WO2011145628A1 - Composition de résine thermoplastique pour boîtiers de lampe, et articles moulés - Google Patents

Composition de résine thermoplastique pour boîtiers de lampe, et articles moulés Download PDF

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Publication number
WO2011145628A1
WO2011145628A1 PCT/JP2011/061345 JP2011061345W WO2011145628A1 WO 2011145628 A1 WO2011145628 A1 WO 2011145628A1 JP 2011061345 W JP2011061345 W JP 2011061345W WO 2011145628 A1 WO2011145628 A1 WO 2011145628A1
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mass
meth
compound
acrylic
polymer
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PCT/JP2011/061345
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English (en)
Japanese (ja)
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浩司 石川
忍 福村
岩本　聡
悠 永谷
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テクノポリマー株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
    • F21S41/50—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by aesthetic components not otherwise provided for, e.g. decorative trim, partition walls or covers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S43/00—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights
    • F21S43/50—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights characterised by aesthetic components not otherwise provided for, e.g. decorative trim, partition walls or covers
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/06—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using friction, e.g. spin welding
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1629—Laser beams characterised by the way of heating the interface
    • B29C65/1635—Laser beams characterised by the way of heating the interface at least passing through one of the parts to be joined, i.e. laser transmission welding
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1677—Laser beams making use of an absorber or impact modifier
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • B29C65/20—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools with direct contact, e.g. using "mirror"
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/342—Preventing air-inclusions
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43—Joining a relatively small portion of the surface of said articles
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7311—Thermal properties
    • B29C66/73117—Tg, i.e. glass transition temperature
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/94—Measuring or controlling the joining process by measuring or controlling the time
    • B29C66/949—Measuring or controlling the joining process by measuring or controlling the time characterised by specific time values or ranges
    • 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
    • B29L2031/747—Lightning equipment
    • 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
    • C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes

Definitions

  • the present invention provides a molded article excellent in impact resistance, heat resistance, molded appearance and weldability, excellent weldability with other resin molded articles, and a beautiful bright appearance after direct vapor deposition.
  • the present invention relates to a thermoplastic resin composition for a housing.
  • Vehicle lamps such as headlamps, tail lamps, stop lamps and the like are generally composed of a resin lens part (hereinafter also referred to as “lamp lens”) and a resin housing part (hereinafter also referred to as “lamp housing”). ing.
  • a resin lens part hereinafter also referred to as “lamp lens”
  • a resin housing part hereinafter also referred to as “lamp housing”.
  • transparent resin such as polymethyl methacrylate (PMMA) and polycarbonate (PC) is used for the resin lens portion
  • ABS resin is used for the resin housing portion from the viewpoint of weight reduction and productivity.
  • a resin composition in which a colorant is blended is used.
  • a method for joining the lamp lens and the lamp housing there are methods such as a hot plate welding method, a laser welding method, and a vibration welding method.
  • the so-called hot plate welding method in which a heated hot plate is pressed against the bonding site to be bonded for several seconds and melted together, and then quickly separated from the hot plate and bonded together, is a cost. It is widely used from the viewpoint of reduction and environmental load reduction.
  • this hot plate welding method when the hot plate is pulled away from the bonding part of the lamp housing, the molten resin is stretched into a thread shape (hereinafter, this phenomenon is referred to as “yarn pulling”). It was. If this adheres to the surface of the molded product of the lamp lens or the lamp housing, the appearance of the product will be poor. Therefore, a resin composition for a lamp housing in which stringing is suppressed has been studied.
  • the laser welding method which is another method for bonding resin members together, abuts the resin member A containing a laser light transmissive material and the resin member B containing a laser light absorptive material.
  • the resin member A is irradiated with a laser beam and transmitted through the resin member A to reach the bonding part of the resin member B to melt the part, and at the same time, the resin member by heat transfer.
  • the bonding part of A is also melted to join the resin members together.
  • This laser welding method is a preferable method in that stringing is suppressed because the members are joined in a state where they are in contact with each other.
  • the resin component constituting the resin member B is decomposed by the irradiation of the laser beam to generate a gas, which is confined in the joint, and bubbles remain, which may deteriorate the appearance of the product after welding. is there.
  • the lamp housing is usually subjected to secondary processing such as painting, metal deposition, and plating in order to increase the brightness of the vehicle lamp.
  • secondary processing such as painting, metal deposition, and plating in order to increase the brightness of the vehicle lamp.
  • the surface of the molded product before the secondary processing needs to have excellent smoothness.
  • undercoat treatment is usually performed, but due to the excellent smoothness, an undercoat layer is not formed on the molded product (hereinafter referred to as “ It is also referred to as “undercoat-less”), and a metal layer or the like may be formed directly, which can lead to a reduction in the cost of the product.
  • a method for improving stringing in the hot plate welding method for example, a method of adding a fluorine resin such as polytetrafluoroethylene to a thermoplastic resin such as an ABS resin (see Patent Document 1), an aromatic polycarbonate and acrylic acid
  • a method of blending with a vinyl copolymer containing an ester rubber polymer (see Patent Document 2), and a specific rubber polymer graft polymer selected from cross-linked acrylic rubber and polyorganosiloxane rubber are essential.
  • the method (refer patent document 3) etc. are disclosed. Although these are effective in improving stringing, they are not sufficient, and none of the secondary processability until undercoatless is satisfied.
  • Patent Document 4 a method for improving thread stringing using an ⁇ -methylstyrene copolymer and a rubber-reinforced styrene graft copolymer as an active ingredient (see Patent Document 4), and a stringing compound containing a tetrafluoroethylene derivative polymer.
  • Patent Document 5 a composition containing a rubber-containing graft copolymer having a specific amount of rubber in a specific range in order to improve the appearance of the joint in the laser welding method (Patent Document) 6) has been proposed.
  • Patent Document 7 As a method for improving the direct vapor deposition property after improving the stringing at the time of hot plate welding or the appearance at the time of laser welding, for example, the above-mentioned Patent Document 7 and, for example, a specific ⁇ -methylstyrene copolymer and small particles are used.
  • Patent Document 8 A method using a composition containing a rubber-containing graft copolymer (see Patent Document 8), a method using a composition containing a graft copolymer having a specific particle diameter and containing a rubber having a particle diameter range (Patent Document) 9) and the like.
  • Patent Document 8 a method using a composition containing a graft copolymer having a specific particle diameter and containing a rubber having a particle diameter range
  • Japanese Patent Laid-Open No. 9-12902 Japanese Patent Laid-Open No. 10-287802 Japanese Patent Laid-Open No. 10-310676 JP 11-199729 A JP-A-11-256044 JP 2004-182835 A JP 2001-002869 A JP 2001-253990 A JP 2003-138089 A
  • the object of the present invention is to give a molded product excellent in impact resistance, heat resistance, molding appearance and weldability (hot plate welding and laser welding), excellent weldability with other resin molded products, and direct It is an object to provide a thermoplastic resin composition for a lamp housing and a molded article containing the same, which can obtain a beautiful brilliant appearance after vapor deposition.
  • the present invention is as follows. 1.
  • the gel content is 70% by mass or more, the degree of swelling with toluene is 5.5 to 30 times, the volume average particle size is 100 to 200 nm, and the volume average particle size and number average particle size are Acrylic rubber obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an acrylic rubber polymer (a1) having a ratio less than 1.1 A polymer reinforced graft resin, [B] an ⁇ -methylstyrene copolymer containing 25 to 85 mass% of structural units derived from ⁇ -methylstyrene, If necessary, [C] Structural units derived from other aromatic vinyl compounds other than ⁇ -methylstyrene, structural units derived from vinyl cyanide compounds, and / or structural units derived from (meth) acrylic acid alkyl ester compounds A copolymer comprising A thermoplastic resin composition for a lamp housing, comprising: The content of the acrylic rubbery polymer (a1) is that
  • thermoplastic resin composition for a lamp housing wherein the content of structural units derived from ⁇ -methylstyrene is 15 to 45% by mass when the total of the units is 100% by mass. 2. Furthermore, in the presence of [D] an organosiloxane rubber and a composite rubber (d1) containing a (co) polymer rubber containing a structural unit derived from an alkyl (meth) acrylate, the glass transition temperature of the homopolymer 2.
  • the composite rubber reinforced graft resin obtained by polymerizing a vinyl monomer containing a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound and a vinyl cyanide compound having a temperature exceeding 0 ° C.
  • the content ratios of the acrylic rubbery polymer (a1) and the composite rubber (d1) are 70 to 99% by mass and 1 to 30% by mass, respectively, when the total of both is 100% by mass 3.
  • the acrylic rubbery polymer (a1) comprises 50 to 100% by mass of (meth) acrylic acid alkyl ester compound (m1-1) in the presence of an alkyl sulfonate and / or an alkyl sulfate ester salt, Other compound (m1-2) copolymerizable with (meth) acrylic acid alkyl ester compound (m1-1) 0 to 50% by mass (however, the sum of (m1-1) and (m1-2) is 100% by mass)
  • thermoplastic resin composition for a lamp housing according to any one of the above. 5.
  • [X] First obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound other than ⁇ -methylstyrene and a vinyl cyanide compound in the presence of the acrylic rubbery polymer (a1).
  • [X] First obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound other than ⁇ -methylstyrene and a vinyl cyanide compound in the presence of the acrylic rubbery polymer (a1).
  • a (meth) acrylic acid alkyl ester compound in which the glass transition temperature of the homopolymer exceeds 0 ° C.
  • the intrinsic viscosity of an acetone soluble polymer obtained by immersing the thermoplastic resin composition for lamp housing in acetone is 0.2 to 1.0 dl / g.
  • thermoplastic resin composition for a lamp housing according to any one of 1 to 7 above which is a molding material for a molded product in which a vapor deposition layer is formed on the surface by direct vapor deposition.
  • thermoplastic resin composition for a lamp housing according to any one of 1 to 8 above which is a molding material for a molded article to which a hot plate welding method and / or a laser welding method is applied.
  • a molded article comprising the thermoplastic resin composition for a lamp housing according to any one of 1 to 9 above.
  • thermoplastic resin composition for a lamp housing of the present invention a molded product excellent in impact resistance, heat resistance, molded appearance and weldability (hot plate welding and laser welding) can be obtained. Excellent weldability with the resin molded product and a beautiful bright appearance after direct vapor deposition.
  • thermoplastic resin composition for a lamp housing of the present invention further contains a composite rubber reinforced graft resin [D], a molded product having more excellent impact resistance can be obtained.
  • (meth) acryl means acryl and methacryl
  • (co) polymer means a homopolymer and a copolymer
  • the thermoplastic resin composition for a lamp housing of the present invention has [A] a gel content of 70% by mass or more and a swelling degree with toluene (hereinafter referred to as “toluene swelling degree”) of 5.5 to 30 times.
  • a swelling degree with toluene
  • an acrylic rubbery polymer (a1) having a volume average particle diameter of 100 to 200 nm and a ratio of the volume average particle diameter to the number average particle diameter of less than 1.1
  • an aromatic vinyl compound And a vinyl monomer containing a vinyl cyanide compound hereinafter also referred to as “vinyl monomer (a2)
  • an acrylic rubbery polymer reinforced graft resin hereinafter referred to as “vinyl monomer (a2)”).
  • Component [A] ”) and [B] an ⁇ -methylstyrene copolymer (hereinafter referred to as“ component ”) containing 25 to 85% by mass of structural units derived from ⁇ -methylstyrene based on the total structural units. [B] ”) and as necessary.
  • component an ⁇ -methylstyrene copolymer
  • [C] structural units derived from other aromatic vinyl compounds other than ⁇ -methylstyrene
  • a copolymer containing a structural unit (hereinafter also referred to as “component [C]”), and the content of the acrylic rubbery polymer (a1) is as follows.
  • the component [C] and the component [C] are 10 to 40% by mass when the total amount is 100% by mass, the structural unit constituting the component [A], and the structure constituting the component [B]
  • the content of the structural unit derived from ⁇ -methylstyrene is 15 to 45% by mass. To do.
  • the component [A] is a resin composition obtained by polymerizing the vinyl monomer (a2) in the presence of the acrylic rubbery polymer (a1) (hereinafter referred to as “graft polymerization”).
  • graft polymerization the acrylic rubbery polymer (a1)
  • rubber reinforced resin an acrylic rubbery polymer reinforced graft resin.
  • This acrylic rubber polymer reinforced graft resin is a resin in which a copolymer of a vinyl monomer (a2) is grafted to an acrylic rubber polymer (a1), and the acrylic rubber polymer Part and a copolymer part containing a structural unit derived from the vinyl monomer (a2).
  • the rubber-reinforced resin obtained by graft polymerization is usually a (co) polymer not grafted to a rubbery polymer (hereinafter referred to as “ungrafted polymer”) in addition to the rubbery polymer-reinforced graft resin. .)including.
  • the composition of this ungrafted polymer depends on the type of vinyl monomer (a2) used. When the vinyl monomer (a2) contains ⁇ -methylstyrene, the resulting ungrafted polymer is Usually, in the composition of this invention, it is contained in component [B].
  • the vinyl monomer (a2) contains an aromatic vinyl compound other than ⁇ -methylstyrene, and a vinyl cyanide compound and / or a (meth) acrylic acid alkyl ester compound
  • the graft polymer is usually contained in the component [C] in the composition of the present invention.
  • the vinyl monomer (a2) contains styrene and ⁇ -methylstyrene, which are aromatic vinyl compounds, and a vinyl cyanide compound and / or a (meth) acrylic acid alkyl ester compound
  • the coalescence may include both components [B] and [C].
  • the acrylic rubbery polymer (a1) has a gel content of 70% by mass or more, a toluene swelling degree of 5.5 to 30 times, a volume average particle diameter of 100 to 200 nm, and a volume average.
  • the acrylic rubbery polymer (a1) usually has a polymer part containing a structural unit derived from a (meth) acrylic acid alkyl ester compound, and is a rubbery (co) polymer at 25 ° C. is there.
