacrylic acid
• the body, acrylic acid amide, methacrylic acid amide and the like can be mentioned.
• the monomer copolymerizable with the maleimide-based copolymer may be used alone or in combination of two or more.
• an unsaturated dicarboxylic acid anhydride monomer is preferable.
• the unsaturated dicarboxylic acid unit can be combined with other polymers having an amino group or an alcohol group terminal. It reacts and the effect as a compatibilizer is obtained.
• the unsaturated dicarboxylic acid anhydride monomer unit is 10% by mass or less, it is preferable because it is excellent in thermal stability, and when the unsaturated dicarboxylic acid anhydride monomer unit is 5% by mass or less, it is further thermal stability. It is preferable because it is excellent in. Specifically, for example, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 2, It is 3, 4, 5, 6, 7, 8, 9, and 10 parts by mass, and may be within the range between any two of the numerical values exemplified here.
• the yellowness (YI) of the maleimide-based copolymer is preferably 0.5 to 3.5, more preferably 2.0 to 3.0. Specifically, for example, 0.5, 1.0, 1.5, 2.0, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, It is 3.2, 3.3, 3.4, 3.5, and may be within the range between any two of the numerical values exemplified here.
• the yellowness of the maleimide-based copolymer can be adjusted, for example, by the weight average molecular weight of the maleimide-based copolymer.
• the yellowness is lowered by reducing the weight average molecular weight of the maleimide-based copolymer, but if the yellowness is less than 0.5, the heat resistance of the maleimide-based copolymer is lowered. Further, the yellowness is increased by increasing the weight average molecular weight of the maleimide-based copolymer, but when the yellowness exceeds 3.5, the fluidity of the maleimide-based copolymer is lowered. In addition, the yellowness may be adjusted by adjusting the amount of the aromatic vinyl monomer unit and the cyanide vinyl monomer unit contained in the maleimide-based copolymer, and the amount of the residual maleimide monomer. Is possible.
• the yellowness (YI) of the maleimide-based copolymer is a value measured by the following procedure according to JIS K-7373. Dissolve 1 g of the maleimide-based copolymer in 25 mL of tetrahydrofuran. After melting, transfer to a square cell for measurement. The color difference is obtained by using a transmission method using a CIE standard D65 light source under the conditions of a temperature of 23 ° C. and a humidity of 50%, using a square cell of a tetrahydrofuran solution as a blank, and the value is defined as yellowness.
• the melt mass flow rate of the maleimide-based copolymer is preferably 25 to 90 g / 10 minutes, more preferably 65 to 80 g / 10 minutes. Specifically, for example, 25, 30, 35, 40, 45, 50, 55, 60, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 80, 85, 90 g / It is 10 minutes and may be within the range between any two of the numerical values exemplified here. If it is less than 25 g / 10 minutes, the fluidity of the mixed resin may decrease, and if it exceeds 90 g / 10 minutes, the impact resistance may decrease.
• the melt mass flow rate is a value measured at 265 ° C. and 10 kg according to JIS K-7210.
• the amount of residual maleimide monomer contained in the maleimide-based copolymer is preferably less than 300 ppm, more preferably less than 200 ppm. When the amount of residual maleimide monomer is 300 ppm or more, the yellowness (YI) of the obtained maleimide-based copolymer may increase.
• the amount of residual maleimide monomer is a value measured under the conditions described below.
• Device name Gas chromatograph GC-2010 (manufactured by Shimadzu Corporation)
• a temperature rise analysis is performed at a column temperature of 80 ° C. (initial).
• the weight average molecular weight of the maleimide-based copolymer is 50,000 to 110,000, preferably 70,000 to 100,000. Specifically, it is, for example, 5, 6, 7, 8, 9, 10, 110,000, and may be within the range between any two of the numerical values exemplified here. If the weight average molecular weight is less than 50,000, the impact resistance is lowered, and if it exceeds 110,000, the fluidity is lowered.
• the weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC), and can be measured under the following conditions.
• the midpoint glass transition temperature (Tmg) of the maleimide-based copolymer is 165 ° C to 200 ° C, preferably 165 ° C to 200 ° C, from the viewpoint of efficiently improving the heat resistance of the kneaded and mixed resin such as ABS resin and ASA resin.
