WO2007052429A1 - Composition de resine thermoplastique - Google Patents

Composition de resine thermoplastique Download PDF

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Publication number
WO2007052429A1
WO2007052429A1 PCT/JP2006/319331 JP2006319331W WO2007052429A1 WO 2007052429 A1 WO2007052429 A1 WO 2007052429A1 JP 2006319331 W JP2006319331 W JP 2006319331W WO 2007052429 A1 WO2007052429 A1 WO 2007052429A1
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Prior art keywords
weight
parts
core
thermoplastic resin
graft copolymer
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PCT/JP2006/319331
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English (en)
Japanese (ja)
Inventor
Toru Terada
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Kaneka Corporation
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to a thermoplastic resin composition containing a thermoplastic resin and a graft copolymer.
  • thermoplastic resin In order to improve the impact resistance of thermoplastic resin, it has been widely used to add a graft copolymer obtained by emulsion polymerization or suspension polymerization to thermoplastic resin.
  • a graft copolymer obtained by emulsion polymerization or suspension polymerization to thermoplastic resin.
  • a salt-bulb resin it is known to incorporate a gen-based or attalylate-based graft copolymer (see, for example, Patent Document 1).
  • (meth) acrylate rubbers have a smaller impact resistance improvement effect than Gen rubbers, and therefore, it is necessary to increase the amount of addition to the thermoplastic resin.
  • the graft copolymer which is an impact modifier, as much as possible in terms of quality or cost. Studies for improving this point have been conducted for many years (for example, see Patent Documents 3 to 5).
  • the problem is that the lubricant bleeds on the surface of the molded body and lowers the surface gloss of the molded body, which is not a satisfactory method.
  • the glass transition temperature of the polymer constituting the outermost layer is 0 ° C or less, and the glass transition of the polymer constituting the second layer from the outermost layer.
  • Proposed a method of blending an impact modifier with a layer structure in which the temperature of the polymer constituting the third layer from the outermost layer is 0 ° C or lower and the temperature force is 60 ° C or higher. (For example, see Patent Document 6).
  • Patent Document 6 since the glass transition temperature of the polymer constituting the outermost layer is as low as 0 ° C or lower and the particles themselves become sticky, the emulsion polymerization latex is suspended.
  • thermoplastic resin composition that satisfies both contradictory physical properties such as improved impact resistance and workability and surface gloss of the molded article at a high V level is still expected. Is the current situation.
  • Patent Document 1 Japanese Patent Publication No. 39-19035
  • Patent Document 2 Japanese Patent Publication No. 51-28117
  • Patent Document 3 Japanese Patent Publication No.42-22541
  • Patent Document 4 Japanese Patent Laid-Open No. 2-1763
  • Patent Document 5 JP-A-8-100095
  • Patent Document 6 Japanese Patent Publication No. 7-74306
  • the present invention provides a novel thermoplastic resin composition that has excellent weather resistance and high impact resistance, and is capable of obtaining good processability and molded article surface brightness. Let it be an issue. Means for solving the problem
  • the present inventor has conducted intensive studies to obtain good workability and molded product surface gloss while maintaining impact resistance. As a result, the core has a specific layer structure.
  • the present invention relates to thermoplastic resin (A) 100 parts by weight, core (bc) 85 to 99.5% by weight and shell (bs) O. 5 to 15% by weight (provided that core and shell the total amount is a thermoplastic ⁇ composition containing the graft copolymer (B) 0. 5 to 20 parts by weight of 100 weight 0/0), in the core (be) force soft polymers (bcs) And at least one intermediate layer made of a hard polymer (bch), and the shell (bs) is made of a hard polymer and forms an outer layer of the graft copolymer (B).
  • the invention relates to a thermoplastic resin composition.
  • a preferred embodiment relates to the above thermoplastic resin composition, wherein the innermost layer and the outermost layer in the core (be) are made of a soft polymer (bcs).
  • the core (be) force is an inner layer composed of at least one soft polymer (bcs), at least one intermediate layer composed of at least one hard polymer (bch) force, and at least one soft polymer.
  • bcs The thermoplastic resin composition according to any one of the above! /, characterized in that it has a multilayer structure having an outer layer that also has a force.
  • the embodiment is that the shell (bs) force (meth) acrylic acid ester 70 to: LOO wt%, and vinyl monomer copolymerizable with (meth) acrylic acid ester 0 to 30
  • the glass transition temperature obtained by polymerizing a monomer mixture consisting of 100% by weight (however, the total amount is 100% by weight) is 20 ° C.
  • the thermoplastic resin composition according to any one of the above, which is the above (co) polymer.
  • the embodiment is such that the hard polymer (bch) force (meth) acrylic acid ester 0-: LO 0% by weight, aromatic bulle monomer 0-: LOO% by weight, (meth) acrylic acid ester And a monomer mixture comprising 0 to 20% by weight of a vinyl monomer copolymerizable with an aromatic vinyl monomer and 0 to 20% by weight of a polyfunctional monomer (however, the total amount is 100% by weight) Is a hard polymer having a glass transition temperature of 20 ° C or higher, wherein the ratio of the hard polymer (bch) in the core (be) is 1 to 15% by weight,
  • the thermoplastic resin composition according to any one of the above.
