Classifications

• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • 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
• • 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
  • C08F212/10—Styrene with 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
  • 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
  • C08F220/42—Nitriles
  • C08F220/44—Acrylonitrile
• • 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
  • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
  • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
• • 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
  • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/12—Copolymers of styrene with unsaturated nitriles

Definitions

• the present invention relates to a graft copolymer resin.
• Rubber-reinforced thermoplastic resin has excellent molding processability, impact resistance, mechanical strength, etc., and is widely used in industrial parts and home electric appliances. In these applications, there are many opportunities to come into contact with various chemicals, detergents, etc., and it is required to impart chemical resistance to the rubber-reinforced thermoplastic resin.
• Patent Documents 1 to 3 describe that a rubber-reinforced thermoplastic resin obtained by graft-polymerizing a predetermined monomer on an acrylic rubber-like polymer has excellent chemical resistance.
• Japanese Unexamined Patent Publication No. 7-173361 Japanese Unexamined Patent Publication No. 8-113689 Japanese Unexamined Patent Publication No. 9-316291
• an object of the present invention is to provide a rubber-reinforced thermoplastic resin having improved chemical resistance, particularly solvent resistance.
• the free resin contained in the graft copolymer resin contains 10 to 35% by mass of a structural unit derived from a (meth) acrylic acid alkyl ester having 4 or more carbon atoms in an alkyl group based on the total amount of the free resin.
• the rubber-like polymer contains a structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms.
• the vinyl-based monomer further contains a (meth) acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms.
• the vinyl-based monomer contains 10 to 30% by mass of a (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group based on the total amount of the vinyl-based monomer.
• the rubber-like polymer contains 50% by mass or more of a structural unit derived from a (meth) acrylic acid alkyl ester having 4 or more carbon atoms in an alkyl group based on the total amount of the rubber-like polymer [1].
• the present invention it is possible to provide a rubber-reinforced thermoplastic resin having improved solvent resistance. Further, the rubber-reinforced thermoplastic resin of the present invention has sufficient weather resistance, impact resistance and fluidity.
• (meth) acrylic acid ester means acrylic acid ester or methacrylic acid ester, and the same applies to similar expressions such as "(meth) acrylate”.
• the graft copolymer resin of the present embodiment is formed by graft-polymerizing a vinyl-based monomer on a rubber-like polymer.
• the graft copolymer resin contains a graft copolymer in which a vinyl-based monomer is graft-polymerized on a rubber-like polymer and a free resin in which vinyl-based monomers are polymerized with each other, and is an unreacted vinyl-based monomer. Etc. may be included.
• the free resin contained in the graft copolymer resin may be produced during the production of the rubber-like polymer, and the monomer that was unreacted during the production of the rubber-like polymer may be used. It may be a free resin produced by reacting during graft polymerization.
• the rubber-like polymer examples include butadiene-based rubber-like polymers such as polybutadiene, styrene-butadiene copolymer, and acrylonitrile-butadiene copolymer; ethylene-propylene copolymer, ethylene-propylene-diene copolymer, and the like.
• (meth) acrylic rubber-like polymers are preferable from the viewpoint of further improving solvent resistance, and are derived from (meth) acrylic acid alkyl esters having an alkyl group having 4 or more carbon atoms.
• a (meth) acrylic rubber-like polymer containing the constituent units of the above is preferable.
• the content of the structural unit derived from the (meth) acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms in the (meth) acrylic rubber-like polymer is 50% by mass or more from the viewpoint of further improving the solvent resistance. Is more preferable, 60% by mass or more is more preferable, and 70% by mass or more is further preferable.
• the upper limit of the content of the structural unit derived from the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group in the (meth) acrylic rubber-like polymer is not particularly limited, but is, for example, 95% by mass or less. Can be done.
• Examples of the (meth) acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms include butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acrylic acid. Octyl and the like can be mentioned.