• the temperature is 170 ° C to 200 ° C. Specifically, for example, it is 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 180, 185, 190, 195, 200 ° C., and any of the numerical values exemplified here 2 It may be within the range between the two.
• the intermediate point glass transition temperature (Tmg) is a measured value under the measurement conditions described below according to JIS K-7121.
• Device name Differential scanning calorimeter Robot DSC6200 (manufactured by Seiko Instruments Inc.) Temperature rise rate: 10 ° C / min
• Tmg midpoint glass transition temperature
• the polymerization mode of the maleimide-based copolymer includes, for example, solution polymerization, bulk polymerization and the like.
• Solution polymerization is preferable from the viewpoint that a maleimide-based copolymer having a more uniform copolymer composition can be obtained by polymerizing while performing addition or the like.
• the solvent for solution polymerization is preferably non-polymerizable from the viewpoint that by-products are difficult to form and adverse effects are small.
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetophenone
• ethers such as tetrahydrofuran and 1,4-dioxane
• aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide and dimethyl.
• Acetone, N-methyl-2-pyrrolidone, etc., and methyl ethyl ketone and methyl isobutyl ketone are preferable because of the ease of solvent removal at the time of volatilization recovery of the maleimide-based copolymer.
• any of continuous polymerization type, batch type (batch type) and semi-batch type can be applied.
• the method for producing the maleimide-based copolymer is not particularly limited, but it can be preferably obtained by radical polymerization, and the polymerization temperature is preferably in the range of 80 to 150 ° C.
• the polymerization initiator is not particularly limited, but known azo compounds such as azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobismethylpropionitrile, and azobismethylbutyronitrile, and benzoyl.
• Peroxide t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethyl
• organic peroxides such as hexanoate, di-t-butyl peroxide, dicumyl peroxide, ethyl-3,3-di- (t-butylperoxy) butyrate can be used, and one of these Seeds or a combination of two or more may be used.
• the amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 to 1.5% by mass, more preferably 0.1 to 1.5% by mass with respect to 100% by mass of all the monomer units. It is 1.0% by mass.
• the amount of the polymerization initiator used is 0.1% by mass or more, a sufficient polymerization rate can be obtained, which is preferable.
• the amount of the polymerization initiator used is 1.5% by mass or less, the polymerization rate can be suppressed, so that reaction control becomes easy and it becomes easy to obtain a target molecular weight.
• a chain transfer agent can be used in the production of the maleimide-based copolymer.
• the chain transfer agent used is not particularly limited, and examples thereof include n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, ⁇ -methylstyrene dimer, ethyl thioglycolate, limonene, turpinolene and the like. be.
• the amount of the chain transfer amount used is not particularly limited as long as the target molecular weight can be obtained, but it should be 0.01 to 0.8% by mass with respect to 100% by mass of all the monomer units. Is preferable, and more preferably 0.1 to 0.5% by mass. When the amount of the chain transfer agent used is 0.01% by mass to 0.8% by mass, the target molecular weight can be easily obtained.
• a method for introducing the maleimide monomer unit of the maleimide-based copolymer a method of copolymerizing a maleimide monomer, an aromatic vinyl monomer, a cyanide vinyl monomer (direct method), or an unsaturated dicarboxylic acid is used.
• An unsaturated dicarboxylic acid by copolymerizing an acid anhydride, an aromatic vinyl monomer, and a vinyl cyanide monomer in advance and then reacting with an unsaturated dicarboxylic acid anhydride group with ammonia or a primary amine.
• post-imidization method There is a method of converting an anhydride group into a maleimide monomer unit. The post-imidization method is preferable because the amount of residual maleimide monomer in the copolymer is small.
• the primary amines used in the postimidization method are, for example, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine and cyclohexyl.
• alkylamines such as amines and decylamines and aromatic amines such as chlor or brom-substituted alkylamines, aniline, toluidine and naphthylamines, of which aniline and cyclohexylamines are preferred.
• These primary amines may be used alone or in combination of two or more.