  • the acrylic rubbery polymer (a1) is a rubber that is not the composite rubber (d1) used for forming the component [D] described later, and is a single weight containing a structural unit derived from a (meth) acrylic acid alkyl ester compound. It may be a polymer or a copolymer containing this structural unit.
  • the copolymer may be a copolymer containing two or more structural units derived from a (meth) acrylic acid alkyl ester compound, a structural unit derived from a (meth) acrylic acid alkyl ester compound, and other structural units.
  • a copolymer containing a structural unit derived from a vinyl monomer may be used.
  • the acrylic rubbery polymer (a1) may be a crosslinked polymer or a non-crosslinked polymer.
  • the (meth) acrylic acid alkyl ester compound used for forming the structural unit derived from the (meth) acrylic acid alkyl ester compound which constitutes the acrylic rubbery polymer (a1), methyl (meth) acrylate, Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, (meth ) Pentyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, ( Examples thereof include dodecyl (meth) acrylate and cyclo
  • These compounds can be used alone or in combination of two or more. Of these, compounds having 1 to 14 carbon atoms in the alkyl group in the ester moiety are preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
  • the compound (vinyl monomer) used for forming other structural units excludes (meth) acrylic acid alkyl ester compounds. It can be a compound having one carbon-carbon double bond and / or a compound having two or more carbon-carbon double bonds.
  • Examples of the compound having one carbon-carbon double bond include aromatic vinyl compounds, vinyl cyanide compounds, amide group-containing unsaturated compounds, alkyl vinyl ethers, and vinylidene chloride. In addition, these compounds may be used independently and may be used in combination of 2 or more type.
  • aromatic vinyl compound examples include styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, ethylstyrene, tert-butylstyrene, ⁇ -methylstyrene, 1,1-diphenylstyrene, N, N-diethyl.
  • -P-aminostyrene N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, vinylnaphthalene, etc. .
  • vinyl cyanide compound examples include acrylonitrile and methacrylonitrile.
  • the amide group-containing unsaturated compound include acrylamide and methacrylamide.
  • alkyl vinyl ether include compounds in which the alkyl group constituting the alkyl portion has 1 to 6 carbon atoms.
  • the compound having two or more carbon-carbon double bonds includes a bifunctional aromatic vinyl compound, a bifunctional (meth) acrylic ester, a trifunctional (meth) acrylic ester, a tetrafunctional (meta ) Acrylic acid ester, pentafunctional (meth) acrylic acid ester, hexafunctional (meth) acrylic acid ester, polyhydric alcohol (meth) acrylic acid ester, and the like.
  • these compounds may be used independently and may be used in combination of 2 or more type.
  • bifunctional aromatic vinyl compound examples include divinylbenzene and divinyltoluene.
  • bifunctional (meth) acrylic acid ester include 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, allyl (meth) acrylate, neopentyl glycol dimethacrylate, and triethylene glycol diacrylate. Examples include acrylate and triethylene glycol dimethacrylate.
  • Examples of the trifunctional (meth) acrylic acid ester include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and the like.
  • Examples of the tetrafunctional (meth) acrylic acid ester include pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate.
  • Examples of the pentafunctional (meth) acrylic acid ester include pentaerythritol pentaacrylate and pentaerythritol pentamethacrylate.
  • Examples of the hexafunctional (meth) acrylic acid ester include dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate.
  • Examples of the (meth) acrylic acid ester of the polyhydric alcohol include (poly) ethylene glycol dimethacrylate.
  • diallyl malate, diallyl fumarate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, bis (acryloyloxyethyl) ether of bisphenol A, and the like can be used. Of these, allyl methacrylate and triallyl cyanurate are preferred.
  • the acrylic rubbery polymer (a1) is preferably a copolymer containing a structural unit derived from a (meth) acrylic acid alkyl ester compound.
  • the content of the structural unit derived from the (meth) acrylic acid alkyl ester compound is preferably 50 to 100% by mass, more The amount is preferably 70 to 100% by mass, more preferably 80 to 100% by mass.
  • the gel content of the acrylic rubbery polymer (a1) is 70% by mass or more, preferably 75% by mass or more, more preferably 80% by mass or more, regardless of the type of structural unit.
  • excellent glitter can be obtained when a metal layer or the like is provided on the surface of the obtained molded product.
  • the gel content is less than 70% by mass, the surface appearance, laser weldability, and glitter after direct vapor deposition of the obtained molded product are inferior.
  • the toluene swelling degree of the acrylic rubbery polymer (a1) is 5.5 to 30 times, preferably 6 to 25 times, more preferably 10 to 23 times, regardless of the type of structural unit. is there.
  • the acrylic rubbery polymer (a1) in the above range is used, a molded article having excellent impact resistance can be obtained, and excellent glitter when a metal layer or the like is disposed on the surface of the obtained molded article. Can be obtained.
  • the toluene swelling degree is less than 5.5 times, the resulting molded article is inferior in impact resistance, weldability, and glitter after direct vapor deposition.
  • the toluene swelling degree exceeds 30 times, the surface appearance and laser weldability of the obtained molded product are inferior, and stringing occurs during hot plate welding.
  • the said gel content and toluene swelling degree can be calculated
  • the insoluble matter is weighed together with the filtered wire mesh (mass is W1 gram), and the weight value (Wm) of the wire mesh is subtracted from the weight value (W1), and the insoluble matter swollen with toluene. Is obtained (the mass is defined as Ws gram).
  • the insoluble matter swollen with toluene contains toluene, it is air-dried at 25 ° C. for 12 hours, and subsequently dried at 60 ° C. for 12 hours using a vacuum dryer. Toluene contained in the minute is removed by drying.
  • the insoluble matter after drying is weighed together with the wire mesh (the mass is W2 grams), and the weight value (Wm) of the wire mesh is subtracted from the measured value (W2) to obtain the dry weight of the insoluble matter (the mass is Wd grams). And). From these weighed values, the gel content and the toluene swelling degree are calculated by the following equations.
  • the gel content and the degree of toluene swelling are the types and amounts of monomers used in producing the acrylic rubbery polymer (a1), the types and amounts of chain transfer agents (molecular weight regulators), and polymerization.
  • the time, polymerization temperature, polymerization conversion rate, and the like are adjusted by appropriately selecting.
  • the volume average particle diameter (hereinafter also referred to as “Mv”) of the acrylic rubbery polymer (a1) is 100 to 200 nm, preferably 105 to 180 nm, from the viewpoint of impact resistance and glitter. Preferably, it is 110 to 170 nm.
  • the particle size distribution (Mv / Mn) represented by the ratio of the volume average particle size (Mv) of the acrylic rubbery polymer (a1) to the number average particle size (hereinafter also referred to as “Mn”). ) Is less than 1.1, preferably less than 1.07, from the viewpoint of impact resistance and glitter. When the Mv is less than 100 nm, the impact resistance and the laser weldability are inferior.
  • Mv and Mn of the acrylic rubbery polymer (a1) can be measured by, for example, “Microtrack UPA150” (trade name) manufactured by HONEYWELL.
  • the acrylic rubber-like polymer (a1) can be obtained by a known production method, but the following copolymer obtained by a production method comprising a first polymerization step and a second polymerization step It is particularly preferable that it is a coalescence (hereinafter referred to as “copolymer (a11)”).
  • Second polymerization step (meth) acrylic acid alkyl ester compound in the presence or absence of alkyl sulfonate and / or alkyl sulfate ester salt (emulsifier (e)) in the presence of the first polymer.
  • Other compounds (m2-3) copolymerizable with the ester compound (m2-1) and the polymerizable unsaturated compound (m2-2) 0 to 49.99% by mass (provided that (m2-1), (m2- 2) and the sum of (m2-3) is 100% by mass) and a monomer (m2) is polymerized in an aqueous medium to obtain a copolymer (a11).
  • the proportion of the amount of the monomers (m1) and (m2) used in the polymerization step is 1 to 50% by mass and 50 to 99% by mass, respectively, when the total of both is 100% by mass. To do.
  • the first polymerization step in the presence of the emulsifier (e), 50 to 100% by mass of the (meth) acrylic acid alkyl ester compound (m1-1), the (meth) acrylic acid alkyl ester compound (m1-1), Monomer (m1) comprising 0-50% by mass of another copolymerizable compound (m1-2) (provided that the total of (m1-1) and (m1-2) is 100% by mass) Is an emulsion polymerization in an aqueous medium to form a first polymer.
  • a polymerization initiator, a chain transfer agent (molecular weight regulator), an electrolyte and the like can be used as necessary.
  • a known method is applied as a specific method of emulsion polymerization.
  • the (meth) acrylic acid alkyl ester compound (m1-1) constituting the monomer (m1) a compound having 1 to 14 carbon atoms of the alkyl group in the ester part is preferably used. N-butyl acrylate and 2-ethylhexyl acrylate are preferably used.
  • the (meth) acrylic acid alkyl ester compound (m1-1) may be used alone or in combination of two or more.
  • a compound having one carbon-carbon double bond is usually used as the other compound (m1-2) copolymerizable with the above (meth) acrylic acid alkyl ester compound (m1-1).
  • a group vinyl compound, a vinyl cyanide compound and the like are preferably used.
  • these compounds may be used independently and can be used in combination of 2 or more type.
  • the proportions of the (meth) acrylic acid alkyl ester compound (m1-1) and the other compound (m1-2) used in the first polymerization step are as follows when the total of both is 100% by mass: It is preferably 50 to 100% by mass and 0 to 50% by mass, more preferably 70 to 100% by mass and 0 to 30% by mass, still more preferably 90 to 100% by mass and 0 to 10% by mass. By setting it as the said ratio, it is excellent in the impact resistance of a molded article, glitter, and laser weldability, and the stringing at the time of hot plate welding is suppressed.
  • the monomer is polymerized in the reaction system in the presence of the emulsifier (e).
  • the emulsifier (e) By using the emulsifier (e), the gel content is 70% by mass or more, the degree of swelling with toluene is 5.5 to 30 times, the volume average particle diameter is 100 to 200 nm, and the volume average particle
  • the 1st polymer for setting it as the acrylic rubber-like polymer (a1) whose ratio of a diameter and a number average particle diameter is less than 1.1 can be manufactured efficiently.
  • alkyl sulfonate examples include alkane sulfonate, alkyl benzene sulfonate, and alkyl naphthalene sulfonate. These compounds may be used alone or in combination of two or more.
  • alkane sulfonate a compound represented by the following general formula (1) can be used.
  • R 1 -SO 3 M (1) (Wherein R 1 is a hydrocarbon group having 8 to 20 carbon atoms, and M is Na or K.)
  • alkylbenzene sulfonate a compound represented by the following general formula (2) can be used.
  • R 2 is a hydrocarbon group having 10 to 18 carbon atoms, and M is Na or K.
  • the said alkyl naphthalene sulfonate can use the compound represented by following General formula (3). (Wherein R 3 is a hydrocarbon group having 3 to 8 carbon atoms, and M is Na or K.)
  • alkyl sulfonate alkane sulfonate and alkyl benzene sulfonate are preferable, and alkyl benzene sulfonate is more preferable.
  • alkylbenzene sulfonate sodium dodecylbenzenesulfonate is particularly preferable.
  • alkyl sulfate ester salt examples include higher alcohol sulfate ester salt, higher alkyl ether sulfate ester salt, sulfated oil, sulfated fatty acid ester, sulfated olefin and the like. These compounds may be used alone or in combination of two or more.
  • alkyl sulfate ester salt examples include sodium octyl sulfate, sodium 2-ethylhexyl sulfate, sodium decyl sulfate, sodium lauryl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate triethanolamine, sodium myristyl sulfate, sodium stearyl sulfate, Examples include sodium cetyl sulfate and sodium polyoxyethylene lauryl ether sulfate.
  • the amount of the emulsifier (e) used is preferably 0.01 to 4.0 parts by mass, more preferably 0.02 to 3.0 parts by mass, when the monomer (m1) is 100 parts by mass. Part, more preferably 0.04 to 2.5 parts by weight.
  • the amount of the emulsifier (e) is in the above range, the first polymer for making the acrylic rubbery polymer (a1) having the above properties can be efficiently produced, and the resulting molding is obtained.
  • the product can be excellent in impact resistance and glitter.
  • the ratio of the amount used is preferably 1 to 99% by mass and 1 to 99% by mass, respectively, when the total of both is 100% by mass. %, More preferably 5 to 95% by mass and 5 to 95% by mass, particularly preferably 10 to 90% by mass and 10 to 90% by mass.
  • a method of using the emulsifier (e) in the first polymerization step a method in which the whole amount is charged all at once into the reaction system before the polymerization, and a part of the emulsifier is added to the reaction system before the polymerization is started. Then, the remainder can be divided or continuously added, or after polymerization has begun, divided or continuously.
  • an organic peroxide, an azo compound, an inorganic peroxide, a redox polymerization initiator, or the like can be used.
  • organic peroxide examples include tert-butyl hydroperoxide, tert-amyl-tert-butyl peroxide, tert-butyl-tert-hexyl peroxide, tert-amyl-tert-hexyl peroxide, di (tert-hexyl).
  • Examples of the azo compound include 2,2′-azobis (isobutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), azocumene, and 2,2′-azobis (2-methylbutyronitrile). 2,2′-azobisdimethylvaleronitrile, 4,4′-azobis (4-cyanovaleric acid), 2- (tert-butylazo) -2-cyanopropane, 2,2′-azobis (2,4,4) 4-trimethylpentane), 2,2′-azobis (2-methylpropane), dimethyl 2,2′-azobis (2-methylpropionate) and the like.
  • Examples of the inorganic peroxide include potassium persulfate, sodium persulfate, and ammonium persulfate.
  • Redox polymerization initiators include sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate and the like as reducing agents, potassium peroxodisulfate, hydrogen peroxide, tert-butyl hydroper What used an oxide etc. as an oxidizing agent can be used.
  • the polymerization initiator is preferably an inorganic peroxide.
  • the amount of the polymerization initiator used is preferably 0.01 to 3.0 parts by mass, more preferably 0.03 to 1.0 parts by mass, when the monomer (m1) is 100 parts by mass. More preferred is 0.05 to 0.75 parts by mass, and particularly preferred is 0.1 to 0.5 parts by mass.