  • the soft polymer (bcs) force (meth) acrylic acid ester is 80 to 99.8% by weight
  • the bull monomer copolymerizable with (meth) acrylic acid ester is 0 to 19. 8% by weight and a monomer mixture consisting of 0.2 to 5% by weight of a polyfunctional monomer (however, the total amount is 100% by weight) and has a glass transition temperature of less than 20 ° C.
  • the thermoplastic resin composition according to any one of the above, wherein the composition is a coalescence.
  • a preferred embodiment relates to the thermoplastic resin composition according to any one of the above, wherein the core (be) has a volume average particle diameter of 0.05 to 0.5 ⁇ m.
  • the embodiment relates to the thermoplastic resin composition according to any one of the above, wherein the thermoplastic resin composition (A) is a salted resin resin.
  • thermoplastic resin composition of the present invention has excellent weather resistance and high impact resistance, and can obtain good processability and surface gloss of a molded article.
  • the graft copolymer (B) of the present invention has a hard polymer force and a core (be) having at least one intermediate layer having a hard polymer (bch) force in the soft polymer (bcs).
  • a structure composed of a shell (bs) for example, a graft copolymer produced by an emulsion polymerization method, a suspension polymerization method, a micro suspension polymerization method, a mini emulsion polymerization method, an aqueous dispersion polymerization method, etc. Coalescence can be used.
  • a graft copolymer produced by an emulsion polymerization method can be suitably used because the structure can be easily controlled.
  • “soft” in the soft polymer means that the glass transition temperature of the polymer is less than 20 ° C., but from the following viewpoint, the polymer The glass transition temperature is preferably less than 0 ° C, and more preferably less than 20 ° C.
  • the graft copolymer (B) in the present invention is converted into a thermoplastic resin such as a salt-bulb resin.
  • the impact-absorbing ability of the polymer component is lowered, and it is difficult to obtain a significant impact resistance improving effect.
  • “hard” in the hard polymer means a force that means that the glass transition temperature of the polymer is 20 ° C. or higher.
  • the glass transition temperature is preferably 30 ° C or higher, more preferably 50 ° C or higher.
  • the graft copolymer (B) in the present invention is blended with a thermoplastic resin (A) such as a salty vinyl resin. In this case, a remarkable workability improvement effect and a surface gloss improvement effect of the molded body may be obtained.
  • the graft copolymer (B) in the present invention is converted into a thermoplastic resin such as a salt-bulb resin.
  • a thermoplastic resin such as a salt-bulb resin.
  • the glass transition temperature of the polymer can be measured by, for example, a differential scanning calorimeter.
  • the value calculated using the Fox formula is used (for example, the glass transition temperature of polymethylmethalate is 105 ° C, and the polybutyl acrylate is -54 ° C). ) O
  • the core (be) having at least one intermediate layer having a hard polymer (bch) force in the soft polymer (bcs) is hard in the core.
  • the core (be) having at least one intermediate layer having a hard polymer (bch) force in the soft polymer (bcs) is hard in the core.
  • the innermost layer and the outermost layer are soft and heavy.
  • Multi-layer structure consisting of coalesced (bcs) with a hard polymer (bch) in the middle layer, in the core
  • a multilayer structure such as a layer structure having one or two or more kinds of soft polymers inside the hard polymer (bch) can be preferably exemplified.
  • the above structures can be used singly or in combination of two or more.
  • the weight ratio of the hard polymer (bch) in the core (be) in the present invention is not particularly limited, but the ratio of the hard polymer (bch) in the core (be) is 1 to 15 wt%. It is preferable that it is 2 to 10% by weight, and more preferably 3 to 8% by weight. When the weight ratio of the hard polymer (bch) in the core (be) exceeds 15% by weight, the impact resistance improvement effect of the thermoplastic resin (A) using the graft copolymer (B) of the present invention Tend to be inferior.
  • the weight ratio of the hard polymer (bch) in the core (be) is less than 1% by weight, for example, it was used as an impact resistance improver for thermoplastic resin such as salt-bulb resin. In some cases, it may be difficult to obtain the effect of improving the workability and the effect of improving the surface gloss of the molded product.
  • the weight ratio of the inner layer to the hard polymer (bch) as the intermediate layer in the core (be) in the present invention is not particularly limited, but the ratio of the inner layer in the core (be) is 8% by weight or more. In addition, it is preferable that the amount is 15% by weight or more, and 24% by weight or more is particularly preferable.
  • the ratio of the inner layer in the core (be) is less than 8% by weight, for example, when it is used as an impact modifier for thermoplastic resin such as salt vinyl resin, The improvement effect and the surface gloss improvement effect of the molded body may be difficult to obtain.
  • the inner layer is called the inner layer with reference to the intermediate layer that also has the hard polymer (bch) force located in the innermost layer. To do.