• the amount of the primary amine added is not particularly limited, but is preferably 0.7 to 1.1 molar equivalents, more preferably 0.85 to 1.05 mol, based on the unsaturated dicarboxylic acid anhydride group. Equivalent. When it is 0.7 mol equivalent or more with respect to the unsaturated dicarboxylic acid anhydride monomer unit in the maleimide-based copolymer, it is preferable because the thermal stability is good. Further, when the equivalent is 1.1 mol equivalent or less, the amount of the primary amine remaining in the maleimide-based copolymer is reduced, which is preferable.
• a catalyst may be used when introducing the maleimide monomer unit by the postimidization method.
• the catalyst can improve the dehydration ring closure reaction in the reaction of ammonia or a primary amine with an unsaturated dicarboxylic acid anhydride group, particularly in the reaction of converting an unsaturated dicarboxylic acid anhydride group to a maleimide group.
• the type of catalyst is not particularly limited, but for example, a tertiary amine can be used.
• the tertiary amine is not particularly limited, and examples thereof include trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylaniline, N, N-diethylaniline and the like.
• the amount of the tertiary amine added is not particularly limited, but is preferably 0.01 molar equivalent or more with respect to the unsaturated dicarboxylic acid anhydride group.
• the temperature of the imidization reaction in the present invention is preferably 100 to 250 ° C, more preferably 120 to 200 ° C. When the temperature of the imidization reaction is 100 ° C. or higher, the reaction rate is sufficiently high, which is preferable from the viewpoint of productivity. When the temperature of the imidization reaction is 250 ° C. or lower, deterioration of physical properties due to thermal deterioration of the maleimide-based copolymer can be suppressed, which is preferable.
• Initial polymerization step Total amount of vinyl cyanide monomer charged, 10 to 90% by mass of aromatic vinyl monomer, 0 to 30% by mass of unsaturated dicarboxylic acid anhydride monomer.
• Medium-term polymerization step The remainder of the charged amount of the aromatic vinyl monomer and the rest of the charged amount of the unsaturated dicarboxylic acid anhydride monomer are divided or continuously, respectively.
• the final polymerization step after the total amount of the unsaturated dicarboxylic acid anhydride monomer is charged in an amount of 1/10 or more of the amount of the aromatic vinyl monomer divided or continuously added.
• Addition and polymerization Imidization step The obtained aromatic vinyl-vinyl cyanide-unsaturated dicarboxylic acid anhydride copolymer is imimized with ammonia or a primary amine to obtain a maleimide-based copolymer.
• a method for removing volatile components such as a solvent used for solution polymerization and unreacted monomers from a solution after solution polymerization of a maleimide-based copolymer or a solution after completion of post-imidization is known.
• Method can be adopted.
• a vacuum devolatilization tank with a heater or a devolatilization extruder with a vent can be used.
• the devolatile maleimide-based copolymer in a molten state is transferred to a granulation process, extruded into a strand shape from a porous die, and processed into a pellet shape by a cold cut method, an aerial hot cut method, or an underwater hot cut method. Can be done.
• a copolymer other than the maleimide-based copolymer and containing a vinyl cyanide monomer unit and an aromatic vinyl monomer unit is further added to the maleimide-based copolymer to further add the maleimide-based copolymer.
• It may be a system copolymer composition.
• the compatibility with the resin to be kneaded is further improved.
• the amount of the copolymer added can be appropriately adjusted depending on the resin to be kneaded or the like. For example, the amount of the copolymer added to 100 parts by mass of the maleimide-based copolymer is 0 to 20 parts by mass, preferably 0. ⁇ 10 parts by mass.
• the amount of the copolymer added to 100 parts by mass of the maleimide-based copolymer may be 0.1 part by mass or more.
• the maleimide-based copolymer composition can also be obtained by further adding a copolymer containing a vinyl cyanide monomer unit and an aromatic vinyl monomer unit to the maleimide-based copolymer as described above. However, it can also be obtained by allowing the copolymer produced during the polymerization of the maleimide-based copolymer to exist without being removed.
• the maleimide-based copolymer composition is a copolymer containing an aromatic vinyl monomer unit, a cyanide vinyl monomer unit, and a maleimide monomer unit, and the content of the maleimide monomer unit is Copolymers of less than 30% by mass may also be included. Further, the maleimide-based copolymer composition may also contain a copolymer composed substantially only of vinyl cyanide monomer units and aromatic vinyl monomer units. The maleimide-based copolymer composition may be obtained by allowing such a copolymer to coexist without being removed from the maleimide-based copolymer.