  • the amount of the polymerization initiator used is in the above range, the first polymer for making the acrylic rubbery polymer (a1) having the above properties can be efficiently produced, and the obtained molded product Can be made excellent in impact resistance and glitter.
  • a method of using the polymerization initiator in the first polymerization step a method in which the whole amount is charged all at once into the reaction system before the polymerization, a part of the polymerization initiator is added to the reaction system before the polymerization, and the polymerization starts. The remainder can be divided or continuously added, or the like.
  • halogenated hydrocarbons such as chloroform and carbon tetrabromide
  • n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan Conventionally known compounds such as mercaptans such as tert-dodecyl mercaptan and thioglycolic acid
  • xanthogens such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide
  • terpinolene and ⁇ -methylstyrene dimer can be used.
  • tert-dodecyl mercaptan is preferred.
  • the amount of the chain transfer agent used is preferably 3 parts by mass or less, more preferably 1 part by mass or less, when the monomer (m1) is 100 parts by mass. If the amount of the chain transfer agent used is too large, the impact resistance of the molded product may be insufficient.
  • a method of using the chain transfer agent in the first polymerization step a method in which the whole amount is charged all at once into the reaction system before polymerization, a part of the chain transfer agent is added to the reaction system before polymerization, and the polymerization starts. The remainder can be divided or continuously added, or the like.
  • the first polymerization step when an electrolyte is used, conventionally known compounds such as potassium sulfate, potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydrogen carbonate, sodium pyrophosphate, potassium phosphate, sodium dithionite, etc. Can be used. These compounds may be used alone or in combination of two or more. Of the above compounds, potassium carbonate, sodium carbonate, sodium bicarbonate and sodium dithionite are preferred.
  • the amount of the electrolyte used is preferably 0.01 to 1.5 parts by mass, more preferably 0.03 to 1.25 parts by mass, even more preferably 100 parts by mass of the monomer (m1). Is 0.05 to 1.0 part by mass.
  • the 1st polymer for setting it as the copolymer (a11) which is the acrylic rubber-like polymer (a1) which has the said property can be manufactured efficiently.
  • a method of using the electrolyte in the first polymerization step a method in which the whole amount is charged all at once into the reaction system before the polymerization, a part is added to the reaction system before the polymerization, and the polymerization is started. The remainder may be divided or continuously added, or after polymerization has started, divided or continuously.
  • the polymerization temperature in the first polymerization step is usually from 65 ° C to 98 ° C, preferably from 70 ° C to 95 ° C.
  • the polymerization time is usually 0.5 to 2.0 hours.
  • the pH of the reaction system in the first polymerization step is not particularly limited, but is usually in the range of 2 to 12.
  • the first polymerization step is completed when the polymerization conversion rate is preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more.
  • the acrylic rubber polymer (a1) having the above properties is obtained even when the second polymerization step is performed using the obtained first polymer. There may not be.
  • the first polymerization step is completed at a polymerization conversion rate of 85% or more, the volume average particle size of the obtained first polymer is usually 40 to 120 nm.
  • the (meth) acrylic acid alkyl ester compound is present in the presence of the first polymer, in the presence or absence of an alkyl sulfonate and / or an alkyl sulfate ester salt (emulsifier (e)).
  • Other compounds (m2-3) copolymerizable with the ester compound (m2-1) and the polymerizable unsaturated compound (m2-2) 0 to 49.99% by mass provided that (m2-1), (m2- 2) and the sum of (m2-3) is 100% by mass) and the monomer (m2) is polymerized in an aqueous medium to obtain a copolymer (a11).
  • the second polymerization step may be performed in the same reaction system as the first polymerization step, or may be performed in a different reaction system.
  • the polymerization may be performed in the presence of the emulsifier (e) or may be performed in the absence of the emulsifier (e). In the latter case, other emulsifiers may be used.
  • a polymerization initiator when an emulsifier is used, a polymerization initiator, a chain transfer agent (molecular weight regulator), an electrolyte, and the like can be used as necessary.
  • a chain transfer agent molecular weight regulator
  • the (meth) acrylic acid alkyl ester compound (m2-1) constituting the monomer (m2) a compound having 1 to 14 carbon atoms in the alkyl group of the ester part is preferably used. N-butyl acrylate and 2-ethylhexyl acrylate are preferably used.
  • the (meth) acrylic acid alkyl ester compound (m2-1) may be used alone or in combination of two or more.
  • the polymerizable unsaturated compound (m2-2) having two or more carbon-carbon double bonds is preferably a bifunctional aromatic vinyl compound, a bifunctional (meth) acrylic acid ester, a trifunctional ( (Meth) acrylic acid ester, tetrafunctional (meth) acrylic acid ester, pentafunctional (meth) acrylic acid ester, hexafunctional (meth) acrylic acid ester, polyhydric alcohol (meth) acrylic acid ester, etc. are used. In particular, allyl methacrylate and triallyl cyanurate are preferably used.
  • the polymerizable unsaturated compound (m2-2) may be used alone or in combination of two or more.
  • the (meth) acrylic acid alkyl ester compound (m2-1) and the other compound (m2-3) copolymerizable with the polymerizable unsaturated compound (m2-2) are usually carbon-carbon diesters.
  • a compound having one heavy bond is used, and an aromatic vinyl compound, a vinyl cyanide compound and the like are preferably used.
  • these compounds may be used independently and can be used in combination of 2 or more type.
  • the proportion of the (meth) acrylic acid alkyl ester compound (m2-1), the polymerizable unsaturated compound (m2-2), and the other compound (m2-3) used in the second polymerization step is the sum of these.
  • 0.01 to 3.0% by mass and 0 to 29.99% by mass more preferably 90 to 99.99% by mass, 0.01 to 2.0% by mass, and 0 to 9.99% by mass.
  • polymerization process is when the sum total of both is 100 mass%, Each of them is preferably 1 to 50% by mass and 50 to 99% by mass, more preferably 3 to 40% by mass and 60 to 97% by mass, and particularly preferably 5 to 35% by mass and 65 to 95% by mass.
  • it is excellent in the impact resistance of a molded article, glitter, and laser weldability, and the stringing at the time of hot plate welding is suppressed.
  • the second polymerization step is a step of polymerizing the monomer (m2) in the presence of the first polymer obtained in the first polymerization step, and the entire amount of the monomer (m2) is reacted with the reaction system.
  • the polymerization may be carried out by adding them all at once, or the polymerization may be carried out while adding the monomer (m2) separately or continuously.
  • the second polymerization step may proceed in the same reaction system as the first polymerization step, or may proceed in a different reaction system.
  • the monomer (m2) is added to the latex containing the first polymer obtained in the first polymerization step, and polymerization is performed.
  • an aqueous medium or the like may be newly added if necessary.
  • the latex containing the first polymer obtained in the first polymerization step may be used as it is.
  • a suspension suspended in an aqueous medium may be used.
  • the second polymerization step proceeds in the presence of the emulsifier (e), a preferred type of the emulsifier (e), a preferred combination of an alkyl sulfonate and an alkyl sulfate ester salt, and a method of using the emulsifier (e) are: These are the same as those in the first polymerization step.
  • the amount of the emulsifier (e) used is preferably 0.01 to 4.0 parts by mass, more preferably 0.02 to 3.3 parts per 100 parts by mass of the monomer (m2). 0 parts by mass, more preferably 0.04 to 2.5 parts by mass.
  • the copolymer (a11) which is the acrylic rubbery polymer (a1) having the above properties can be efficiently produced, and the obtained molding is obtained.
  • the product can be excellent in impact resistance and glitter.
  • a polymerization initiator a chain transfer agent (molecular weight regulator), an electrolyte, or the like
  • the same compounds and methods of use as those used in the first polymerization step are preferably used. It is done. About the usage-amount of each component, the same quantity can be used as what replaced the monomer (m1) with the monomer (m2).
  • the polymerization temperature in the second polymerization step is usually from 65 ° C to 98 ° C, preferably from 70 ° C to 95 ° C.
  • the polymerization time is usually from 2.0 to 8.0 hours.
  • the pH of the reaction system in the second polymerization step is not particularly limited, but is usually in the range of 2-12.
  • the second polymerization step is completed when the polymerization conversion rate is preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more.
  • a copolymer (a11) that is an acrylic rubbery polymer (a1) having the above properties can be produced efficiently.
  • the polymerization conversion rate is lowered to complete the polymerization, the resulting acrylic rubber-like polymer has a small particle size and may have insufficient impact resistance.
  • Examples of the acrylic rubbery polymer (a1) include the copolymer (a11) obtained as described above, and an acrylic rubbery polymer obtained by a conventionally known method. Can be used.
  • Examples of the method for the enlargement treatment include a method of adding an acid such as acetic anhydride, acetic acid, nitric acid, phosphoric acid to the latex containing the polymer for enlargement. Among these, acetic anhydride is preferable, and thereby an acrylic rubber polymer (a1) having no variation in particle diameter after enlargement can be obtained.
  • acrylic rubbery polymer (a1) any polymer that is not enlarged and polymer that is enlarged may be used, or a combination thereof may be used.
  • the vinyl monomer (a2) subjected to polymerization is a monomer containing an aromatic vinyl compound and a vinyl cyanide compound, and if necessary , (Meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, amino group-containing unsaturated compounds, amide group-containing unsaturated compounds, epoxy group-containing An unsaturated compound, an oxazoline group-containing unsaturated compound, and the like may be included.
  • the total amount of the aromatic vinyl compound and the vinyl cyanide compound in the vinyl monomer (a2) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 80%. To 100% by mass.
  • the aromatic vinyl compound is not particularly limited, but has no substituent such as a functional group.
  • substituent such as a functional group.
  • examples thereof include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene and the like. These compounds can be used alone or in combination of two or more. Of these, styrene and ⁇ -methylstyrene are preferable, and styrene is particularly preferable.
  • vinyl cyanide compound examples include acrylonitrile, methacrylonitrile, ethacrylonitrile, ⁇ -ethylacrylonitrile, ⁇ -isopropylacrylonitrile and the like. These compounds can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.
  • Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples include cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. These compounds can be used alone or in combination of two or more.
  • maleimide compound examples include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methyl Phenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N-naphthylmaleimide, N- Examples thereof include cyclohexylmaleimide. Of these, N-phenylmaleimide is preferred.
  • these compounds can be used individually or in combination of 2 or more.
  • a method for introducing a structural unit derived from a maleimide compound into the component [A] for example, a method of copolymerizing an unsaturated dicarboxylic anhydride of maleic anhydride and then imidizing it may be used. .
  • Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These compounds can be used alone or in combination of two or more.
  • Examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. These compounds can be used alone or in combination of two or more.
  • hydroxyl group-containing unsaturated compound examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth ) 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylic acid 2 (Meth) acrylic acid ester having a hydroxyl group such as a compound obtained by adding ⁇ -caprolactone to hydroxyethyl; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy- ⁇ -methyl styrene, m-hydroxy- ⁇ -methylstyrene, p-hydroxy- ⁇ -methylstyrene, 2-hydroxymethyl-methyl
  • amino group-containing unsaturated compound examples include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, (meth) acrylic acid 2 -Dimethylaminoethyl, 2-diethylaminoethyl (meth) acrylate, 2- (di-n-propylamino) ethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 2- (meth) acrylic acid 2- Diethylaminopropyl, 2- (di-n-propylamino) propyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, 3- (di) (meth) acrylate -N-propylamino) prop
  • amide group-containing unsaturated compound examples include (meth) acrylamide, N-methylol (meth) acrylamide, 3-dimethylaminopropyl (meth) acrylamide and the like. These compounds can be used alone or in combination of two or more.
  • Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, and methallyl glycidyl ether. These compounds can be used alone or in combination of two or more.
  • Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline.
  • preferred graft resins are as follows. (1) Resin obtained by polymerizing vinyl monomer (a2-1) comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of acrylic rubbery polymer (a1) (2) Acrylic Obtained by polymerizing a vinyl monomer (a2-2) comprising an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester compound in the presence of a rubber-based polymer (a1)
  • the component [A] is composed of an acrylic rubbery polymer part and a copolymer part containing a structural unit derived from the vinyl monomer (a2) as described above.
  • the content of the acrylic rubbery polymer part constituting this component [A] is preferably 5 to 80 parts by weight with respect to a total of 100 parts by weight of the acrylic rubbery polymer part and the copolymer part.
  • the amount is preferably 10 to 70 parts by mass, more preferably 10 to 65 parts by mass.
  • strengthening graft resin may fall.
  • the content of the acrylic rubbery polymer part is too small, the impact resistance may not be sufficient.
  • the method for producing the component [A] is not particularly limited, and a known method can be applied.
  • the graft polymerization method may be emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a polymerization method combining these. Of these, emulsion polymerization is preferred.
  • an ungrafted polymer is by-produced in addition to the component [A].
  • the amount of the acrylic rubbery polymer (a1) and the vinyl monomer (a2) used is 100% in total from the viewpoint of impact resistance and glitter.
  • % Preferably 5 to 90% by mass and 10 to 95% by mass, more preferably 10 to 80% by mass and 20 to 90% by mass, still more preferably 30 to 70% by mass and 30 to 70% by mass, respectively. %.
  • the vinyl monomer (a2) is added all at once in the presence of the total amount of the acrylic rubber polymer (a1), and polymerization is started.
  • the polymerization may be carried out in portions or continuously.
  • the vinyl monomer (a2) may be added all at once to initiate polymerization, or may be divided or continuously. May be added. At this time, you may add the remainder of the said acrylic rubber-like polymer (a1) collectively, in the middle of reaction, dividing
  • a polymerization initiator When performing emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water, and the like are used.
  • the polymerization initiator and the chain transfer agent are as described above.
  • the polymerization initiator a redox polymerization initiator is preferable.
  • the amount of the polymerization initiator used is usually 0.1 to 1.5% by mass with respect to the total amount of the vinyl monomer (a2).
  • the polymerization initiator can be added to the reaction system all at once or continuously.