  • the weight ratio of the outer layer to the hard polymer (bch) as the intermediate layer in the core (be) in the present invention is not particularly limited, but the ratio of the outer layer in the core (be) is 15% by weight or more. It is preferable to be 30% by weight or more, and 40% by weight or more is particularly preferable. When the proportion of the outer layer in the core (be) is less than 15% by weight, for example, when used as an impact modifier for thermoplastic resin such as salted bull resin, the impact resistance is improved. The effect may be difficult to obtain.
  • Intermediate layer made of hard polymer (bch) When there are a plurality of layers, the outer layer is referred to as the outer layer with reference to the intermediate layer made of the hard polymer (bch) located in the outermost layer.
  • the multilayer structure of the graft copolymer of the present invention for example, a force layer (be) and a shell (bs) that are generally a layer structure in which the core (be) is completely covered with the seal (bs).
  • the amount of shell for forming the layer structure may be insufficient.
  • the core (be) may not have a complete layer structure, and a part of the core (be) may be covered with the shell (bs).
  • a structure obtained by graft polymerization of a beryl monomer that is a constituent element of () can also be suitably used. Note that the concept of the multilayer structure described above also applies to the case where the multilayer structure is formed in the core (be) or the shell (bs) in the present invention.
  • composition of the shell (bs) in the graft copolymer (B) is not particularly limited! , but from the viewpoint of the dispersibility of the graft copolymer to the thermoplastic ⁇ (A) (B), for example, a (meth) acrylic acid ester 70-100 wt 0/0, and (meth) acrylic acid ester A polymer or copolymer having a glass transition temperature of 20 ° C. or higher obtained by polymerizing a monomer mixture consisting of 0 to 30% by weight of a copolymerizable vinyl monomer (total amount is 100% by weight) is preferable. Can be exemplified.
  • (meth) acryl means acryl and Z or methacryl.
  • the composition of the hard polymer (bch) in the core in the graft copolymer (B) is not particularly limited, but from the viewpoint of quality typified by processability of the obtained thermoplastic resin composition,
  • (meth) acrylic acid ester 0-: LOO% by weight, aromatic vinyl monomer 0-100% by weight, vinyl unit copolymerizable with (meth) acrylic acid ester and aromatic butyl monomer A polymer having a glass transition temperature of 20 ° C or higher, obtained by polymerizing a monomer mixture consisting of 0 to 20% by weight of a monomer and 0 to 20% by weight of a polyfunctional monomer (however, the total amount is 100% by weight).
  • a hard polymer can be suitably exemplified.
  • the composition of the soft polymer (bcs) in the core of the graft copolymer (B) is a poly (meth) acrylate-based rubber-like polymer in terms of weather resistance and the like.
  • preferred bur from the viewpoint of quality as typified by impact resistance of the thermoplastic ⁇ composition obtained, for example, (meth) acrylic acid ester 80 to 99.8 weight 0/0, (meth) acrylic acid Copolymerized with ester Glass transition by polymerizing a monomer mixture consisting of 0 to 19.8% by weight of a possible vinyl monomer and 0.2 to 5% by weight of a polyfunctional monomer (however, the total amount is 100% by weight)
  • Preferable is a soft polymer having a temperature of less than 20 ° C.
  • the volume average particle diameter of the core (be) in the graft copolymer (B) of the present invention is not particularly limited, and the repulsive force is 0.05 to 0.5 / zm. Further, it is more preferably 0.08 to 0.3 ⁇ m, and further preferably 0.1 to 0.25 m. If the volume average particle diameter of the core (be) in the Draft copolymer (B) exceeds 0.5 ⁇ m, the impact resistance improvement effect tends to be difficult to be manifested. There is a possibility that the quality such as surface gloss of the molded body molded using the fat composition may be deteriorated.
  • volume average particle diameter of the core (be) in the graft copolymer (B) is less than 0.05 ⁇ m, the impact resistance improving effect tends to be exhibited.
  • the volume average particle diameter can be measured, for example, by using MICROTRAC UPA150 (manufactured by Nikkiso Co., Ltd.).
  • the structure of the core (be) in general, a structure having a high effect of increasing the stress concentration degree can be suitably used from the viewpoint of highly improving the impact resistance.
  • thermoplastic resin (A) when blended with the thermoplastic resin (A), is highly representative in terms of weather resistance and surface gloss of the molded body, as well as exhibiting high impact resistance. It is possible to obtain a thermoplastic resin composition that does not deteriorate the physical properties.
  • the above-mentioned graft copolymer (B) can be produced according to a known method.
  • General production methods are described in, for example, JP-A-2002-363372 and JP-A-2003-119396. This is described in detail in Kaihei 9-286830. However, it is not limited to these.
  • the graft copolymer (B) that can be used in the present invention is not limited to the above-mentioned polymer.
  • the following monomer group force is selected from one or more kinds.
  • a polymer comprising a single or mixture of polymers obtained by copolymerization or graft polymerization of a monomer composition mainly composed of monomers can be used.
  • Examples of the monomer group include: (1) methyl acrylate, ethyl acetate, butyl acrylate, 2-ethyl hexyl acrylate, octyl acrylate, dodecyl acrylate.
  • Nillanes (4) vinyl carboxylic acids such as acrylic acid and methacrylic acid, (5) burcyans such as acrylo-tolyl and meta-tallow-tolyl, and (6) halogenation of butyl chloride, butyl bromide, chloroprene, etc.
