WO2015141836A1 - ビニル重合体粉体、熱可塑性樹脂組成物及びその成形体 - Google Patents
ビニル重合体粉体、熱可塑性樹脂組成物及びその成形体 Download PDFInfo
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- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
Definitions
- the present invention relates to a vinyl polymer powder, a resin composition containing the same, and a molded body thereof.
- Measures of molding processability of engineering plastics include melt fluidity and melt tension.
- melt fluidity When the melt fluidity is high, it is easy to obtain a large and / or thin molded body at the time of injection molding. If the melt tension is high, molding defects such as jetting at the time of injection molding, blow molding, and drawdown at the time of vacuum molding are less likely to occur.
- the resin composition containing the fluidity improver and the melt tension improver is molded at a high temperature, impurities remaining in the fluidity improver and the melt tension improver, There is a risk of damaging the appearance and mechanical strength of the molded body. Therefore, the resin composition is also strongly required to improve thermal stability during high temperature molding.
- the total content of magnesium ions, calcium ions, aluminum ions, barium ions, and zinc ions with respect to the total mass of the vinyl polymer powder is 350 ppm or less, and ammonium ions with respect to the total mass of the vinyl polymer powder.
- Measurement method of free flow properties A measuring instrument consisting of a pedestal on which the tray is set, a funnel with a shutter at the tube opening, a support that holds the funnel above the pedestal, and a support post to which the support is fixed is installed in a horizontal location. To do. The shutter of the funnel is closed, and 120 cm 3 of powder is uniformly placed in the funnel.
- a measuring instrument consisting of a pedestal on which the tray is set, a funnel with a shutter at the tube opening, a support that holds the funnel above the pedestal, and a support post to which the support is fixed is installed in a horizontal location.
- the shutter of the funnel is closed, and 120 cm 3 of powder is uniformly placed in the funnel.
- open the shutter drop the powder, and immediately set the saucer on the pedestal.
- a method for producing a vinyl polymer powder comprising the following step (1) and step (2).
- Step (2) A step of coagulating the vinyl polymer latex to form a slurry having a pH of 6 or less, generating a precipitate, and collecting the precipitate as a vinyl polymer powder.
- the method for producing a vinyl polymer powder according to [12] wherein in the step (2), the vinyl polymer latex is coagulated using an acid.
- the method for producing a vinyl polymer powder according to [12] wherein the pH of the slurry is 4 or less in the step (2).
- a vinyl polymer powder that can be mixed with an engineering plastic to obtain a resin composition having excellent molding processability and high thermal stability during high-temperature molding, and having excellent powder characteristics.
- an engineering plastic to obtain a resin composition having excellent molding processability and high thermal stability during high-temperature molding, and having excellent powder characteristics.
- thermoplastic resin composition excellent in molding processability and having high thermal stability during high-temperature molding and a molded body using the same.
- FIG. 1 shows a measuring instrument used for evaluation of free flow properties.
- the vinyl polymer powder in the first aspect of the present invention contains a vinyl polymer, the glass transition temperature of the vinyl polymer is 0 ° C. or higher, and magnesium ions with respect to the total mass of the vinyl polymer powder, The total content of calcium ions, aluminum ions, barium ions, and zinc ions is 350 ppm or less, the ammonium ion content is 100 ppm or less, and the acid value is 2 with respect to the total mass of the vinyl polymer powder. It is a vinyl polymer powder having a bulk density of 0.10 to 0.60 g / cm 3 and not more than 0.5 mgKOH / g.
- the vinyl polymer in the first aspect of the present invention has a glass transition temperature of 0 ° C. or higher. If the glass transition temperature of the vinyl polymer is 0 ° C. or higher, it is difficult to lower the thermal deformation temperature of the resin composition mixed with the engineering plastic. From the above viewpoint, the glass transition temperature of the vinyl polymer is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, particularly preferably 80 ° C. or higher, and most preferably 90 ° C. or higher. In addition, the glass transition temperature of the vinyl polymer is preferably 200 ° C. or less, more preferably 150 ° C. or less, and further preferably 120 ° C. or less in view of ease of powder recovery. Specifically, the glass transition temperature of the vinyl polymer is preferably 30 to 150 ° C, more preferably 60 to 120 ° C.
- the glass transition temperature can be measured by the following method. Using a differential scanning calorimetry (DSC) apparatus (model name “DSC6200” manufactured by Seiko Instruments Inc.), the glass transition temperature of the polymer is measured according to JIS K7121. The numerical value of the extrapolation glass transition start temperature is used as the glass transition temperature.
- DSC differential scanning calorimetry
- the glass transition temperature of the vinyl polymer can be appropriately controlled by a commonly used method.