  • the chain transfer agent mercaptans are preferable, and tert-dodecyl mercaptan is particularly preferable. Moreover, the usage-amount of the said chain transfer agent is 5 mass% or less normally with respect to the said vinylic monomer (a2) whole quantity.
  • the chain transfer agent can be added to the reaction system all at once or continuously.
  • Examples of the emulsifier include anionic surfactants and nonionic surfactants.
  • Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Is mentioned.
  • Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more. The amount of the emulsifier used is usually 0.01 to 5% by mass with respect to the total amount of the vinyl monomer (a2).
  • Emulsion polymerization can be carried out under known conditions depending on the type and formulation of the vinyl monomer (a2), the polymerization initiator and the like.
  • the polymerization temperature at the time of polymerizing the vinyl monomer (a2) is usually 40 ° C. to 80 ° C., preferably 50 ° C. to 75 ° C.
  • the polymerization time is usually 4 to 8 hours.
  • the pH of the reaction system in the emulsion polymerization is not particularly limited, but is usually in the range of 8 to 12, preferably 9 to 12. Formation of component [A] can be efficiently advanced by advancing polymerization while maintaining the pH of the reaction system in the above range.
  • Emulsion polymerization is terminated when the polymerization conversion rate is preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more.
  • the polymerization conversion rate is preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more.
  • the latex containing the component [A] is usually subjected to coagulation of the resin component with a coagulant to form a powder or the like. Thereafter, it is purified by washing with water, etc., dried and collected.
  • coagulation conventionally known coagulants are used, and inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and calcium acetate; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid are used.
  • the rubber reinforced resin obtained as described above usually contains the component [A] and the ungrafted polymer. Therefore, when separating the component [A] and the ungrafted polymer, for example, 1 g of the rubber reinforced resin. Is added to 20 to 30 ml of acetone, followed by stirring at 25 ° C. for 2 to 6 hours to separate and recover the generated insoluble matter and soluble matter (acetone soluble polymer).
  • the acetone-soluble polymer corresponds to an ungrafted polymer, and is contained in the component [B] and / or the component [C] depending on the type of the vinyl monomer (a2) used as described above. There is something to be done.
  • the graft ratio in the component [A], that is, the proportion of the copolymer containing a structural unit derived from the vinyl monomer (a2) grafted to the acrylic rubber polymer (a1) is moldability, From the viewpoint of impact resistance, brightness, etc., it is preferably 5 to 200% by mass, more preferably 10 to 150% by mass, and still more preferably 20 to 120% by mass. If the graft ratio is too low, the impact resistance of the molded product may not be sufficient. On the other hand, if the graft ratio is too high, moldability may not be sufficient.
  • S is a rubber-reinforced resin obtained by graft polymerization, put into acetone, shaken using a shaker (temperature 25 ° C., 2 hours), and then centrifuged using a centrifuge.
  • Mass (g) of insoluble matter (temperature 60 ° C., dried for 12 hours) obtained by separation (temperature 0 ° C., rotation speed 28,000 rpm, 1 hour) and separation of insoluble matter and soluble matter, T Is the mass (g) of the acrylic rubber-like polymer (a1) contained in the rubber-reinforced resin.
  • the mass of the acrylic rubbery polymer (a1) can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.
  • the graft ratio is, for example, the type and amount of polymerization initiator used in the production of component [A], the type and amount of chain transfer agent, the vinyl monomer (a2) supply method and supply time, The polymerization temperature, polymerization time and the like can be adjusted by appropriately selecting.
  • the component [B] is a copolymer containing a predetermined amount of a structural unit derived from ⁇ -methylstyrene (hereinafter also referred to as “structural unit (b1)”).
  • structural unit (b1) a structural unit derived from ⁇ -methylstyrene
  • the copolymer obtained by (1) may be used.
  • the content of the structural unit (b1) is 25 to 85% by mass, preferably 30 to 80% by mass, based on the total amount of all the structural units constituting the component [B].
  • component [A] is a graft resin comprising an acrylic rubbery polymer part and a copolymer part containing a structural unit (b1) derived from ⁇ -methylstyrene
  • this graft resin Is not included in component [B]. That is, the component [B] is structurally independent from the component [A].
  • the composition of the present invention contains this component [B], excellent moldability and heat resistance can be obtained.
  • the component [B] is a copolymer including the structural unit (b1), and further includes another structural unit (hereinafter referred to as “structural unit (b2)”).
  • This structural unit (b2) is a structural unit derived from a vinyl monomer copolymerizable with ⁇ -methylstyrene.
  • the vinyl monomer copolymerizable with ⁇ -methylstyrene is particularly preferably a vinyl cyanide compound.
  • aromatic vinyl compounds excluding ⁇ -methylstyrene
  • acrylic Acid ester compounds maleimide compounds
  • unsaturated acid anhydrides carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, amino group-containing unsaturated compounds, amide group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, oxazolines And group-containing unsaturated compounds.
  • the compound illustrated as a vinyl-type monomer (a2) which can be used for formation of the said component [A] is applied to each compound. And these compounds may be used independently and may be used in combination of 2 or more type.
  • component [B] examples include ⁇ -methylstyrene and a vinyl cyanide compound copolymer (B1), ⁇ -methylstyrene, other aromatic vinyl compounds (excluding ⁇ -methylstyrene), and cyanide.
  • acrylonitrile is preferred as the vinyl cyanide compound
  • styrene is preferred as the other aromatic vinyl compound
  • methyl methacrylate is preferred as the (meth) acrylic ester compound.
  • the intrinsic viscosity (in methyl ethyl ketone, 30 ° C.) of the component [B] is preferably 0.2 to 1.0 dl / g, more preferably 0.25 to 0.8 dl / g, from the viewpoint of moldability and heat resistance. g.
  • the intrinsic viscosity can be determined as follows. The intrinsic viscosity is determined by dissolving the component [B] in methyl ethyl ketone, preparing five different concentrations, and measuring the reduced viscosity at each concentration at 30 ° C. using an Ubbelohde viscosity tube.
  • the component [B] may be used alone or in combination of two or more.
  • the component [B] when the component [B] is a separately prepared copolymer, it can be formed by known emulsion polymerization, solution polymerization, bulk polymerization or the like.
  • the content ratio of the component [A] and the component [B] is preferably 10 to 80% by mass and 20 to 90% by mass, respectively, when the total of both is 100% by mass, More preferred are 15 to 70% by mass and 30 to 85% by mass, still more preferred are 20 to 65% by mass and 35 to 80% by mass, and particularly preferred are 35 to 65% by mass and 35 to 65% by mass.
  • the content ratio of the component [A] and the component [B] is in the above range, a molded product excellent in impact resistance, heat resistance, molded appearance, weldability, glitter and the like can be obtained.
  • impact resistance may fall.
  • heat resistance and glitter may fall.
  • structural unit (c1) an aromatic vinyl compound other than ⁇ -methylstyrene
  • structural unit (c2) a structural unit derived from a vinyl cyanide compound
  • the component [C] may be derived from the above-mentioned component [A] or an ungrafted polymer formed when the component [D] described later is produced.
  • the content of the structural unit (c1) is preferably 10 to 100% by mass, more preferably 20 to 100%, based on the total amount of all the structural units constituting the component [C]. % By mass, more preferably 30 to 90% by mass.
  • the said component [A] is a graft resin which consists of an acryl-type rubber-like polymer part and the copolymer part containing a structural unit (c1)
  • the said component [D] mentioned later is composite
  • these graft resins are not included in the component [C]. That is, the component [C] is structurally independent from the components [A] and [D].
  • the composition of this invention contains this component [C], it can be excellent in molding processability and the surface appearance property of the molded product obtained.
  • the said component [C] is illustrated below, These polymers may be contained independently and may be contained in 2 or more types of combinations.
  • (1) Copolymer containing structural units (c1) and (c2) (2) Copolymer containing structural units (c1) and (c3) (3) Structural units (c1), (c2) and (c3) (4) A polymer comprising the structural unit (c1)
  • the content ratio of the structural units (c1) and (c2) is 100 in total from the viewpoint of molding processability and chemical resistance.
  • mass% it is preferably 50 to 95 mass% and 5 to 50 mass%, more preferably 60 to 95 mass% and 5 to 40 mass%, respectively.
  • the content ratio of the structural units (c1) and (c3) is 100% by mass from the viewpoint of molding processability, glitter and the like.
  • % Preferably 10 to 90% by mass and 10 to 90% by mass, more preferably 20 to 80% by mass and 20 to 80% by mass, respectively.
  • the content ratio of the structural units (c1), (c2), and (c3) is such as molding processability, glitter, and suppression of stringing. From the viewpoint, when the total of these is 100% by mass, preferably 5 to 35% by mass, 1 to 25% by mass, and 45 to 75% by mass, more preferably 10 to 30% by mass, and 5 to 20% by mass, respectively. % And 55 to 75% by mass.
  • aromatic vinyl compound forming the structural unit (c1) styrene is preferable.
  • vinyl cyanide compound forming the structural unit (c2) acrylonitrile is preferable.
  • a (meth) acrylic acid ester compound which forms the said structural unit (c3) methyl methacrylate is preferable.
  • the component [C] may further contain another structural unit (hereinafter referred to as “structural unit (c4)”).
  • structural unit (c4) include maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, amino group-containing unsaturated compounds, amide group-containing unsaturated compounds.
  • a saturated compound, an epoxy group-containing unsaturated compound, an oxazoline group-containing unsaturated compound, and the like can be given.
  • the upper limit of the content of the structural unit (c4) is preferably 100% by mass of the total of all the structural units constituting the component [C]. Is 50 mass%, more preferably 40 mass%, still more preferably 30 mass%.
  • the intrinsic viscosity (in methyl ethyl ketone, 30 ° C.) of the component [C] is preferably 0.2 to 1.0 dl / g, more preferably from the viewpoints of moldability, heat resistance and surface appearance of the obtained molded product. Is 0.25 to 0.8 dl / g.
  • the intrinsic viscosity of the component [C] can be determined in the same manner as the intrinsic viscosity of the component [B].
  • the component [C] may be used alone or in combination of two or more.
  • the component [C] when the component [C] is a separately prepared copolymer, it can be formed by known emulsion polymerization, solution polymerization, bulk polymerization or the like.
  • the content is preferably 70 when the total amount of the components [A], [B] and [C] is 100% by mass. It is not more than mass%, more preferably 5 to 60 mass%, still more preferably 10 to 50 mass%, particularly preferably 15 to 40 mass%.
  • the said component [C] is contained at 70 mass% or less, the molded article which was more excellent in heat resistance can be obtained, and the stringing at the time of welding is suppressed.
  • the intrinsic viscosity (in methyl ethyl ketone, 30 ° C.) of the mixture of the above-mentioned components [B] and [C] is molding processability, molding appearance and glitter.
  • it is preferably 0.2 to 1.0 dl / g, more preferably 0.25 to 0.8 dl / g.
  • the mixture of the above components [B] and [C] is a component corresponding to an ungrafted polymer in the composition of the present invention.
  • the composition of the present invention is added to acetone, followed by stirring at 25 ° C. for 2 to 6 hours, then removing insoluble components and recovering the recovered acetone-soluble components. From this, a method of removing acetone is applied.
  • the recovered product after removing acetone is referred to as “acetone-soluble polymer”.
  • the composition of the present invention further comprises a homopolymer in the presence of an organosiloxane rubber and a composite rubber (d1) containing a (co) polymer rubber having a structural unit derived from an alkyl (meth) acrylate.
  • a composite rubber (d1) containing a (co) polymer rubber having a structural unit derived from an alkyl (meth) acrylate.
  • the glass transition temperature of (meth) acrylic acid alkyl ester compound, aromatic vinyl compound and vinyl cyanide compound containing vinyl cyanide compound (hereinafter also referred to as “vinyl monomer (d2)”).
  • a composite rubber-reinforced graft resin [D] hereinafter also referred to as “component [D]”.
  • the component [D] is a resin in which the copolymer of the vinyl monomer (d2) is grafted to the composite rubber (d1), like the component [A], and the composite rubber portion; It is a resin comprising a copolymer part containing a structural unit derived from a vinyl monomer (d2).
  • the composite rubber (d1) used for forming the component [D] is composed of an organosiloxane rubber and a (co) polymer rubber having a structural unit derived from a (meth) acrylic acid alkyl ester, It is a compounded rubber that is not independent of each other due to entanglement of the two.
  • the organosiloxane rubber is preferably a polyorganosiloxane (d1-1) described later, and the (co) polymer rubber containing a structural unit derived from the (meth) acrylic acid alkyl ester is a poly (meta) described later.
  • Acrylic acid ester (d1-2) is preferred.
  • the composite rubber (d1) containing the polyorganosiloxane (d1-1) and the poly (meth) acrylic acid ester (d1-2) includes an alkyl (meth) acrylate in the presence of the polyorganosiloxane (d1-1).
  • organo A rubber obtained by a method of polymerizing siloxane can be used.
  • the former method is preferable, and the method will be described in detail below.
  • the polyorganosiloxane (d1-1) is preferably one in which a cyclic organosiloxane is linked via a graft crossing agent, and a cyclic organosiloxane having three or more members and a polyorganosiloxane graft crossing agent (hereinafter referred to as “A product obtained by emulsion polymerization of an organosiloxane mixture containing a “siloxane cross-linking agent”) is preferred.
  • the organosiloxane mixture may contain a polyorganosiloxane crosslinking agent (hereinafter referred to as “siloxane crosslinking agent”) as necessary.
  • Cyclic organosiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane Etc. These may be used alone or in combination of two or more.
  • the siloxane crossing agent is bonded to the cyclic organosiloxane via a siloxane bond to form a bond with the poly (meth) acrylic acid ester (d1-2) or the vinyl monomer (d2) described later. What can be done is preferred. From the viewpoint of reactivity with the cyclic organosiloxane, an alkoxysilane compound having a vinyl group is preferred.