• the upper limit of the carbon number of the alkyl group in the (meth) acrylic acid alkyl ester having 4 or more carbon atoms of the alkyl group is not particularly limited, but may be, for example, 15 or less or 10 or less.
• the acrylic rubber-like polymer may be crosslinked with a crosslinking agent.
• the cross-linking agent include divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl phthalate, dicyclopentadiene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol hexa (meth).
• Acrylate 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triallyl cyanurate, triallyl isocyanurate and the like.
• the acrylic rubber-like polymer is a structural unit derived from a monomer other than the above-mentioned monomer, for example, a constituent unit derived from a conjugated diene-based monomer, an aromatic vinyl-based monomer, or a vinyl cyanide-based monomer. May have.
• Conjugated diene monomers include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, chloroprene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene. Etc., and one type or two or more types can be used.
• aromatic vinyl-based monomer examples include styrene, ⁇ -methylstyrene, paramethylstyrene, bromstyrene and the like, and one or more of them can be used.
• vinyl cyanide-based monomer examples include acrylonitrile, methacrylonitrile, etacrylonitrile, fumaronitrile, and the like, and one or more of them can be used.
• the content of the structural unit derived from the conjugated diene-based monomer, the aromatic vinyl-based monomer, or the vinyl cyanide-based monomer in the rubber-like polymer is independently, for example, 30% by mass or less, more preferably 20. It can be mass% or less, more preferably 10 mass% or less.
• the lower limit of the content is not particularly limited, but each can be independently set to, for example, 1% by mass or more.
• the rubbery polymer of the present embodiment can be produced by a conventionally known method, for example, emulsion polymerization.
• a polymerization initiator, an emulsifier, a polymerization modifier and the like may be used.
• polymerization initiator examples include water-soluble polymerization initiators such as potassium persulfate, sodium persulfate, and ammonium persulfate, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and diisopropylbenzene hydro.
• water-soluble polymerization initiators such as potassium persulfate, sodium persulfate, and ammonium persulfate
• cumene hydroperoxide benzoyl peroxide
• t-butyl hydroperoxide examples include oil-soluble polymerization initiators such as peroxide and 1,1,3,3-tetramethylbutylhydroperoxide.
• the emulsifier examples include carboxylates, sulfates, sulfonates, and the like. Specific examples of the emulsifier preferably used include potassium oleate, dipotassium alkenyl succinate, sodium rosinate, potassium rosinate, sodium dodecylbenzenesulfonate and the like.
• polymerization modifier examples include alkyl mercaptans such as n-dodecyl mercaptan and t-dodecyl mercaptan.
• the rubbery polymer preferably has a gel content of 75 to 90% from the viewpoint of improving the impact resistance of the graft copolymer resin.
• the gel content of the rubbery polymer is measured, for example, by the method of Examples described later.
• the graft copolymer resin of the present embodiment preferably contains the above rubber-like polymer in an amount of 10 to 90% by mass, more preferably 30 to 80% by mass. It is more preferable to contain 40 to 70% by mass.
• the vinyl-based monomer used for the above-mentioned graft polymerization includes a vinyl cyanide-based monomer and an aromatic vinyl-based monomer.
• the vinyl-based monomer preferably further contains a (meth) acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms.
• the vinyl cyanide-based monomer, the aromatic vinyl-based monomer, and the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group the same ones as described above can be preferably used.
• the content of the vinyl cyanide-based monomer used in the graft polymerization is, for example, 10 to 40% by mass, preferably 15 to 35% by mass, and more preferably 20 to 30% by mass, based on the total amount of the vinyl-based monomer. Can be%.
• the content of the aromatic vinyl-based monomer used in the graft polymerization is, for example, 40 to 80% by mass, preferably 45 to 75% by mass, and more preferably 50 to 70% by mass, based on the total amount of the vinyl-based monomer. Can be%.