• the maleimide-based copolymer thus obtained can be kneaded and mixed with various resins to improve the heat resistance of the obtained resin composition.
• the various resins are not particularly limited, but are acrylonitrile-butadiene-styrene copolymer resin (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer resin (ASA resin), and acrylonitrile-ethylene / propylene rubber-.
• ABS resin acrylonitrile-butadiene-styrene copolymer resin
• ASA resin acrylonitrile-styrene-acrylic rubber copolymer resin
• SAN resin styrene-acrylonitrile copolymer resin
• the blending ratio of the maleimide-based copolymer and these resins is one or more selected from the group consisting of 5 to 40% by mass of the maleimide-based copolymer, ABS resin, ASA resin, AES resin and SAN resin.
• the amount of the resin is preferably 60 to 95% by mass, more preferably 10 to 30% by mass of the maleimide-based copolymer, one or two selected from the group consisting of ABS resin, ASA resin, AES resin and SAN resin.
• the above resin is 70 to 90% by mass.
• the maleimide-based copolymer composition is used instead of the maleimide-based copolymer, the effect of improving the heat resistance of the resin composition can be similarly obtained, and the impact resistance of the resin composition can be obtained. Hue does not deteriorate.
• the method for kneading and mixing the maleimide-based copolymer and various resins is not particularly limited, but a known melt-kneading technique can be used.
• Suitable melt kneading devices include screws such as single-screw extruders, fully-engaged co-rotating twin-screw extruders, fully-engaged non-directional rotating twin-screw extruders, and non- or incompletely-engaged twin-screw extruders. There are extruders, Banbury mixers, coniders and mixing rolls.
• the maleimide-based copolymer and these resins are kneaded and mixed, a stabilizer, an ultraviolet absorber, a flame retardant, a plasticizer, a lubricant, a glass fiber, an inorganic filler, a colorant, an antistatic agent, etc. are further added. It doesn't matter. Further, the maleimide-based copolymer composition can be kneaded and mixed with various resins in the same manner as the maleimide-based copolymer, and additives can be added.
• maleimide-based copolymer (A-1) 20 parts by mass of styrene, 10 parts by mass of acrylonitrile, 5 parts by mass of maleic acid anhydride, 0.1 part by mass of t-butylperoxy-2-ethylhexanoate, ⁇ -in an autoclave having a volume of about 120 liters equipped with a stirrer. 0.5 parts by mass of methylstyrene dimer and 12 parts by mass of methylethylketone were charged, the gas phase part was replaced with nitrogen gas, and then the temperature was raised to 92 ° C. over 40 minutes with stirring.
• maleimide-based copolymer (A-2) 20 parts by mass of styrene, 21 parts by mass of acrylonitrile, 5 parts by mass of maleic acid anhydride, 0.1 part by mass of t-butylperoxy-2-ethylhexanoate, ⁇ -in an autoclave having a volume of about 120 liters equipped with a stirrer. 0.5 parts by mass of methylstyrene dimer and 12 parts by mass of methylethylketone were charged, the gas phase part was replaced with nitrogen gas, and then the temperature was raised to 92 ° C. over 40 minutes with stirring.
• maleimide-based copolymer (A-5) 20 parts by mass of styrene, 10 parts by mass of acrylonitrile, 5 parts by mass of maleic acid anhydride, 0.1 part by mass of t-butylperoxy-2-ethylhexanoate, ⁇ -in an autoclave having a volume of about 120 liters equipped with a stirrer. 0.5 parts by mass of methylstyrene dimer and 12 parts by mass of methylethylketone were charged, the gas phase part was replaced with nitrogen gas, and then the temperature was raised to 92 ° C. over 40 minutes with stirring.
• maleimide-based copolymer (A-6) 20 parts by mass of styrene, 10 parts by mass of acrylonitrile, 5 parts by mass of maleic acid anhydride, 0.1 part by mass of t-butylperoxy-2-ethylhexanoate, ⁇ -in an autoclave having a volume of about 120 liters equipped with a stirrer. 0.5 parts by mass of methylstyrene dimer and 12 parts by mass of methylethylketone were charged, the gas phase part was replaced with nitrogen gas, and then the temperature was raised to 92 ° C. over 40 minutes with stirring.