  • alkoxysilane compound examples include ⁇ -methacryloyloxyethyldimethoxymethylsilane, ⁇ -methacryloyloxypropyldimethoxymethylsilane, ⁇ -methacryloyloxypropylmethoxydimethylsilane, ⁇ -methacryloyloxypropyltrimethoxysilane, and ⁇ -methacryloyloxypropylethoxydiethyl.
  • Methacryloyloxysilane such as silane, ⁇ -methacryloyloxypropyldiethoxymethylsilane, ⁇ -methacryloyloxybutyldiethoxymethylsilane; vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane; vinylphenyl such as p-vinylphenyldimethoxymethylsilane Silane; ⁇ -mercaptopropyldimethoxymethylsilane, ⁇ -mercaptopropyltrimethoxysilane, etc. It includes mercaptosilane. These compounds may be used alone or in combination of two or more.
  • siloxane crosslinking agent a compound having 3 or 4 functional groups capable of binding to the cyclic organosiloxane is preferable.
  • examples of such compounds include trialkoxyalkylsilanes such as trimethoxymethylsilane; trialkoxyarylsilanes such as triethoxyphenylsilane; tetraalkoxys such as tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, and tetrabutoxysilane.
  • Silane etc. are mentioned. These may be used alone or in combination of two or more. Of these, tetraalkoxysilane is preferable, and tetraethoxysilane is particularly preferable.
  • the ratio of these components used is preferably 60 to 99 when the total of these components is 100% by mass. 0.9 mass%, 0.1-10 mass%, and 0-30 mass%.
  • the particularly preferred amount of the cyclic organosiloxane used is 70 to 99.9% by mass.
  • the emulsion polymerization of the organosiloxane mixture includes the following methods. (1) A method in which an emulsifier and water are added to an organosiloxane mixture to obtain a latex, and the latex is made into fine particles, and then this is mixed with an acid catalyst and reacted. (2) An emulsifier is added to the organosiloxane mixture. A method of adding an acid catalyst together with water to make a latex, making the latex fine particles and reacting
  • the emulsifier examples include anionic emulsifiers such as sodium alkylbenzene sulfonate, sodium alkyl sulfonate, and sodium polyoxyethylene alkyl sulfate. These compounds may be used alone or in combination of two or more. Of these, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferred.
  • the amount of the emulsifier used is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the organosiloxane mixture in order to maintain a stable dispersion state of the latex. Further, the upper limit is preferably 15 parts by mass in order to avoid coloration caused by the emulsifier itself and coloration due to deterioration of the thermoplastic resin composition.
  • the acid catalyst examples include sulfonic acids such as alkylsulfonic acid, alkylbenzenesulfonic acid, and alkylnaphthalenesulfonic acid; and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These may be used alone or in combination of two or more. Of these, alkylbenzene sulfonic acid is preferable because n-dodecylbenzene sulfonic acid is more preferable because it is excellent in stabilizing action of the latex containing polyorganosiloxane.
  • the amount of the acid catalyst used is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the organosiloxane mixture.
  • the acid catalyst in the method (1) it is preferable to use an acid catalyst aqueous solution dissolved in water. It is preferable that the acid catalyst aqueous solution is heated to a high temperature, and then the finely divided latex is dropped into the aqueous solution at a constant rate to advance the polymerization reaction.
  • This method (1) is preferable because the particle diameter of the resulting polyorganosiloxane can be easily controlled.
  • the acid catalyst may be used as it is, or an acid catalyst aqueous solution obtained by dissolving in water may be used. Then, the acid catalyst or the acid catalyst aqueous solution can be added to and mixed with the organosiloxane mixture, the emulsifier and the water.
  • the latex is made into fine particles by a homomixer that makes the hydrophobic substance in the latex fine particles by shearing force by high-speed rotation, a homogenizer that makes fine particles by jetting power from a high-pressure generator, etc.
  • a high-pressure emulsification apparatus such as a homogenizer is preferable because a latex having a small particle size distribution width of the organosiloxane mixture can be obtained.
  • the polymerization time for forming the polyorganosiloxane (d1-1) is preferably about 1 hour after the end of the dropwise addition of the latex.
  • the polymerization time is preferably 2 hours or more, more preferably 5 hours or more.
  • the polymerization temperature is preferably 50 ° C. or higher, more preferably 80 ° C. or higher.
  • Emulsion polymerization can be stopped by cooling the reaction solution and further neutralizing with an alkaline substance such as sodium hydroxide, potassium hydroxide, sodium carbonate or the like.
  • the volume average particle diameter of the polyorganosiloxane (d1-1) obtained by the above operation is preferably 120 nm or less, more preferably 100 nm or less. However, the lower limit is usually 60 nm.
  • a monomer (mm) containing a (meth) acrylic acid alkyl ester compound is polymerized to obtain polyorganosiloxane (d1-1) and poly (poly (siloxane)).
  • a composite rubber (d1) containing a (meth) acrylic acid ester (d1-2) can be obtained.
  • the monomer (mm) may be only a (meth) acrylic acid alkyl ester compound, or may be composed of a (meth) acrylic acid alkyl ester compound and another compound.
  • the (meth) acrylic acid alkyl ester compound is preferably a compound having 1 to 14 carbon atoms in the alkyl group of the ester moiety. Specific examples are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate.
  • Tert-butyl (meth) acrylate pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, (meth) Nonyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.
  • Examples of the (meth) acrylic acid alkyl ester compounds include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, hexyl methacrylate, 2-ethylhexyl (meth) acrylate, dodecyl methacrylate and methacrylic acid. Tridecyl acid is preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
  • the other compound is not particularly limited as long as it is a compound copolymerizable with the (meth) acrylic acid alkyl ester compound, and has one carbon-carbon double bond excluding the (meth) acrylic acid alkyl ester compound.
  • Examples thereof include compounds and compounds having two or more carbon-carbon double bonds.
  • the other compound is preferably a compound having two or more carbon-carbon double bonds, and is a poly (meth) acrylate graft grafting agent (hereinafter referred to as “acrylic crosslinking agent”) and poly (meth).
  • acrylic crosslinking agent a poly (meth) acrylate graft grafting agent
  • a crosslinking agent for acrylic esters hereinafter referred to as “acrylic crosslinking agent” is preferably used.
  • the acrylic crossover agent is preferably a compound having a different reactivity with the (meth) acrylic acid ester compound at a plurality of carbon-carbon double bonds contained in the molecule.
  • the acrylic crossing agent include allyl (meth) acrylate, triallyl cyanurate, triallyl isocyanurate and the like. These may be used alone or in combination of two or more.
  • the acrylic crosslinking agent is preferably a compound that forms a crosslinked structure in the poly (meth) acrylic acid ester (d1-2).
  • acrylic crosslinking agent examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and neopentyl.
  • examples include glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethyloltetra (meth) acrylate, and divinylbenzene. These may be used alone or in combination of two or more.
  • the monomer (mm) may be composed of a (meth) acrylic acid alkyl ester compound and an acrylic crossing agent, or a (meth) acrylic acid alkyl ester compound, an acrylic crossing agent, and an acrylic crosslinking agent. It may consist of:
  • the use ratio of the above (meth) acrylic acid alkyl ester compound, acrylic cross-linking agent and acrylic cross-linking agent is preferably 80 to 99.99% by mass, and 0.0. 01 to 10% by mass and 0 to 10% by mass.
  • the particularly preferred amount of the (meth) acrylic acid alkyl ester compound is 90 to 99.99% by mass.
  • the poly (meth) acrylic acid ester (d1-2) has a sufficient graft polymerization origin. If it is at most mass%, the rubber elasticity of the poly (meth) acrylic acid ester (d1-2) can be maintained. If the amount of the acrylic crosslinking agent used in the monomer (mm) is 10% by mass or less, the rubber elasticity of the poly (meth) acrylic acid ester (d1-2) can be maintained.
  • the amount of the monomer (mm) used for polymerization in the presence of the polyorganosiloxane (d1-1) is preferably 400 when the polyorganosiloxane (d1-1) is 100 parts by mass.
  • the amount is from 9,900 parts by weight, more preferably from 900 to 1,900 parts by weight.
  • the composite rubber (d1) using the polyorganosiloxane (d1-1) and the monomer (mm) for example, it is necessary for the latex containing the polyorganosiloxane (d1-1).
  • a polymerization initiator, an emulsifier, a chain transfer agent (molecular weight regulator), etc. polymerization is performed while supplying a monomer (mm).
  • the monomer (mm) may be supplied all at once or in a divided manner, and further continuously.
  • the supplied monomer (mm) may be as it is, or an emulsion prepared in advance using a mixture containing the monomer (mm), an emulsifier, and water is used. May be. In the case of the latter, you may use the emulsion which atomized the monomer (mm).
  • polymerization initiator examples include organic peroxides, azo compounds, inorganic peroxides, redox type polymerization initiators, and the like.
  • redox type polymerization initiators are preferred, and in particular, a combination of ferrous sulfate, sodium pyrophosphate, glucose, and hydroperoxide, and a combination of ferrous sulfate, disodium ethylenediaminetetraacetate, longalite, and hydroperoxide. Etc. are preferred.
  • the amount of the polymerization initiator used is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass when the monomer (mm) is 100 parts by mass.
  • the composite rubber (d1-1) can be efficiently produced, and the resulting molded product is excellent in impact resistance and glitter. be able to.
  • the emulsifier examples include carboxylates such as sodium sarcosine, fatty acid potassium, fatty acid sodium, dipotassium alkenyl succinate, and rosin acid soap; alkyl sulfate ester; sodium alkylbenzene sulfonate; sodium alkyl sulfonate; polyoxyethylene alkyl sodium sulfate, etc.
  • Anionic emulsifiers are mentioned. These compounds may be used alone or in combination of two or more.
  • the latex at the time of emulsion polymerization can be stably maintained and the polymerization conversion rate can be increased.
  • the same emulsifier used for the production of the polyorganosiloxane (d1-1) may be used as the emulsifier.
  • the polymerization temperature when polymerizing the monomer (mm) is usually 65 ° C. to 98 ° C., preferably 70 ° C. to 95 ° C.
  • the polymerization time is usually 0.5 to 6 hours.
  • the volume average particle diameter of the composite rubber (d1) obtained by the above steps is preferably 50 to 150 nm, more preferably 60 to 120 nm.
  • the ratio of the volume average particle diameter to the number average particle diameter is preferably 2 or less, more preferably 1.5 or less, and particularly preferably 1.1 or less.
  • the gel content is preferably 70% by mass or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, and the toluene swelling degree is preferably 2 to 30 times, more preferably 6 to 25 times. It is.
  • the composite rubber (d1) obtained as described above contains a poly (meth) acrylic acid ester (d1-2) containing a structural unit derived from the monomer (mm) in the polyorganosiloxane (d1-1). ) Grafted product form, or polyorganosiloxane (d1-1) and poly (meth) acrylate ester (d1-2) containing structural units derived from the monomer (mm). An intertwined cross-linked network is formed, and is substantially in a form that cannot be separated from each other.
  • the latex containing the composite rubber (d1) contains poly (meth) acrylic acid ester (d1-2) containing a structural unit derived from the monomer (mm) and a polyorganosiloxane (d1-1). Independently, it may be contained while liberated.
  • the composite rubber (d1) can be further subjected to an enlargement treatment as required in the same manner as in the case of the acrylic rubbery polymer (a1).
  • the vinyl monomer (d2) used for forming the component [D] is a (meth) acrylic acid alkyl ester compound, aromatic vinyl compound and vinyl cyanide compound whose homopolymer has a glass transition temperature exceeding 0 ° C. including.
  • the (meth) acrylic acid alkyl ester compound in which the glass transition temperature of the homopolymer exceeds 0 ° C. include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methyl acrylate and the like.
  • the aromatic vinyl compound and the vinyl cyanide compound the aromatic vinyl compound and the cyanidated vinyl compound that can be used in the vinyl monomer (a2) can be applied.
  • the aromatic vinyl compound contains ⁇ -methylstyrene
  • it contains structural units derived from ⁇ -methylstyrene as in the case of producing the component [A] using the acrylic rubbery polymer (a1).
  • the (co) polymer may be formed as an ungrafted polymer, when a copolymer containing a structural unit derived from ⁇ -methylstyrene is produced, this copolymer is added to the component [B]. included.
  • the proportion of the (meth) acrylic acid alkyl ester compound in which the glass transition temperature of the homopolymer exceeds 0 ° C. contained in the vinyl monomer (d2) Therefore, when the total of the (meth) acrylic acid alkyl ester compound, the aromatic vinyl compound and the vinyl cyanide compound is 100% by mass, it is preferably 40 to 60% by mass.
  • the ratio of the amounts of the aromatic vinyl compound and the vinyl cyanide compound contained in the vinyl monomer (d2) is preferably 10 to 90, respectively, when the total of both is 100% by mass. Mass% and 10 to 90 mass%.
  • the proportion of the total amount of the (meth) acrylic acid alkyl ester compound, aromatic vinyl compound and vinyl cyanide compound in which the glass transition temperature of the homopolymer exceeds 0 ° C. contained in the vinyl monomer (d2) is as follows:
  • the amount is preferably 70 to 100% by mass, more preferably 85 to 100% by mass, based on the total amount of the vinyl monomer (d2).
  • the vinyl monomer (d2) may be composed of a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound and a vinyl cyanide compound having a glass transition temperature of a homopolymer exceeding 0 ° C., Furthermore, other monomers ((meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds whose homopolymer has a glass transition temperature of 0 ° C. or lower , An amino group-containing unsaturated compound, an amide group-containing unsaturated compound, an epoxy group-containing unsaturated compound, an oxazoline group-containing unsaturated compound, etc.).
  • the proportion of the composite rubber (d1) and the vinyl monomer (d2) used in the production of the component [D] is 100 from the viewpoint of the balance between the impact resistance and the glitter of the molded product.
  • mass% it is preferably 30 to 90 mass% and 10 to 70 mass%, more preferably 50 to 85 mass% and 15 to 50 mass%, still more preferably 70 to 80 mass% and 20 to 30 mass%, respectively. % By mass.