- the glass transition temperature of the vinyl polymer can be controlled within a desired range by appropriately selecting the type of monomer component used in the polymerization, the composition ratio of the monomer components constituting the polymer, the molecular weight of the polymer, etc. can do.
- a monomer mixture containing a monomer having a glass transition temperature of 0 ° C. or higher of the homopolymer may be polymerized.
- the glass transition temperature of the homopolymer standard analytical values described in Wiley publication “POLYMER HANDBOOK” or the like may be adopted.
- the glass transition temperature of the vinyl polymer is generally determined by the composition ratio of the monomer components constituting the polymer, but also varies depending on the molecular weight of the polymer. Specifically, the higher the molecular weight of the polymer, the higher the glass transition temperature, and the lower the molecular weight, the lower the glass transition temperature.
- the total content of magnesium ions, calcium ions, aluminum ions, barium ions, and zinc ions contained in the vinyl polymer powder in the first aspect of the present invention is based on the total mass of the vinyl polymer powder. 350 ppm or less.
- the resin is made catalytic by extruding, molding heat and / or moisture when blended with engineering plastics, especially polyester and polycarbonate. Therefore, the thermal stability during high temperature molding deteriorates.
- the total content of magnesium ions, calcium ions, aluminum ions, barium ions, and zinc ions contained in the vinyl polymer powder is preferably 100 ppm or less with respect to the total mass of the vinyl polymer powder. 50 ppm or less is more preferable, 25 ppm or less is more preferable, and 10 ppm or less is most preferable.
- the total content of sodium ions and potassium ions contained in the vinyl polymer powder of the present invention is preferably 100 ppm or less, more preferably 50 ppm or less, and more preferably 40 ppm or less, based on the total mass of the vinyl polymer powder. More preferred is 30 ppm or less. If the total of sodium ions and potassium ions in the vinyl polymer powder is 100 ppm or less, the resin composition blended with engineering plastics, particularly polyester and polycarbonate, is excellent in thermal stability during high temperature molding.
- the content of metal ions in the vinyl polymer powder can be measured by the following method.
- test solution 1 g of a sample is weighed in a platinum dish, dry-ashed with an electric heater, dissolved in hydrochloric acid and distilled water, and made up to 50 ml with distilled water to prepare a test solution.
- the amount of metal ions of this test solution is quantified using an ICP emission spectrometer (model name “IRIS Interpid II XSP” manufactured by Thermo Scientific).
- the content of ammonium ions contained in the vinyl polymer powder in the first aspect of the present invention is 100 ppm or less with respect to the total mass of the vinyl polymer powder.
- the resin is made catalytic by extruding, molding heat and / or moisture when blended with engineering plastics, especially polyester and polycarbonate. Therefore, the thermal stability during high temperature molding deteriorates.
- ammonium ion content is preferably 10 ppm or less.
- the content of ammonium ions in the vinyl polymer powder can be measured by the following method. After crushing the sample, weigh it into a volumetric flask. Distilled water is added and sonicated to extract ammonium ions. The extracted ammonium ions are quantified by an ion chromatograph analyzer (model name “IC-2010” Tosoh Corporation).
- the acid value of the vinyl polymer powder in the first embodiment of the present invention is 2.5 mgKOH / g or less. If the acid value of the vinyl polymer powder is higher than the specified amount, the resin will be decomposed catalytically by heat and / or moisture when blended with engineering plastics, especially polyester and polycarbonate. Sex worsens.
- the acid value of the vinyl polymer powder is preferably 2.0 mgKOH / g or less. More specifically, it is preferably 0 to 2.5 mgKOH / g, and more preferably 0 to 2.0 mgKOH / g.
- the acid value of the vinyl polymer powder can be measured, for example, by the following method.
- the solvent is not particularly limited as long as it can dissolve the vinyl polymer powder.
- these solvents may be used individually by 1 type, and may use 2 or more types together.
- the total content of magnesium ions, calcium ions, aluminum ions, barium ions, and zinc ions is 350 ppm or less, the content of ammonium ions is 100 ppm or less, and the acid weight is 2.5 mgKOH / g or less.
- Combined powder is obtained by polymerizing vinyl monomer by emulsion polymerization, miniemulsion polymerization, fine suspension polymerization, etc., and reducing the amount of contaminants remaining in the powder when the resulting polymer emulsion is recovered as a powder. Can be obtained.
- a latex of a polymer obtained by emulsion polymerization of a vinyl monomer in the presence of a nonionic anion emulsifier is coagulated to form a slurry having a pH of 6 or less, and the precipitated vinyl polymer is recovered as a powder.
- examples thereof include a method for reducing the amount of auxiliary raw materials used for vinyl monomer polymerization and powder recovery, and a method for washing vinyl polymer powder with a large amount of water and / or solvent.