• the content of the (meth) acrylic acid alkyl ester in which the alkyl group has 4 or more carbon atoms in the vinyl-based monomer used in the graft polymerization is the total amount of the vinyl-based monomer from the viewpoint of further improving the solvent resistance. It is preferable that the content is 10 to 30% by mass based on the above.
• the free resin contained in the graft copolymer resin of the present embodiment is composed of a (meth) acrylic acid alkyl ester having 10 to 35% by mass of an alkyl group having 4 or more carbon atoms based on the total amount of the free resin. Includes units.
• the graft copolymer resin of the present embodiment can be produced by a conventionally known method, and for example, a polymerization method such as an emulsion polymerization method, a suspension polymerization method, or a bulk polymerization method can be used.
• a polymerization method such as an emulsion polymerization method, a suspension polymerization method, or a bulk polymerization method
• the latex of the graft copolymer resin can be obtained by graft-polymerizing the above-mentioned vinyl-based monomer on the above-mentioned rubber-like polymer.
• the latex of the graft copolymer resin is solidified by a known method, and the powder of the graft copolymer resin can be obtained by undergoing a washing, dehydrating, and drying step.
• the free resin means a resin that can be separated from the graft copolymer resin by the following procedures (A) and (B).
• the type of structural unit contained in the free resin can be determined by applying a known method such as pyrolysis gas chromatography. Further, the content of the structural unit contained in the free resin, particularly the structural unit derived from the vinyl cyanide-based monomer, the aromatic vinyl-based monomer and the (meth) acrylic acid alkyl ester, is the CHN described in Examples. The content of each structural unit can be obtained and calculated by applying analysis, oxygen analysis, or the like.
• the content of the free resin in the graft copolymer resin can be adjusted by, for example, the following method.
• A The content of the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group in the vinyl-based monomer used for the graft polymerization is adjusted to, for example, 10 to 30% by mass.
• B As the emulsifier used in the production of the rubber-like polymer, for example, rosin acid or a derivative thereof is used.
• a polymerization modifier for example, t-dodecyl mercaptan, is added during the production of the rubbery polymer.
• the graft copolymer resin of the present embodiment can be mixed with various thermoplastic resins to obtain a thermoplastic resin composition.
• the thermoplastic resin include polystyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, polymethyl methacrylate, styrene-maleic anhydride copolymer, styrene-maleimide copolymer, and styrene-acrylonitrile-maleimide.
• HIPS rubber reinforced polystyrene
• ABS resin acrylonitrile-butadiene-styrene resin
• AES resin acrylonitrile-ethylene propylene-styrene resin
• MBS resin methyl methacrylate-butadiene-styrene resin
• AS resin n-butyl acrylate-styrene resin
• AS resin polycarbonate, polyamide, polybutylene terephthalate, polyethylene terephthalate, and polyphenylene oxide.
• the content of the graft copolymer resin when the graft copolymer resin is mixed with the thermoplastic resin to obtain a thermoplastic resin composition is not particularly limited, and the type of the graft copolymer resin, the thermoplastic resin, etc. It can be appropriately adjusted in consideration of the above, and for example, it can be 10 to 50% by mass based on the total amount of the thermoplastic resin composition.
• thermoplastic resin composition can be obtained in the form of pellets by melt-kneading using a known device such as a Banbury mixer, a roll mill, or a twin-screw extruder. Further, the obtained thermoplastic resin composition can be appropriately blended with a plasticizer, a lubricant, a flame retardant, a pigment, a filler, a fiber strengthening agent and the like, if necessary. Further, the thermoplastic resin composition thus obtained can be molded by injection molding, extrusion molding, compression molding, injection compression molding, blow molding or the like.
• an emulsifier aqueous solution prepared by dissolving 0.75 parts by weight of sodium dodecylbenzenesulfonate (in terms of solid content) in a mixed solution of 85 parts by weight of butyl acrylate and 0.60 parts by weight of allyl methacrylate and 24 parts by weight of deionized water. It was added continuously over time. After the dropping, the mixture was held for 3.5 hours to obtain a crosslinked butyl acrylate rubber latex (a-1).