  • the soft polymer (bcs) in the graft copolymer ( ⁇ ) is a (meth) acrylic acid containing an alkyl group containing 1 to 22 carbon atoms from the viewpoint of highly improving impact resistance.
  • the carbon number of the (meth) acrylic acid alkyl esters is not necessarily limited, for example, if the carbon number exceeds 22, the polymerizability may be inferior. 22 or less (meth) acrylic acid alkyl esters can be preferably used. More preferably, (meth) acrylic acid alkyl esters having 12 or less carbon atoms, which are generally used as a soft polymerization phase of a (meth) acrylic acid ester impact modifier, are preferably used. Can be used.
  • the soft polymer (bcs) in the graft copolymer (B) is a (meth) acrylic acid alkyl ester containing an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms.
  • the use amount of the multifunctional monomer (crosslinking agent and Z or graft crossing agent) used for forming the core (be) in the graft copolymer (B) of the present invention is such that impact resistance is high. From the viewpoint of improving the content, it is preferably 0.2 to 5% by weight based on the core (be), more preferably 0.2 to 2% by weight. If the amount of the polyfunctional monomer used to form the core (be) in the graft copolymer (B) exceeds 5% by weight, the impact resistance improving effect may be difficult to be exhibited.
  • the amount of the polyfunctional monomer used for forming the core (be) in the graft copolymer (B) is less than 0.2% by weight, the shape of the graft copolymer cannot be maintained during molding. There is a possibility that the effect of improving impact resistance may be manifested.
  • the amount of the polyfunctional monomer in the entire core (be) is 0 for the hard polymer (bcs) in the inner layer rather than the hard polymer (bch) as the intermediate layer in the core (be). As long as it is 2 to 5% by weight, the amount of the polyfunctional monomer used is 0% by weight.
  • the ratio of the core (be) to the shell (bs) in the graft copolymer (B) of the present invention is as follows. 15% by weight (however, the total amount of the core and the shell is 100% by weight), and further, the core (bc) is 88 to 98% by weight, and the shell (bs) is 2 to 12% by weight. It is more preferable.
  • the ratio of the core (be) is less than 85% by weight, the impact resistance improving effect of the thermoplastic resin (A) using the graft copolymer (B) of the present invention tends to be inferior.
  • the thermoplastic resin (A) in the present invention includes, for example, a salty resin resin, a (meth) acrylic resin, a styrene resin, a carbonate resin, an amide resin, Ester-based resin, olefin-based resin and the like can be preferably used. However, it is not limited to these.
  • the graft copolymer (B) according to the present invention can exhibit an excellent effect, particularly when used as an impact resistance improver for a salt-bulb-based resin.
  • the resin (A) is preferably a salted vinyl resin.
  • a salty vinyl resin means a salty vinyl homopolymer or a copolymer containing at least 70% by weight of a unit that is also induced by a salty bulle force.
  • the thermoplastic rosin composition of the present invention uses a graft copolymer (B) that has high impact resistance, excellent workability, and can obtain a good surface gloss. Thus, it is possible to achieve an excellent balance of physical properties that was difficult to achieve.
  • the content of the graft copolymer (B) in the thermoplastic resin composition is not particularly limited. However, from the viewpoint of quality and cost, 0.5 to 20% by weight with respect to 100 parts by weight of the thermoplastic resin (A). It is desirable that the amount is 0.5 to 5 parts: 1 to 7 parts by weight is particularly preferable.
  • the content of the graft copolymer (B) in the thermoplastic resin composition exceeds 20 parts by weight, the impact resistance improvement effect is sufficient, but the quality other than the impact resistance deteriorates. There is a possibility and cost may increase.
  • the content of the graft copolymer (B) in the thermoplastic resin composition is less than 0.5 parts by weight, it may be difficult to obtain a sufficient impact resistance improving effect.
  • thermoplastic resin composition of the present invention may contain additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, a pigment, an antistatic agent, a lubricant, and a processing aid as necessary. It can be added as appropriate.
  • thermoplastic resin composition of the present invention As a method for producing the thermoplastic resin composition of the present invention, a known method without particular limitation can be adopted. For example, after mixing thermoplastic resin (A) and graft copolymer (B) in advance using a Henschel mixer, tumbler, etc., single screw extruder, twin screw extruder, Banbury mixer, heating roll, etc. A method of obtaining a resin composition by melting and kneading using the above can be employed.
  • thermoplastic resin (A) and graft copolymer (B) in advance using a Henschel mixer, tumbler, etc., single screw extruder, twin screw extruder, Banbury mixer, heating roll, etc.
  • a method of obtaining a resin composition by melting and kneading using the above can be employed.
  • a glass reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet, and monomer and emulsifier addition device was charged with 160 parts by weight of deionized water and 0.04 part by weight of sodium lauryl sulfate in a nitrogen stream. The temperature was raised to 50 ° C. with stirring. Next, a mixture of butyl acrylate (hereinafter also referred to as BA) 8.98 parts by weight, aryl methacrylate (hereinafter also referred to as AMA) 0.02 parts by weight, and methane hydrate peroxide 0.01 parts by weight was charged.