  • the method for producing the component [D] is not particularly limited, and in the presence of the composite rubber (d1), a part of the vinyl monomer (d2) is supplied for polymerization, and then the remainder is supplied. Examples thereof include a method of proceeding polymerization and a method of proceeding polymerization by supplying the entire amount of the vinyl monomer (d2) in the presence of the composite rubber (d1). In the present invention, component [D] obtained by the former method is preferred.
  • a (meth) acrylic acid alkyl ester compound in which the glass transition temperature of the homopolymer exceeds 0 ° C. is graft-polymerized, and then ⁇ -methylstyrene is contained.
  • a vinyl monomer (d2) containing a non-aromatic vinyl compound and a vinyl cyanide compound can be added for polymerization.
  • thermoplastic resin composition containing the component [D] obtained by using the vinyl monomer (b2) in this way is used, a molded article particularly excellent in impact resistance and glitter is obtained. be able to.
  • the composite rubber (d1) is preferably a composite rubber obtained by emulsion polymerization of the monomer (mm) in the presence of the polyorganosiloxane (d1-1).
  • Graft polymerization can be performed in the same manner as in the production method of the component [A]. If necessary, water, an emulsifier, a polymerization initiator, a chain transfer agent and the like can be added to the reaction system. As these emulsifiers, polymerization initiators, chain transfer agents and the like, the compounds exemplified in the production method of the component [A] can be used.
  • the graft ratio in the component [D], that is, the proportion of the copolymer containing the structural unit derived from the vinyl monomer (d2) grafted on the composite rubber (d1) is determined by molding processability, impact resistance, From the viewpoint of glitter, etc., it is preferably 5 to 200% by mass, more preferably 10 to 150% by mass, and still more preferably 20 to 120% by mass. If the graft ratio is too low, the impact resistance of the molded product may not be sufficient. On the other hand, if the graft ratio is too high, moldability may not be sufficient.
  • the content of the component [D] is preferably 1 to 35 parts by mass, more preferably 1 to 25, when the component [A] is 100 parts by mass. Part by mass.
  • the content of the component [D] is in the above range, the resulting molded article has an excellent balance between heat resistance and glitter.
  • the composition of the present invention contains the component [D], the acrylic rubbery polymer (a1) constituting the component [A] and the composite rubber constituting the component [D] (
  • the content ratio of d1) is preferably 80 to 99% by mass and 1 to 20% by mass, more preferably 85 to 99% by mass and 1 to 15% by mass, when the total of both is 100% by mass. More preferably, they are 90 to 98% by mass and 2 to 10% by mass.
  • the resulting molded article has an excellent balance between heat resistance and glitter.
  • the content of the acrylic rubbery polymer (a1) is 100 masses of the total of the components [A], [B], and [C] from the viewpoint of impact resistance of the molded product. %, It is 10 to 40% by mass, preferably 12 to 35% by mass, more preferably 15 to 25% by mass. Further, when the composition of the present invention contains the component [D], the content of the acrylic rubbery polymer (a1) is determined from the component [A], from the viewpoint of impact resistance of the molded product. When the total of [B], [C] and [D] is 100% by mass, it is preferably 32 to 39% by mass, more preferably 34 to 39% by mass, still more preferably 36 to 39% by mass. is there.
  • the content of the structural unit (b1) is, from the viewpoint of heat resistance of the molded product, a structural unit constituting the component [A], a structural unit constituting the component [B], and
  • the total of the structural units constituting the component [C] is 100% by mass, it is 15 to 45% by mass, preferably 15 to 40% by mass, more preferably 18 to 35% by mass.
  • the content of the structural unit (b1) is, from the viewpoint of heat resistance of the molded product, a structural unit constituting the component [A],
  • the total of the structural unit constituting component [B], the structural unit constituting component [C], and the structural unit constituting component [D] is 100% by mass, it is preferably 15 to 45% by mass. More preferably, it is 15 to 40% by mass, still more preferably 18 to 35% by mass.
  • the content of the structural unit (b1) may be derived only from the component [B], or derived from the component [B], and the component [A] and / or the component [D]. It may be.
  • the component [A] is a vinyl monomer (a2) containing an aromatic vinyl compound containing ⁇ -methylstyrene and a vinyl cyanide compound in the presence of the acrylic rubber polymer (a1).
  • the component [D] is a vinyl resin containing an aromatic vinyl compound containing ⁇ -methylstyrene and a vinyl cyanide compound in the presence of the composite rubber (d1). In the case of a graft resin obtained by polymerizing the monomer (d2).
  • the composition of the present invention may contain other thermoplastic resins, additives, and the like to be described later in addition to the component [D] as long as the required performance is not impaired.
  • the upper limit of the content is the total amount of the above components [A], [B] and [C], or the above components [A], [C]
  • the total amount of B], [C] and [D] is 100 parts by mass, it is preferably 30 parts by mass, more preferably 20 parts by mass, and even more preferably 10 parts by mass.
  • a preferred composition is obtained by the following method.
  • a rubber reinforced resin containing a first acrylic rubbery polymer reinforced graft resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound other than methylstyrene and a vinyl cyanide compound hereinafter, ⁇ -methylstyrene copolymer (hereinafter referred to as “raw material [X]”) and 25 to 85% by mass of the structural unit derived from [Y] ⁇ -methylstyrene based on the total structural unit (hereinafter referred to as “the raw material [X]”).
  • composition (R1) a raw material (hereinafter also referred to as “raw material (S1)”) (hereinafter referred to as “composition (R1)”).
  • a rubber reinforced resin (hereinafter also referred to as “raw material [Z]”) containing a first composite rubber reinforced graft resin obtained by polymerizing a nil compound, and a raw material (hereinafter referred to as “raw material (S2)”) Composition) (hereinafter referred to as “composition (R2)”).
  • the raw materials (S1) and (S2) may contain other thermoplastic resins in addition to the components [C] and [D].
  • the raw material [X] contains an aromatic vinyl compound and a vinyl cyanide compound other than ⁇ -methylstyrene in the presence of the acrylic rubber polymer (a1)
  • graft resin (Ar) First acrylic rubbery polymer reinforced graft resin (hereinafter also referred to as “graft resin (Ar)”) grafted to the rubbery polymer (a1), and other aromatics other than ⁇ -methylstyrene
  • a copolymer containing a structural unit derived from a vinyl compound and a structural unit derived from a vinyl cyanide compound (a structural unit derived from a (meth) acrylic acid alkyl ester compound may be included.
  • (Cr1) Also referred to as “copolymer (Cr1)”.
  • the graft resin (Ar) is included in the component [A]
  • the copolymer (Cr1) is included in the component [C].
  • the raw material [Y] is an ⁇ -methylstyrene copolymer contained in the component [B], and the raw material [Y] prepared in advance can be used as it is.
  • the ratio of the amounts of the raw materials [X] and [Y] used to make the composition (R1) is preferably 10 to 90% by mass and 10 to 10% when the total of both is 100% by mass, respectively. 90% by mass, more preferably 20 to 85% by mass and 15 to 80% by mass, still more preferably 30 to 80% by mass and 20 to 70% by mass.
  • the raw material (S1) is prepared by separately blending a copolymer corresponding to the component [C] (hereinafter referred to as “copolymer [W1]”) as described above. You can also.
  • the copolymer [W1] include a copolymer composed of the structural units (c1) and (c2), a copolymer composed of the structural units (c1) and (c3), and the structural units (c1), (c2 ) And (c3). These may be used alone or in combination of two or three kinds.
  • the proportion of these amounts used is 100% by mass of the total of the three.
  • the graft resin (Ar) constituting the raw material [X] is contained in the component [A] as described above, and the copolymer (Cr1) It is contained in component [C].
  • the raw material [Y] is an ⁇ -methylstyrene copolymer contained in the component [B], and the raw material [Y] prepared in advance can be used as it is.
  • the raw material [Z] polymerizes a (meth) acrylic acid alkyl ester compound in which the glass transition temperature of the homopolymer exceeds 0 ° C.
  • a composite rubber reinforced graft resin hereinafter also referred to as “graft resin (Dr)”
  • graft resin (Dr) a structural unit derived from an aromatic vinyl compound excluding ⁇ -methylstyrene
  • a copolymer (which may contain a structural unit derived from a (meth) acrylic acid alkyl ester compound.
  • copolymer (Cr2) hereinafter also referred to as “copolymer (Cr2)”).
  • the graft resin (Dr) is included in the component [D]
  • the copolymer (Cr2) is included in the component [B] and / or the component [C]. Therefore, in the composition (R2), the graft resin (Dr) is included in the component [D], and the mixture of the copolymers (Cr1) and (Cr2) is included in the components [B] and [C]. .
  • the ratio of the amounts of the raw materials [X], [Y] and [Z] used to make the composition (R2) is preferably 10 to 89, respectively, when the total of the three members is 100% by mass. % By mass, 10-89% by mass and 1-30% by mass, more preferably 20-83% by mass, 15-78% by mass and 2-25% by mass, still more preferably 30-77% by mass, 20-67% by mass. And 3 to 20% by mass.
  • the raw material (S2) is prepared by separately blending a copolymer corresponding to the component [C] (hereinafter referred to as “copolymer [W2]”) as described above. You can also.
  • the copolymer [W2] include a copolymer composed of the structural units (c1) and (c2), a copolymer composed of the structural units (c1) and (c3), and the structural units (c1), (c2 ) And (c3). These may be used alone or in combination of two or three kinds.
  • the ratio of these amounts used is the sum of the four. Is preferably 10 to 89% by mass, 9 to 89% by mass, 1 to 30% by mass, and 1 to 60% by mass, more preferably 20 to 83% by mass, and 13 to 78% by mass, respectively. %, 2 to 25% by weight and 2 to 50% by weight, more preferably 30 to 77% by weight, 17 to 67% by weight, 3 to 20% by weight and 3 to 40% by weight.
  • the composition (R1) is obtained by mixing the raw materials (S1), but the raw materials [X] and [Y] (and the copolymer [W1]) are obtained by the same polymerization method. Can be made into a resin mixture comprising a graft resin (Ar), a raw material [Y] and a copolymer (Cr1) (and a copolymer [W1]) in a latex or a resin solution, and obtained by recovering this. Composition. The same applies to the composition (R2).
  • the form of the composition of the present invention is not particularly limited, but is preferably a melt-kneaded product. Therefore, when the compositions (R1) and (R2) are melt-kneaded, the raw materials (S1) and (S2) are respectively converted into a single screw extruder, a twin screw extruder, a Banbury mixer, and a pressure. A method using a kneader or the like such as a kneader and (two) rolls is applied. At the time of kneading, the respective components may be kneaded in a lump or may be kneaded while being divided and blended.
  • the kneading temperature is preferably 200 ° C. to 300 ° C., more preferably 220 ° C. to 280 ° C.
  • thermoplastic resins that can be blended are obtained by polymerizing vinyl monomers in the presence of other rubbery polymers excluding the acrylic rubbery polymer (a1).
  • other rubber-reinforced resins such as ABS resin and AES resin, poly (meth) acrylic acid alkyl ester resins such as PMMA, polyvinyl chloride resin, polyamide resin, polycarbonate resin, polyester resin, polyphenylene oxide resin and the like can be mentioned. . These may be contained independently and 2 or more types may be contained.
  • additives that can be incorporated into the composition include fillers, metal powders, reinforcing agents, plasticizers, compatibilizers, thermal stabilizers, light stabilizers, antioxidants, ultraviolet absorbers, pigments, electrification Examples thereof include an inhibitor, a lubricant, a flame retardant, and an antibacterial agent.
  • the thermoplastic resin composition for a lamp housing of the present invention is preferably a molding material for a molded product in which a vapor deposition layer is formed on the surface thereof by direct vapor deposition.
  • Direct vapor deposition is a method in which a vapor deposition layer of metal or the like is formed directly on the surface of a molded product by a vacuum vapor deposition method, a sputtering method or the like without providing an undercoat layer.
  • a specific method of direct vapor deposition for example, a molded product is placed in a container whose pressure is reduced to about 10 ⁇ 3 to 10 ⁇ 4 Pa, and a vapor deposition material vaporized or sublimated in the container is used for the molded product.
  • vapor deposition material When vapor deposition material is vaporized or sublimated, known means such as resistance heating and high frequency induction are appropriately selected.
  • metal oxides etc. other than metals such as aluminum, chromium, zinc, gold
  • the molded product before vapor deposition may be subjected to a treatment for improving adhesion by RF plasma, ion gun irradiation or the like in advance, but according to the composition of the present invention, That process can be omitted.
  • the thermoplastic resin composition for a lamp housing of the present invention is preferably a molding material for a molded product to which a hot plate welding method and / or a laser welding method is applied.
  • the hot plate welding method is a method in which a heated hot plate is pressed against each bonding site of two molded articles to melt the resin, and the bonding sites are quickly brought into contact with each other to be joined.
  • a specific method of hot plate welding a metal plate whose surface is coated with a fluororesin or the like is heated to a temperature equal to or higher than the melting point of the resin constituting the molded product, for example, 200 ° C. to 260 ° C.
  • the (hot plate) is pressed against the bonding part of the two molded products, for example, for 8 to 15 seconds to melt the resin.
  • the metal plate (hot plate) is pulled away from the molded product, the parts to be bonded are brought into contact with each other, and held for 5 to 15 seconds, for example, so that both are joined.
  • a hot plate heated to a high temperature of 260 ° C. or higher a solid metal plate that is not surface-treated is usually used.
  • the welding method in this case is the same as that of the metal plate coated with a fluororesin or the like. According to the composition of the present invention, stringing when the hot plate is pulled away from the molded product is suppressed, so that the appearance of the joined product is not impaired.
  • the resin member A containing the laser light transmitting material and the resin member B containing the laser light absorbing material are brought into contact with each other, and the resin member A is irradiated with the laser light.
  • the resin member B is made to reach the bonding part of the resin member B while allowing A to pass therethrough, and at the same time, the bonding part of the resin member A is melted by heat transfer to join the resin members together.
  • the composition of the present invention is suitable for forming the resin member B.