• an emulsifier aqueous solution prepared by dissolving 2.125 parts by weight of potassium rosinate (in terms of solid content) in a mixed solution of 85 parts by weight of butyl acrylate and 0.60 parts by weight of allyl methacrylate and 24 parts by weight of deionized water. It was added continuously over 3 hours. After the dropping, the mixture was held for 3.5 hours to obtain a crosslinked butyl acrylate rubber latex (a-4).
• the graft copolymer weight is the same as in the production of the graft copolymer resin (A-1) except that the crosslinked butyl rubber acrylate rubber latex (a-1) is used instead of the crosslinked butyl rubber acrylate rubber latex (a-1).
• a coalesced resin (A-6) was produced.
• a mixture of 12.5 parts by weight of acrylonitrile and 37.5 parts by weight of styrene and 16 parts by weight of deionized water were mixed with 1.0 part by weight of potassium loginate and 0 parts by weight of t-butyl hydroperoxide.
• An aqueous emulsifier solution in which 28 parts by weight (in terms of solid content) was dissolved was continuously added dropwise over 6 hours. After the dropping, the mixture was held for 2 hours to obtain a graft copolymer resin (A-7).
• the graft copolymer resin (A-8) was produced in the same manner as in the production of the graft copolymer resin (A-4) except that the addition time of the aqueous emulsifier solution was changed from 6 hours to 1 hour.
• the graft copolymer resin (A) was produced in the same manner as in the production of the graft copolymer resin (A-4) except that the amounts of acrylonitrile, styrene and butyl acrylate added to the mixed solution were changed to the amounts shown in Table 2. -9), (A-10), and (A-12) were produced.
• a graft copolymer resin (A-11) was produced in the same manner as in the above-mentioned production of the graft copolymer composition (A-4) except that methyl methacrylate (MMA) was used instead of butyl acrylate.
• MMA methyl methacrylate
• graft copolymer resin (A-12) [Powdering of graft copolymer resin (A-12)] A graft copolymer resin (A-12) was used instead of the graft copolymer resin (A-1), and powdering was attempted in the same manner as in the production of the graft copolymer resin (B-1). The copolymer resin had hardened and could not be powdered. Therefore, the graft copolymer resin (A-12) was excluded from the subsequent evaluation.
• Free resin composition analysis was performed on the graft copolymer resin powders (B-1) to (B-11). Specifically, for the measurement sample prepared by the following method, the amount of acrylonitrile was calculated from the amount of nitrogen by the following CHN analysis, the amount of butyl acrylate was calculated from the amount of oxygen by the following oxygen (O) analysis, and acrylonitrile and styrene were added. The total amount of butyl acrylate was taken as 100%, and the balance obtained by subtracting the calculated amounts of acrylonitrile and butyl acrylate was calculated as the amount of styrene.
• the amount of butyl acrylate (BA amount) in the free resin was calculated based on the amount of acrylonitrile, the amount of butyl acrylate, and the amount of styrene.
• the results are shown in Table 2.
• the graft copolymer resin powders (B-3) to (B-10) are examples, and the graft copolymer resin powders (B-1), (B-2) and (B-11) are comparative examples. Corresponds to each.
• copolymer (C-1) A copolymer (C-1) composed of 74.5 parts by weight of styrene and 25.5 parts by weight of acrylonitrile was obtained by a known massive polymerization method. As a result of measuring the reducing viscosity of the obtained copolymer (C-1) by the following method, the reducing viscosity was 0.62 dl / g. After dissolving in N, N-dimethylformamide to prepare a solution having a concentration of 0.4 g / 100 ml, the reduced viscosity is determined from the flow time measured at 30 ° C. using a Canon Fenceke type viscosity tube.
• melt volume flow rate in terms of 10kg load; was measured (unit cm 3/10 min).

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