  • BA butyl acrylate
  • AMA aryl methacrylate
  • a core having a volume average particle diameter of 0.19 m measured by MICROTRAC UPA150 (manufactured by Nikkiso Co., Ltd.) was obtained.
  • a mixture of 12.00 parts by weight of MMA, 3.00 parts by weight of BA, and 0.03 parts by weight of tamenno and id-peroxide was continuously added at 50 ° C over 1 hour.
  • 0.01 part by weight of cumene hydride peroxide was added, and stirring was further continued for 1 hour to complete the polymerization.
  • the polymerization conversion rate of the monomer component was 99.3%.
  • 3% by weight A latex of graft copolymer A with a core having a layer of 85% by weight and a shell having a Tg of 57 ° C. and a weight of 15% by weight was obtained.
  • a latex of graft copolymer A 100 parts by weight of polymer solid content
  • a 1.5 wt% sodium alginate (Algitex LL, manufactured by Kimiki Co., Ltd.) aqueous solution (aqueous solution measured with a B-type viscometer) A viscosity of 120 mPa's) was added so that the solid content of sodium alginate was 0.4 parts by weight with respect to 100 parts by weight of the graft copolymer A, and the mixture was stirred and mixed for 3 minutes to prepare a mixed latex.
  • a mixed latex with a temperature of 5 ° C was swirled with a swirling conical nozzle, a type of pressurized nozzle, with a nozzle diameter of 0.6 mm, spray pressure of 3.7 kgZcm 2 trowel, and a height of 5 m from the liquid level at the bottom of the tower. It sprayed so that it might become a droplet with a volume average droplet diameter of about 200 m in a cylindrical apparatus with a diameter of 60 cm.
  • a 30% strength by weight salt-calcium aqueous solution is mixed with air with a two-fluid nozzle so that the salt-calcium solid content is 5 to 15 parts by weight with respect to 100 parts by weight of the graft copolymer A.
  • Droplet size 0.1 ⁇ Sprayed with LO / zm.
  • the mixed latex droplets dropped in the tower were put into a receiving tank containing a 1.0% by weight calcium chloride aqueous solution at 5 ° C at the bottom of the tower and recovered.
  • aqueous solution of coagulated latex particles an aqueous solution of 5 wt% potassium palmitate is added so that the potassium palmitate solid content is 1.5 parts by weight with respect to 100 parts by weight of the graft copolymer A solid content. Then, after the heat treatment, dehydration and drying were carried out to prepare white rosin powder.
  • thermoplastic rosin composition preparation of molded article, and evaluation
  • Salt vinyl resin (Kanevinyl S—1001, Kanechi Co., Ltd., average polymerization degree 1000) 100 parts by weight, lead-based one-pack stabilizer (LGC3203, ACROS) 4.5 parts by weight, acid Titanium 4.5 parts by weight, calcium carbonate 8 parts by weight, methyl metatalylate polymer (specific viscosity at 30 ° C of a solution of 0.1 g of this polymer dissolved in 100 ml of black mouth form is 0.5 Less than 5 parts by weight of methyl metatalylate polymer) (Kaneace PA-20, manufactured by Kane force Co., Ltd.) 0.5 parts by weight and graft copolymer A7 parts by weight were blended with a Henschel mixer and powdered. I got a compound.
  • a glass reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet, and monomer and emulsifier addition device was charged with 160 parts by weight of deionized water and 0.04 part by weight of sodium lauryl sulfate in a nitrogen stream. The temperature was raised to 50 ° C. with stirring. Next, a mixture of 8.98 parts by weight of BA, 0.02 parts by weight of AMA and 0.01 parts by weight of tamennoide-peroxide was charged, and 10 minutes later, 0.01 part by weight of disodium ethylenediamine tetraacetate and ferrous sulfate.
  • a mixed solution prepared by dissolving 5 parts by weight of 0.007 heptahydrate in 5 parts by weight of distilled water and 0.2 part by weight of sodium formaldehydesulfoxylate were charged. After stirring for 1 hour, 0.2 parts by weight of sodium lauryl sulfate was dissolved in 2 parts by weight of distilled water and charged, followed by BA 16.86 parts by weight, AMA 0.04 parts by weight and cumene hydride peroxide 0.03 parts by weight. The monomer mixture, which is a partial force, was added dropwise over 1 hour. After stirring for 1 hour, a mixture of monomers having 2.10 parts by weight of MMA and 0.01 parts by weight of cumene hydride peroxide was added dropwise over 10 minutes.
  • White latex powder was prepared in the same manner as in Example 1, using the latex of graft copolymer B.
  • a molded product was obtained in the same manner as in Example 1 except that this graft copolymer B was used, and the Charpy strength was measured. Table 1 shows the Charpy strength results, surface gloss, and extrusion torque during extrusion.
  • a glass reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet, and monomer and emulsifier addition device was charged with 160 parts by weight of deionized water and 0.04 part by weight of sodium lauryl sulfate in a nitrogen stream. The temperature was raised to 50 ° C. with stirring. Next, a mixture of 8.98 parts by weight of BA, 0. 2 parts by weight of AMAO. 0,01 parts by weight of tamenoid oxide was added, and 10 minutes later, 0.01 part by weight of disodium ethylenediamine tetraacetate and ferrous sulfate.