• maleimide-based copolymer (A-7) 20 parts by mass of styrene, 20 parts by mass of acrylonitrile, 5 parts by mass of maleic acid anhydride, 0.1 part by mass of t-butylperoxy-2-ethylhexanoate, ⁇ -in an autoclave having a volume of about 120 liters equipped with a stirrer. 0.5 parts by mass of methylstyrene dimer and 12 parts by mass of methylethylketone were charged, the gas phase part was replaced with nitrogen gas, and then the temperature was raised to 92 ° C. over 40 minutes with stirring.
• maleimide-based copolymer (A-8) 20 parts by mass of styrene, 15 parts by mass of acrylonitrile, 5 parts by mass of maleic acid anhydride, 0.1 part by mass of t-butylperoxy-2-ethylhexanoate, ⁇ -in an autoclave having a volume of about 120 liters equipped with a stirrer. 0.5 parts by mass of methylstyrene dimer and 12 parts by mass of methylethylketone were charged, the gas phase part was replaced with nitrogen gas, and then the temperature was raised to 92 ° C. over 40 minutes with stirring.
• the weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC), and was measured under the following conditions.
• Device name SYSTEM-21 Shodex (manufactured by Showa Denko KK) Column: 3 PL gel MIXED-B (manufactured by Polymer Laboratories) in series Temperature: 40 ° C Detection: Differential Refractometer Solvent: Tetrahydrofuran Concentration: 2% by mass Calibration curve: Prepared using standard polystyrene (PS) (manufactured by Polymer Laboratories).
• PS polystyrene
• Tmg Melt glass transition temperature
• Examples 1 to 8 and Comparative Examples 1 to 8 (kneading and mixing of a maleimide-based copolymer and ABS resin) After blending the maleimide-based copolymers A-1 to A-12 and the commercially available ABS resin "GR-3000" (manufactured by Denka Co., Ltd.) in the blending ratios shown in Tables 3 and 4, two Extruded into pellets using a shaft extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.). Using this pellet, a test piece was prepared by an injection molding machine, and each physical property value was measured. The results are shown in Tables 3 and 4.
• test piece was measured by the 50 method (load 50 N, heating rate 50 ° C./hour) using a test piece having a thickness of 10 mm ⁇ 10 mm and a thickness of 4 mm.
• the measuring machine used was an HDT & VSPT test device manufactured by Toyo Seiki Seisakusho Co., Ltd.
• a crack was observed at 23 ° C. after 48 hours by a 1/4 ellipsoid method having a test piece shape of 316 ⁇ 20 ⁇ 2 mm, a semi-major axis of 250 mm, and a semi-minor axis of 150 mm.
• the test piece was manufactured by press-molding pellets at 260 ° C. and cutting out to eliminate the influence of molding strain.
• the chemical was carried out using toluene.
• the critical strain was calculated by the following formula.
• the maleimide-based copolymers A-1 to A-8 of the present invention have a molecular weight as shown in Examples 1 to 8 without reducing the content of the maleimide monomer unit in the composition. By lowering the temperature, a high midpoint glass transition temperature (Tmg) and a high melt mass flow rate were realized. However, when the molecular weight was lowered by a certain amount or more, the chemical resistance was lowered as in Comparative Example 7.
• the maleimide-based copolymers B-1 to B-7 that do not fall within the scope of the present invention are outside the scope of the present invention, and from Comparative Example 1 in which these maleimide-based copolymers and ABS resin are kneaded and mixed.
• the resin composition of Comparative Example 7 was inferior in impact resistance, fluidity, and chemical resistance.
• the maleimide-based copolymer of the present invention has an excellent balance of chemical resistance, heat resistance, impact resistance, and fluidity by being mixed and mixed with compatible ABS resin, ASA resin, AES resin, and SAN resin. Since the resin composition can be obtained and the fluidity of the mixed resin can be increased, the molding speed can be increased and the production speed can be improved. Further, since the yellowness (YI) of the molded product can be lowered, it can be applied to white applications.

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