  • Examples of the laser light absorbing material to be blended include black pigments such as carbon black (for example, acetylene black, lamp black, thermal black, furnace black, channel black, ketjen black), red pigments such as Bengala, molyb
  • black pigments such as carbon black (for example, acetylene black, lamp black, thermal black, furnace black, channel black, ketjen black)
  • red pigments such as Bengala
  • molyb examples include inorganic pigments such as orange pigments such as date orange, white pigments such as titanium oxide, and organic pigments such as yellow pigments, orange pigments, red pigments, blue pigments, and green pigments.
  • Laser light sources used for laser welding include gas lasers such as Ar laser (510 nm), He—Ne laser (630 nm) and CO 2 laser (10,600 nm), liquid lasers such as dye laser (400 to 700 nm), and YAG lasers. Examples thereof include solid lasers such as (1,064 nm) and semiconductor lasers (655 to 980 nm). A semiconductor laser is preferably used in terms of beam quality and cost.
  • the molded product of the present invention is a molded product (lamp housing or the like) obtained using the composition of the present invention. That is, the molded article of the present invention contains the composition of the present invention. Since the composition is excellent in molding processability, injection molding method, sheet extrusion molding method, vacuum molding method, profile extrusion molding method, compression molding method, hollow molding method, differential pressure molding method, blow molding method, foam molding method, gas Suitable for injection molding method and the like. Further, the molded product of the present invention may be subjected to a metallization treatment using a direct vapor deposition method in which a metal layer is formed by vacuum vapor deposition, sputtering, or the like on the surface without forming an undercoat layer. it can.
  • the metallized molded article is excellent in glitter. This surface may be left as it is, but for example, a top coat layer can be formed by painting, plasma polymerization or the like in order to protect it from the occurrence of scratches due to dust or the like, oxidation degradation, and the like.
  • the physical properties and the measurement methods related to the evaluation are as follows.
  • the volume average particle size (Mv) and number average particle size (Mn) of the acrylic rubber polymer in the latex are “Microtrack” manufactured by HONEYWELL. It was measured at 25 ° C. using “UPA150”. The unit is nm. From this measured value, the particle size distribution Mv / Mn was calculated.
  • Toluene swelling degree and gel content of acrylic rubbery polymer The toluene swelling degree and gel content were determined by the following methods. About 0.2 gram of the acrylic rubbery polymer was weighed (mass is Wr), charged into 25 ml of toluene, and lightly stirred.
  • Charpy impact strength Measured according to ISO 179. Load 2J, the unit is kJ / m 2.
  • (6) Deflection temperature under load Measured according to ISO 75. The unit is ° C.
  • a flat black molded product of 55 mm ⁇ 2.4 mm (equipped with a side gate of 4 mm ⁇ 1 mm at the center of one side of 55 mm) was obtained.
  • the surface of this molded product was visually observed, and the appearance was determined according to the following criteria.
  • X The gloss was insufficient, and flow marks and color separation were recognized.
  • Hot plate weldability (thread pulling)
  • the black composition used for the evaluation of the surface appearance in (7) above is supplied to an electric injection molding machine “Erject NEX30” (trade name) manufactured by Nissei Plastic Industry Co., Ltd., and injection molding (resin temperature 220 ° C. To 260 ° C.) to obtain a plate-shaped test piece of 60 mm ⁇ 30 mm ⁇ 3 mm.
  • This test piece was conditioned for 3 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%, and then tested on a hot plate under the following conditions using a hot plate test piece welding tester (manufactured by Ida Seisakusho).
  • the plate-shaped test piece (referred to as “L-1”) in (8) above was used.
  • acrylic resin “Acrypet VH-4” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. is supplied to the same injection molding machine (resin temperature 220 ° C. to 270 ° C.) as the test piece (L-1).
  • a transparent test piece (referred to as “L-2”) having the same size as that of L-1) was produced and used as an adherend.
  • the test piece (L-1) and the transparent test piece (L-2) are laser-applied to the surface of the transparent test piece (L-2) in a state in which both ends are overlapped. Both were welded by irradiation with light.
  • the welding conditions are as follows. ⁇ Laser welding conditions> Equipment Laser welding machine “NOVOLAS-C” manufactured by Leister (model name) Laser output 16A Laser scanning speed in the horizontal direction 30 mm / second, welding width 2 mm Welding length 10mm Pressure 7kg / cm 2
  • the black composition used for the evaluation of the surface appearance in (7) above is supplied to an injection molding machine “IS-170FA” (model name) manufactured by Toshiba Machine Co., Ltd., and injection molding (resin The lamp housing having a predetermined shape was obtained. Next, an aluminum deposited film having a thickness of 120 nm was formed on the surface of the lamp housing by sputtering. Thereafter, a plasma polymerized film of HMDS (1,1,1,3,3,3-hexamethyldisilazane) was formed on the surface of the vapor-deposited film to obtain a molded article for evaluating glitter.
  • the sputtering conditions and plasma polymerization conditions are as follows.
  • ⁇ Sputtering conditions Equipment Vacuum deposition system “VRSP350MD” (model name) manufactured by Shin Meiwa Kogyo Co., Ltd. Pressure after roughing 5.0 Pa Pressure after completion of main pulling 5.0 ⁇ 10 -3 Pa Introducing gas Argon 100 sccm Degree of vacuum during film formation 0.7 Pa ⁇ Plasma polymerization conditions> Introduction gas HMDS 30sccm Degree of vacuum during polymerization 1.5 Pa
  • the diffuse reflectance was measured for the resulting molded article for evaluation of glitter using a digital reflectometer “TR-1100AD” (model name) manufactured by Tokyo Denshoku Co., Ltd. The unit is%.
  • Synthesis Example 1-1 (1) Preparation of chemical solution 91.3 parts of n-butyl acrylate (hereinafter abbreviated as “BA”) and 0.7 part of allyl methacrylate (hereinafter abbreviated as “AMA”) were mixed, Monomer mixture (I) was prepared. Further, 1 part of potassium persulfate (hereinafter abbreviated as “KPS”) was dissolved in 99 parts of water to prepare a polymerization initiator aqueous solution (hereinafter abbreviated as “OXI aqueous solution (I)”). .
  • BA n-butyl acrylate
  • AMA allyl methacrylate
  • KPS potassium persulfate
  • Second polymerization step A reactor containing the latex was charged with one third of the monomer mixture (I) and 7 parts of an OXI aqueous solution (I), and polymerization was started at 75 ° C.
  • One hour after the start of the polymerization when the internal temperature of the reactor reached 75 ° C., one third of the monomer mixture (I) and 7 parts of the OXI aqueous solution (I) were further fed to conduct the polymerization.
  • the remaining one third of the monomer mixture (I) and 7 parts of OXI aqueous solution (I) were supplied, and polymerization was continued.
  • Synthesis Example 1-2 A latex containing an acrylic rubber polymer (a-2) was obtained in the same manner as in Synthesis Example 1-1 except that 0.5 part of sodium hydrogen carbonate was added in the first polymerization step.
  • the polymerization conversion rate at the end of the first polymerization step was 97.1%
  • the volume average particle diameter (Mv) of the rubber-like polymer particles in the obtained latex was 75 nm
  • the diameter (Mv) was 157 m
  • the particle size distribution Mv / Mn was 1.04.
  • the toluene swelling degree was 21 and the gel content was 82.0%.
  • the results are shown in Table 1.
  • Synthesis Example 1-3 (1) Preparation of chemical solution 79 parts of BA and 1 part of AMA were mixed to prepare monomer mixture (II). Further, in 10 parts of water, 0.01 parts of disodium ethylenediaminetetraacetate (hereinafter abbreviated as “EDTA”), 0.002 parts of ferrous sulfate (hereinafter abbreviated as “FES”), and Sodium formaldehyde sulfoxylate (hereinafter abbreviated as “NFS”) (0.3 parts) was dissolved to prepare a sulfoxylate-based reducing agent aqueous solution (hereinafter abbreviated as “SFS aqueous solution (I)”). .
  • EDTA disodium ethylenediaminetetraacetate
  • FES ferrous sulfate
  • NFS Sodium formaldehyde sulfoxylate
  • CHP cumene hydride peroxide
  • CAT aqueous solution (I) aqueous polymerization initiator solution
  • Second polymerization step The reactor containing the latex is charged with the remaining 15% of the SFS aqueous solution (I), and immediately thereafter, 70% of the monomer mixture (II) and the CAT aqueous solution (I). 40% of each was continuously added over 1 hour and 30 minutes to initiate the polymerization. During this time, the internal temperature of the reactor was maintained at 60 ° C. After completion of the addition, the mixture was aged at the same temperature for 30 minutes. Thereafter (2 hours after the start of polymerization), the remaining 30% of the monomer mixture (II) and the remaining 30% of the CAT aqueous solution (I) were continuously added over 1 hour, and the polymerization was continued. .
  • Synthesis Example 1-4 Preparation of chemical solution 99.8 parts of BA and 0.2 part of AMA were mixed to prepare monomer mixture (III). Further, as the polymerization initiator aqueous solution, the same OXI aqueous solution (I) as used in Synthesis Example 1-1 was used. Furthermore, 1 part of disproportionated potassium rosinate soap and 1 part of KPS were dissolved in 99 parts of water to prepare a polymerization initiator aqueous solution (hereinafter abbreviated as “OXI aqueous solution (II)”).
  • OXI aqueous solution (II) a polymerization initiator aqueous solution
  • the polymerization conversion rate at the end of the second polymerization step was 97.7%
  • the volume average particle size (Mv) of the acrylic rubber polymer (a-4) in the obtained latex was 192 nm
  • the particle size distribution Mv. / Mn was 1.09.
  • the toluene swelling degree was 32 and the gel content was 41%.
  • the results are shown in Table 1.
  • Synthesis Example 1-5 In the first polymerization step, the amount of SDBS charged to the reactor was 0.1 part, and 0.03 part of PHS and 1.5 part of sodium carbonate were used in combination as in the same manner as in Synthesis Example 1-1. A latex containing an acrylic rubbery polymer (a-5) was obtained. The polymerization conversion rate at the end of the first polymerization step was 96.8%, and the volume average particle size (Mv) of the acrylic rubbery polymer (a-5) in the obtained latex was 146 nm. The volume average particle size (Mv) at the end was 222 m, and the particle size distribution Mv / Mn was 1.09. Further, the degree of toluene swelling was 18, and the gel content was 89.6%. The results are shown in Table 1.
  • Synthesis Example 1-6 (1) Preparation of chemical solution 100 parts of BA and 0.3 part of triallyl cyanurate were mixed to prepare a monomer mixture (IV). Further, as the polymerization initiator aqueous solution, the OXI aqueous solution (I) prepared in Synthesis Example 1-1 was used. (2) Manufacture of acrylic rubbery polymer In a glass reactor equipped with a stirrer, raw material and auxiliary agent addition device, thermometer, heating device, etc. , Abbreviated as “SPP”.) 0.3 parts was charged. Thereafter, the reaction system was heated under a nitrogen stream while stirring the system.
  • particle diameter enlargement treatment of the acrylic rubbery polymer was carried out by the method described in JP-A-2003-138089. 0.15 parts of SDSB was added to a reactor containing a latex containing 100 parts of the acrylic rubbery polymer. Thereafter, 60 parts of a 5% aqueous acetic acid solution was continuously added over 30 minutes with stirring while maintaining the internal temperature of the reactor at 25 ° C. to 30 ° C. (particle diameter enlargement treatment). Then, after the addition of the acetic acid aqueous solution was completed, 20 parts of a 10% sodium hydroxide aqueous solution was continuously added over 10 minutes. As a result, a latex containing an acrylic rubber polymer (a-6) having an enlarged particle size was obtained. The volume average particle diameter (Mv) of the acrylic rubber polymer in the obtained latex was 157 nm, and the particle diameter distribution Mv / Mn was 1.15. The results are shown in Table 1.
  • Synthesis Example 1-7 In the first polymerization step, an acrylic rubber polymer (a-7) was prepared in the same manner as in Synthesis Example 1-1 except that the amounts of water and SDBS charged into the reactor were 200 parts and 2 parts, respectively. Got. The polymerization conversion rate at the end of the second polymerization step was 99.4%, the volume average particle size (Mv) of the acrylic rubber polymer (a-7) in the obtained latex was 81 nm, and the particle size distribution Mv. / Mn was 1.04. The toluene swelling degree was 15 and the gel content was 90.7%. The results are shown in Table 1.
  • Synthesis Example 1-8 In the first polymerization step, the amount of SDBS charged into the reactor is 0.05 parts, and in the second polymerization step, the latex obtained in the first step is added to one third of the monomer mixture (I).
  • An acrylic rubber polymer (a-8) was obtained in the same manner as in Synthesis Example 1-1 except that the amount of SDBS charged was 0.45 part.
  • the polymerization conversion rate at the end of the second polymerization step was 98.7%
  • the volume average particle size (Mv) of the acrylic rubber-like polymer (a-8) in the obtained latex was 278 nm
  • the particle size distribution Mv. / Mn was 1.04.
  • the toluene swelling degree was 14 and the gel content was 91.4%.
  • the results are shown in Table 1.
  • Synthesis Example 1-9 An acrylic rubber-like polymer was prepared in the same manner as in Synthesis Example 1-1 except that a monomer mixture consisting of 90 parts BA and 2 parts AMA was used instead of the monomer mixture (I). (A-9) was obtained. The polymerization conversion rate at the end of the second polymerization step was 99.3%, the volume average particle diameter (Mv) of the acrylic rubber polymer (a-9) in the obtained latex was 116 nm, and the particle diameter distribution Mv. / Mn was 1.03. The toluene swelling degree was 5 and the gel content was 91%. The results are shown in Table 1.
  • Synthesis Example 1-10 In the state in which the first polymerization step in Synthesis Example 1-1 was performed and latex was accommodated in the reactor, the second polymerization step was performed as a single unit consisting of 91.7 parts BA and 0.3 parts AMA. The total amount of the body mixture and 21 parts of the OXI aqueous solution (I) shown in Synthesis Example 1-1 were charged all at once, and polymerization was started at 75 ° C. Thereafter, a polymerization reaction was carried out for 3 hours while maintaining the internal temperature of the reactor at 75 ° C. to obtain an acrylic rubbery polymer (a-10).