  • a mixed solution prepared by dissolving 5 parts by weight of 0.007 heptahydrate in 5 parts by weight of distilled water and 0.2 part by weight of sodium formaldehydesulfoxylate were charged. After stirring for 1 hour, 0.2 parts by weight of sodium lauryl sulfate was dissolved in 2 parts by weight of distilled water, and then charged with 27.94 parts by weight of BA, 0.06 parts by weight of AMA and 0.05 parts by weight of cumene hydride port. The monomer mixture, which is a partial force, was added dropwise over 1.5 hours. After stirring for 1 hour, a mixture of MMA (3.00 parts by weight) and cumene hydride-peroxide (0.01 parts by weight) was added dropwise over 10 minutes.
  • a molded product was obtained in the same manner as in Example 1 except that this graft copolymer C was used, and the Charpy strength was measured. Table 1 shows the Charpy strength results, surface gloss, and extrusion torque during extrusion.
  • Table 1 shows the composition and Tg of each core layer of the graft copolymer obtained in Examples and Comparative Examples, the particle diameter of the core, the ratio of the hard polymer in the core, the composition and Tg of the shell, and the graft copolymer.
  • the impact strength (Charby strength) of the body was shown.
  • Example 1 From Example 1 and Comparative Examples 1 and 2, if the shell ratio in the graft copolymer (B) is in the range of 0.5 to 15% by weight, the motor load during low extrusion and high It can be seen that a high impact resistance improvement effect can be obtained simultaneously with the 60 ° surface gloss of the molded product.
  • a mixture of 7.60 parts by weight of MMA, 0.40 parts by weight of BA, and 0.02 parts by weight of cumene-hydrated peroxide was added continuously to this core at 50 ° C. over 30 minutes. After completion of the addition, 0.01 part by weight of tamennoide-peroxide was added, and stirring was further continued for 1 hour to complete the polymerization.
  • the polymerization conversion rate of the monomer component was 99.6%.
  • a latex of graft copolymer D having 92% by weight of the core having a layer of 3% by weight of the hard polymer with respect to the core and 8% by weight of silica having a Tg of 92 ° C. was obtained.
  • Graft copolymer D latex is cooled to a temperature of 5 ° C and swirling is a type of pressure nozzle A flow-type conical nozzle with a nozzle diameter of 0.6 mm, a spray pressure of 3.7 kgZcm 2 trowel, a height of 5 m from the liquid level at the bottom of the tower, and a cylindrical device with a diameter of 60 cm. It sprayed so that it might become a 200-m droplet. At the same time, a 30% strength by weight aqueous salty calcium solution is mixed with air with a two-fluid nozzle so that the salty calcium solid content is 5 to 15 parts by weight with respect to 100 parts by weight of the graft copolymer D.
  • aqueous solution of coagulated latex particles an aqueous solution of 5% by weight potassium palmitate is added so that the potassium palmitate solid content is 1.5 parts by weight with respect to 100 parts by weight of the graft copolymer D solid content. Then, after the heat treatment, dehydration and drying were carried out to prepare white rosin powder.
  • thermoplastic rosin composition preparation of molded article, and evaluation
  • Salt vinyl resin (Kanevinyl S—1001, Kanechi Co., Ltd., average polymerization degree 1000) 100 parts by weight, lead-based one-pack stabilizer (LGC3203, ACROS) 4.5 parts by weight, acid Titanium 4.5 parts by weight, calcium carbonate 8 parts by weight, methyl metatalylate polymer (specific viscosity at 30 ° C of a solution of 0.1 g of this polymer dissolved in 100 ml of black mouth form is 0.5 Less than 5 parts by weight of methyl metatalylate polymer) (Kaneace PA-20, manufactured by Kane force Co., Ltd.) 0.5 parts by weight, and graft copolymer D6 parts by weight with a Henschel mixer I got a compound.
  • the obtained powder compound was subjected to a molding temperature condition of 17 to 27 to 37 to 47 0 01702703704: 1757 180Z180Z175Z185Z206Z206Z206Z206Z206.
  • the modified window frame was molded at C, screw rotation speed of 22rpm, and discharge rate of lOOkgZ.
  • An impact resistance test piece was prepared from the obtained window frame molded body, and Charpy strength was measured according to JIS K-7111.
  • Table 2 shows the results of Charpy strength, surface gloss, and screw torque during extrusion.
  • thermometer, stirrer, reflux condenser, nitrogen inlet, monomer and emulsifier addition device A glass reactor was charged with 160 parts by weight of deionized water and 0.04 parts by weight of sodium lauryl sulfate, and the temperature was raised to 50 ° C. while stirring in a nitrogen stream. Next, a mixture of 2-EHA 8.98 parts by weight, AM AO.
  • White latex powder was prepared in the same manner as in Example 2 using the latex of graft copolymer E.
  • a molded product was obtained in the same manner as in Example 2 except that this graft copolymer E was used, and the Charpy strength was measured. Table 2 shows the Charpy strength results, surface gloss, and extrusion torque during extrusion.
  • a glass reactor equipped with a thermometer, stirrer, reflux condenser, nitrogen inlet, and monomer and emulsifier addition device was charged with 160 parts by weight of deionized water and 0.04 part by weight of sodium lauryl sulfate in a nitrogen stream. The temperature was raised to 50 ° C. with stirring. Next, a mixture of 2-EHA 8.98 parts by weight, AM AO.
  • a core having a volume average particle diameter measured by UPA150 (manufactured by Nikkiso Co., Ltd.) of 0.16 / zm was obtained.
  • 0.02 parts by weight of cumene hydride peroxide was continuously added as a shell at 50 ° C. over 30 minutes.
  • tamenoid mouth peroxide 0.01 part by weight was added and stirring was continued for another hour to complete the polymerization.
  • the polymerization conversion rate of the monomer component was 99.0%.
  • a latex of graft copolymer E having 92% by weight of the core having a polymer layer of 3% by weight of Tg-10 ° C. and 8% by weight of the shell having a Tg of 92 ° C. was obtained.
  • White latex resin powder was prepared in the same manner as in Example 2 using the latex of graft copolymer F.
  • a molded product was obtained in the same manner as in Example 2 except that this graft copolymer F was used, and the Charpy strength was measured. Table 2 shows the Charpy strength results, surface gloss, and extrusion torque during extrusion.
  • Table 2 shows the composition and Tg of each core layer of the graft copolymer obtained in Examples and Comparative Examples, the particle diameter of the core, the ratio of the hard polymer in the core, the composition and Tg of the shell, and the graft copolymer.
  • the impact strength (Charby strength) of the body was shown.
  • a core with a diameter of 0.14 m was obtained.
  • 3.00 parts by weight of MMA was continuously added as a shell at 70 ° C for 5 minutes. After completion of the addition, stirring was continued for 1 hour to complete the polymerization.
  • the polymerization conversion rate of the monomer component was 98.5%.
  • a latex of graft copolymer G having 97% by weight of the core having a hard polymer layer of 1% by weight with respect to the core and 3% by weight of the shell having a Tg of 105 ° C. was obtained.
  • thermoplastic rosin composition preparation of molded article, and evaluation
  • Salt vinyl resin (Kane Vinyl S-1001, Kaneshi Co., Ltd., average polymerization degree 1000) 100 parts by weight, lead-based one-pack stabilizer (LGC3203, ACROS) 4.5 parts by weight, acid Titanium 4.5 parts by weight, calcium carbonate 8 parts by weight, methyl metatalylate polymer (specific viscosity at 30 ° C of a solution of 0.1 g of this polymer dissolved in 100 ml of black mouth form is 0.5 Less than 5 parts by weight of methyl metatalylate polymer) (Kaneace PA-20, manufactured by Kanechi Co., Ltd.) 0.5 parts by weight, and graft copolymer G5 parts by weight with a Henschel mixer I got a compound.
  • Table 3 shows the results of Charpy strength, surface gloss, and screw torque during extrusion.
  • a core having a volume average particle diameter of 0.14 m To obtain a core having a volume average particle diameter of 0.14 m. To this core, 3.00 parts by weight of MMA was continuously added as a shell at 70 ° C for 5 minutes. After completion of the addition, stirring was continued for 1 hour to complete the polymerization. The polymerization conversion rate of the monomer component was 98.3%. As described above, a latex of 97% by weight of the core having a hard polymer layer of 5% by weight with respect to the core and 3% by weight of the shell copolymer G having a Tg of 105 ° C. was obtained.
  • White latex powder was prepared in the same manner as in Example 1 using the latex of graft copolymer H.
  • a molded body was obtained in the same manner as in Example 4 except that this graft copolymer H was used, and the Charpy strength was measured.
  • Table 3 shows the Charpy strength results, surface gloss, and extrusion torque during extrusion.
  • White latex resin powder was prepared in the same manner as in Example 1 using the graft copolymer I latex.
  • a molded product was obtained in the same manner as in Example 4 except that this graft copolymer I was used, and the Charpy strength was measured.
  • Table 3 shows the Charpy strength results, surface gloss, and extrusion torque during extrusion.
  • a latex of graft copolymer J having 97% by weight of the core having a layer of 15% by weight of the hard polymer with respect to the core and 3% by weight of the shell having a Tg of 105 ° C. was obtained.
  • White latex powder was prepared in the same manner as in Example 1 using the latex of graft copolymer J.
  • a molded product was obtained in the same manner as in Example 4 except that this graft copolymer J was used, and the Charpy strength was measured.
  • Table 3 shows the Charpy strength results, surface gloss, and extrusion torque during extrusion.
  • a molded body was obtained in the same manner as in Example 4 except that this graft copolymer K was used, and the Charpy strength was measured.
  • Table 3 shows the Charpy strength results, surface gloss, and extrusion torque during extrusion.