  • the polymerization conversion rate at the end of the reaction in the second polymerization step was 99.2%
  • the volume average particle size (Mv) of the acrylic rubbery polymer (a-10) in the obtained latex was 121 nm
  • the particle size distribution Mv. / Mn was 1.03.
  • the toluene swelling degree was 42 and the gel content was 81.9%.
  • the results are shown in Table 1.
  • Synthesis Example 1-11 instead of the monomer mixture (I), an acrylic resin was used in the same manner as in Synthesis Example 1-1 except that a monomer mixture consisting of 91.95 parts BA and 0.05 parts AMA was used. A rubbery polymer (a-11) was obtained. The polymerization conversion rate at the end of the second polymerization step was 98.3%, the volume average particle size (Mv) of the acrylic rubber polymer (a-11) in the obtained latex was 118 nm, and the particle size distribution Mv. / Mn was 1.03. The toluene swelling degree was 23 and the gel content was 64.7%. The results are shown in Table 1.
  • Synthesis Example 1-12 1.96 parts of ⁇ -methacryloyloxypropyldimethoxymethylsilane and 98.04 parts of organosiloxane were mixed to obtain 100 parts of an organosiloxane mixture. To 100 parts of this organosiloxane mixture, 313 parts of a solution prepared by dissolving 0.68 parts of sodium dodecylbenzenesulfonate in deionized water was added, and the mixture was stirred at 10,000 rpm for 5 minutes using a homomixer. Thereafter, the organosiloxane latex was made fine by passing it twice through a homogenizer at a pressure of 300 kg / cm 2 .
  • Synthesis Example 2-1 (1) Preparation of chemical solution 73 parts of styrene (hereinafter abbreviated as “ST”), 27 parts of acrylonitrile (hereinafter abbreviated as “AN”), and tert-dodecyl mercaptan (hereinafter referred to as “chain transfer agent”). (Abbreviated as “TDM”) 0.3 parts were mixed to prepare a monomer mixture (V). Further, 0.05 part of EDTA, 0.005 part of FES and 0.25 part of NFS are dissolved in 100 parts of water to prepare a sulfoxylate-based reducing agent aqueous solution (hereinafter abbreviated as “SFS aqueous solution (II)”). did.
  • ST styrene
  • AN acrylonitrile
  • NFS tert-dodecyl mercaptan
  • BHP tert-butyl hydroperoxide
  • CAT aqueous solution (II) polymerization initiator aqueous solution
  • magnesium sulfate (coagulant) was added to the latex to coagulate the rubber reinforced resin (X-1). Thereafter, washing with water and drying were performed to recover the rubber-reinforced resin (X-1).
  • Table 2 shows the graft ratio and the intrinsic viscosity of the ungrafted polymer.
  • Synthesis Example 2-6 (1) Preparation of chemical solution 28 parts of ST and 12 parts of AN were mixed to prepare a monomer mixture (VI). Further, 0.02 part of SPP, 0.004 part of FES and 0.2 part of crystalline glucose (hereinafter abbreviated as “CDX”) are dissolved in 10 parts of water, and a sugar-containing pyrophosphate-based reducing agent aqueous solution (hereinafter, referred to as “CDX”) is dissolved. (Abbreviated as “DX aqueous solution (I)”).
  • Synthesis Examples 2-7 to 2-11 instead of the acrylic rubbery polymer (a-1), the acrylic rubbery polymers (a-7) to (a-11) shown in Table 2 were used. Rubber reinforced resins (X-7) to (X-11) were obtained in the same manner as in Synthesis Example 2-1, except that the monomer mixture having the composition shown was used. Table 2 shows the graft ratio of each resin and the intrinsic viscosity of the ungrafted polymer.
  • Synthesis Example 2-12 The latex containing 75 parts of the composite rubber (d-1) obtained in Synthesis Example 1-12 was set to 75 ° C. Thereafter, while stirring the latex, polymerization was carried out while dropping a mixed liquid consisting of 0.07 part of BHP and 12.5 parts of MMA over 20 minutes, and this state was maintained for 30 minutes after completion of the dropping. Next, while maintaining the reaction system at 75 ° C., polymerization was carried out while dropping a mixed liquid consisting of 0.07 parts of BHP, 9.5 parts of styrene and 3.0 parts of acrylonitrile over 25 minutes. After completion of the dropping, the reaction system was maintained at 75 ° C. for 1 hour with stirring to complete the polymerization.
  • a latex containing a rubber-reinforced resin (Z-1) composed of an acrylic rubbery polymer-reinforced graft resin and an ungrafted polymer was obtained.
  • a coagulant was added to the latex to coagulate the rubber reinforced resin (Z-1).
  • washing with water and drying were performed to recover the rubber-reinforced resin (Z-1).
  • Table 2 shows the graft ratio and the intrinsic viscosity of the ungrafted polymer.
  • the form of the rubber reinforced resin (Z-1) used for producing the composition is as follows.
  • hydrophobic silica “R-972” (trade name) manufactured by Nippon Aerosil Co., Ltd. Drying (hot air inlet temperature 180 ° C.) while supplying 0.05 parts with respect to 100 parts of reinforced resin (Z-1), consisting of rubber reinforced resin (Z-1) and silica A powder was obtained. In the following examples, this powder was used when producing the composition.
  • thermoplastic resin composition The polymer ( ⁇ -methylstyrene copolymer and the like) to be blended in the thermoplastic resin composition is as follows. Synthesis Example 3-1 (Synthesis of ⁇ -methylstyrene copolymer Y-1) (1) Preparation of chemical solution 70 parts of ⁇ -methylstyrene (hereinafter abbreviated as “AMS”), 5 parts of ST, 25 parts of AN and 0.02 part of TDM were mixed to prepare a monomer mixture (VII).
  • AMS ⁇ -methylstyrene copolymer Y-1
  • EDTA 0.015 part of EDTA, 0.005 part of FES and 0.4 part of NFS were dissolved in 20 parts of water to prepare a reducing agent aqueous solution (hereinafter abbreviated as “SFS aqueous solution (III)”).
  • SDS aqueous solution (III) a reducing agent aqueous solution
  • MHP 0.25 part of p-menthane hydroperoxide
  • CAT aqueous solution (III) an aqueous polymerization initiator solution
  • Synthesis Example 3-2 (Synthesis of styrene / acrylonitrile copolymer W-1) (1) Preparation of chemical solution 74 parts of ST, 26 parts of AN and 0.5 part of TDM were mixed to prepare a monomer mixture (VIII). Further, 0.1 part of EDTA, 0.005 part of FES and 0.2 part of NFS were dissolved in 10 parts of water to prepare a reducing agent aqueous solution (hereinafter abbreviated as “SFS aqueous solution (IV)”).
  • SFS aqueous solution (IV) a reducing agent aqueous solution
  • IHP diisopropylbenzene hydroperoxide
  • CAT aqueous solution (IV) a polymerization initiator aqueous solution
  • aqueous CAT solution (IV) was fed to the reactor. Then, after maintaining the reaction system at 70 ° C. for 1 hour, the polymerization reaction was completed. As a result, a latex containing a styrene / acrylonitrile copolymer (W-1) was obtained. Thereafter, magnesium sulfate (coagulant) was added to the latex to coagulate the styrene / acrylonitrile copolymer (W-1). Next, washing with water and drying were performed to recover a powder composed of the styrene / acrylonitrile copolymer (W-1). The intrinsic viscosity (in methyl ethyl ketone, 30 ° C.) was 0.42 dl / g.
  • Synthesis Example 3-3 (Synthesis of methyl methacrylate / styrene / acrylonitrile copolymer W-2) (1) Preparation of chemical solution 65 parts of methyl methacrylate (hereinafter abbreviated as “MMA”), 20 parts of ST, 15 parts of AN and 0.2 part of TDM were mixed to prepare a monomer mixture (IX). Further, the SFS aqueous solution (IV) and the CAT aqueous solution (IV) prepared in Synthesis Example 3-2 were used.
  • antioxidants The following antioxidants were used.
  • Comparative Example 1 contains components [A], [B], and [C], but ⁇ -methylstyrene with respect to the total amount of all structural units constituting components [A], [B], and [C]. This is an example in which the content of the derived structural unit is too small, and the heat resistance, hot plate weldability (a lot of stringing) and laser weldability (appearance of the joint portion) were inferior.
  • Comparative Example 2 is an example in which the components [A], [B] and [C] are contained, but the content of the acrylic rubbery polymer is too small, and impact resistance, hot plate weldability (a lot of stringing) ) And laser weldability were inferior.
  • Comparative Example 3 contains components [A], [B], and [C], but ⁇ -methylstyrene with respect to the total amount of all structural units constituting components [A], [B], and [C]. This is an example in which the content of the derived structural unit is too small, and the heat resistance, hot plate weldability (a lot of stringing) and laser weldability (appearance of the joint portion) were inferior.
  • Comparative Example 4 is an example of a composition containing an acrylic rubbery polymer reinforced graft resin obtained using an acrylic rubbery polymer having a small volume average particle diameter, and has impact resistance and laser weldability (bonding). Part strength) was inferior.
  • Comparative Example 5 is an example of a composition having too much acrylic rubbery polymer content, and a test piece could not be produced and could not be evaluated.
  • Comparative Example 6 is an example of a composition containing an acrylic rubber polymer reinforced graft resin obtained by using an acrylic rubber polymer having a high toluene swelling degree, and was poor in laser weldability and glitter.
  • Comparative Example 7 is an example of a composition containing an acrylic rubber polymer reinforced graft resin obtained using an acrylic rubber polymer having a large volume average particle diameter, and has poor laser weldability and glitter. It was.
  • Comparative Example 8 is an example of a composition containing an acrylic rubbery polymer reinforced graft resin obtained by using an acrylic rubbery polymer having a large particle size distribution (M v / M n ). , Hot plate weldability (a lot of stringing), laser weldability and glitter were poor.
  • Comparative Example 9 is an example of a composition containing an acrylic rubbery polymer reinforced graft resin obtained by using an acrylic rubbery polymer having a small volume average particle diameter, and has impact resistance and laser weldability (bonding). Part strength) was inferior.
  • Comparative Example 10 is an example of a composition containing an acrylic rubber polymer reinforced graft resin obtained by using an acrylic rubber polymer having a large volume average particle diameter, and has a surface appearance, laser weldability (bonding) Part appearance) and glossiness were inferior.
  • Comparative Example 11 is an example of a composition containing an acrylic rubbery polymer reinforced graft resin obtained by using an acrylic rubbery polymer having a low degree of toluene swelling, and has impact resistance, hot plate weldability (yarn) There were many pulls) and laser weldability (strength of the joint).
  • Comparative Example 12 is an example of a composition containing an acrylic rubber polymer reinforced graft resin obtained by using an acrylic rubber polymer having a high toluene swelling degree.
  • Comparative Example 13 is an example of a composition containing an acrylic rubber polymer reinforced graft resin obtained using an acrylic rubber polymer having a low gel content. The appearance and strength) and glitter were poor.
  • Examples 1 to 13 are examples of compositions included in the present invention, and were excellent in the balance of impact resistance, heat resistance, surface appearance, hot plate weldability, laser weldability, and glitter.
  • thermoplastic resin composition for a lamp housing of the present invention is suitable for forming a lamp housing constituting a vehicular lamp such as a head lamp, a tail lamp, and a stop lamp.
  • L-1 Plate-shaped test piece (test piece made of the composition of the present invention)
  • L-2 Transparent test piece (test piece made of a laser light transmissive material)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Non-Portable Lighting Devices Or Systems Thereof (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

La présente invention concerne une composition de résine thermoplastique pour boîtiers de lampe, qui comprend : une résine greffée renforcée avec un polymère élastomère acrylique ; et un copolymère de α-méthylstyrène qui contient de 25 à 85 % en masse de motifs structuraux dérivés de α-méthylstyrène. La résine greffée est une résine obtenue par polymérisation d'un composant de monomère vinylique qui comprend à la fois un composé vinylique aromatique et un composé de cyanure de vinyle en présence d'un polymère élastomère acrylique qui a une teneur en gel de 70 % en masse ou plus, un degré de gonflement dans du toluène de 5,5 à 30 fois, un diamètre de particule moyen en volume de 100 à 200 nm, et un rapport du diamètre de particule moyen en volume au diamètre de particule moyen en nombre inférieur à 1,1.
PCT/JP2011/061345 2010-05-18 2011-05-17 Composition de résine thermoplastique pour boîtiers de lampe, et articles moulés WO2011145628A1 (fr)

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JP6547352B2 (ja) * 2015-03-19 2019-07-24 東レ株式会社 熱可塑性樹脂組成物
JP6707817B2 (ja) * 2015-08-05 2020-06-10 東レ株式会社 熱可塑性樹脂組成物およびその製造方法
JP6628029B2 (ja) * 2015-10-05 2020-01-08 テクノＵｍｇ株式会社 レーザー溶着用熱可塑性樹脂組成物及びその成形品
KR101926740B1 (ko) * 2015-11-30 2018-12-07 주식회사 엘지화학 열가소성 수지 조성물 및 이로부터 제조되는 성형품
JP6795308B2 (ja) * 2016-02-12 2020-12-02 テクノＵｍｇ株式会社 熱可塑性樹脂組成物
JP6709658B2 (ja) * 2016-03-29 2020-06-17 テクノＵｍｇ株式会社 熱可塑性樹脂組成物およびそれを用いた成形品
JP6980445B2 (ja) * 2017-07-28 2021-12-15 テクノＵｍｇ株式会社 熱可塑性樹脂組成物及び成形品
JP7267679B2 (ja) * 2018-03-29 2023-05-02 テクノＵｍｇ株式会社 熱可塑性樹脂組成物及びその成形品
JP7107998B2 (ja) * 2020-08-19 2022-07-27 テクノＵｍｇ株式会社 レーザー溶着における吸収材用熱可塑性樹脂組成物
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