  • Table 3 shows the composition and Tg of each core layer of the graft copolymer obtained in Examples and Comparative Examples, the particle diameter of the core, the ratio of the hard polymer in the core, the composition and Tg of the shell, and the graft copolymer. Weight ratio of shell in polymer, and graft copolymer obtained in Examples and Comparative Examples The motor load, the 60 ° surface gloss of the surface of the molded body, and the impact strength (Charby strength) of the molded body were shown.
  • White latex powder was prepared in the same manner as in Example 1, using the latex of graft copolymer L.
  • a molded product was obtained in the same manner as in Example 4 except that this graft copolymer L was used, and the Charpy strength was measured.
  • Table 4 shows the Charpy strength results, surface gloss, and extrusion torque during extrusion.
  • a molded product was obtained in the same manner as in Example 4 except that this graft copolymer M was used, and the Charpy strength was measured. Table 4 shows the Charpy strength results, surface gloss, and extrusion torque during extrusion.
  • a molded product was obtained in the same manner as in Example 4 except that this graft copolymer N was used, and the Charpy strength was measured. Table 4 shows the Charpy strength results, surface gloss, and extrusion torque during extrusion.
  • a latex of graft copolymer O having 97% by weight of the core having 5% by weight of a hard polymer in the innermost layer and 3% by weight of the shell having a Tg of 105 ° C. was obtained.
  • white rosin powder was prepared in the same manner as in Example 1.
  • a molded product was obtained in the same manner as in Example 4 except that this graft copolymer O was used, and the Charpy strength was measured. Table 4 shows the Charpy strength results, surface gloss, and extrusion torque during extrusion.
  • Table 4 shows the composition and Tg of each core layer of the graft copolymers obtained in Examples and Comparative Examples, the particle diameter of the core, the ratio of the hard polymer in the core, the composition and Tg of the shell, and the graft copolymer.
  • the weight ratio of the shell in the polymer, the motor load when the graft copolymer obtained in the examples and comparative examples was blended with thermoplastic resin, and extrusion molding, 60 ° surface gloss of the molded body, molding
  • the impact strength (Charby strength) of the body was shown.
  • the shell (bs), the core (be), the soft polymer (bcs) in the core, and the hard polymer (bch) in the core are within the ranges specified in the present invention.
  • a high impact resistance improving effect can be obtained simultaneously with a low motor load at the time of extrusion and a 60 ° surface gloss of a high molding. That is, it can be seen that a thermoplastic resin composition having excellent weather resistance and high impact resistance and capable of obtaining good processability and molded product surface gloss can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne une nouvelle composition de résine thermoplastique présentant une résistance aux intempéries et une forte résistance aux chocs, réalisant une bonne capacité de transformation et une bonne luminosité de surface d’un article moulé. La présente invention concerne une composition de résine thermoplastique contenant 100 parties en poids d’une résine thermoplastique (A) et de 0,5 à 20 % en poids d’un copolymère greffé (B) composé de 85 à 99,5 % en poids de noyau (bn) et de 0,5 à 15 % en poids de coquille (bc) (à condition que la somme du noyau et de la coquille soit égale à 100 % en poids), caractérisée en ce que le noyau (bn) possède au moins une couche intercalaire de polymère dur (bnd) dans un polymère mou (bnm) et que la coquille (bc) se compose d'un polymère dur et constitue une couche externe du copolymère greffé (B).
PCT/JP2006/319331 2005-11-07 2006-09-28 Composition de resine thermoplastique WO2007052429A1 (fr)

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JP2005-322204 2005-11-07

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6032849A (ja) * 1983-08-04 1985-02-20 Mitsubishi Rayon Co Ltd 熱可塑性樹脂用耐衝撃性改質剤
JPS63152612A (ja) * 1986-10-06 1988-06-25 ザ　ダウ　ケミカル　カンパニー 架橋されかつグラフトされたオーバーポリマーアクリレートゴム
JPH0649150A (ja) * 1992-06-05 1994-02-22 Sumitomo Chem Co Ltd 多層構造重合体、その製造方法及び該重合体含有帯電防止性樹脂組成物
JPH1087762A (ja) * 1996-09-12 1998-04-07 Sekisui Chem Co Ltd 塩化ビニル系グラフト共重合体及びその製造方法
JP2000053830A (ja) * 1998-08-07 2000-02-22 Kuraray Co Ltd ポリ塩化ビニル組成物並びにその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6032849A (ja) * 1983-08-04 1985-02-20 Mitsubishi Rayon Co Ltd 熱可塑性樹脂用耐衝撃性改質剤
JPS63152612A (ja) * 1986-10-06 1988-06-25 ザ　ダウ　ケミカル　カンパニー 架橋されかつグラフトされたオーバーポリマーアクリレートゴム
JPH0649150A (ja) * 1992-06-05 1994-02-22 Sumitomo Chem Co Ltd 多層構造重合体、その製造方法及び該重合体含有帯電防止性樹脂組成物
JPH1087762A (ja) * 1996-09-12 1998-04-07 Sekisui Chem Co Ltd 塩化ビニル系グラフト共重合体及びその製造方法
JP2000053830A (ja) * 1998-08-07 2000-02-22 Kuraray Co Ltd ポリ塩化ビニル組成物並びにその製造方法

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