- the “subsidiary raw material” means a raw material other than the vinyl monomer used in the production of the vinyl polymer powder.
- a latex of a polymer obtained by emulsion polymerization of a vinyl monomer in the presence of a nonionic anionic emulsifier is coagulated to form a slurry having a pH of 6 or less, and the precipitated vinyl polymer is powdered.
- a method of recovering as a body is preferred.
- the bulk density of the vinyl polymer powder in the first embodiment of the present invention is 0.10 to 0.60 g / cm 3 .
- the bulk density of the vinyl polymer powder is preferably 0.20 g / cm 3 or more, and more preferably 0.30 g / cm 3 or more.
- 0.20 to 0.60 g / cm 3 is preferable, and 0.30 to 0.60 g / cm 3 is more preferable.
- the bulk density of the vinyl polymer powder refers to that measured according to JIS K6720 after mixing 0.1 g of zeolite powder with about 120 cm 3 of a sample.
- the free flow property of the vinyl polymer powder in the first aspect of the present invention is preferably 15 g / 10 seconds or more.
- the free flow property is 15 g / 10 seconds or more, the powder handling property is excellent.
- the free flow property of the vinyl polymer powder is more preferably 20 g / 10 seconds or more. Specifically, 15 to 60 g / 10 seconds is preferable, and 20 to 60 g / 10 seconds is more preferable.
- the free flow property of the vinyl polymer powder refers to that obtained by the following measuring method.
- FIG. 1 shows a measuring instrument used for evaluation of free flow properties.
- This measuring instrument includes a pedestal 41 on which a tray 40 is set, a funnel 43 having a shutter 42 provided at the tube opening, a support tool 44 that holds the funnel 43 above the pedestal 41, and a support post on which the support tool 44 is fixed. 45.
- the shutter 42 can open and close the tube opening of the funnel 43, and the shutter 42 is designed so that the powder in the funnel 43 falls onto the tray 40 when the shutter 42 is opened.
- the support column 45 is provided perpendicular to the pedestal 41 and is designed to hold the support tool 44 so that the support tool 44 is horizontal with the pedestal 41.
- the inner diameter of the upper part of the cylinder mouth in the funnel 43 is 8 mm
- the inner diameter of the lower part of the cylinder mouth of the funnel 43 is 20 mm
- the angle of the side surface of the opening of the funnel 43 is 20 °.
- the distance from the upper part of the cylinder mouth in the funnel to the tray 40 is 38 mm. Evaluation of the free flow property using this measuring device is performed as follows. First, a measuring instrument is installed in a horizontal place, the shutter 42 of the funnel 43 is closed, and 120 cm 3 of powder is uniformly placed in the funnel 43. Next, the shutter is opened to drop the powder, and the tray 40 whose tare (the empty weight of the tray 40) has been measured in advance is set on the base 41 immediately.
- the content of fine powder contained in the vinyl polymer powder is preferably small.
- the content of the component having a particle diameter of 38 ⁇ m or less contained in the vinyl polymer powder is preferably 0 to 15% by mass, and more preferably 0 to 10% by mass.
- content of a component with a particle diameter of 38 micrometers or less can be measured with the following method. After 2 mg of the sample is mixed with 10 mg of zeolite powder, the particle size distribution is measured using a continuous acoustic sieving meter (model name “Robot Shifter RPS-95” manufactured by Seishin Enterprise Co., Ltd.).
- a total of 8 meshes of # 20, # 32, # 42, # 60, # 100, # 150, # 250, and # 400 are used, and the component having passed through the # 400 mesh is a component having a particle diameter of 38 ⁇ m or less.
- a method for reducing the content of styrene for example, a latex of a polymer obtained by emulsion polymerization of a vinyl monomer in the presence of a nonionic anionic emulsifier is coagulated to form a slurry having a pH of 6 or less, and the precipitated vinyl polymer is used as a powder.
- the recovery method include a method of sieving the vinyl polymer powder and removing a component having a particle diameter of 38 ⁇ m or less.
- a latex of a polymer obtained by emulsion polymerization of a vinyl monomer in the presence of a nonionic anionic emulsifier is coagulated to form a slurry having a pH of 6 or less, and the precipitated vinyl polymer is powdered.
- a method of recovering as a body is preferred.
- the vinyl polymer preferably has a mass average molecular weight of 5,000 to 20,000,000.
- the weight average molecular weight of the vinyl polymer is preferably 5,000 to 200,000, more preferably 10,000 to 150,000, still more preferably 15,000 to 100,000, and 20,000 to 100,000 is particularly preferred and 30,000-75,000 is most preferred.
- the mass average molecular weight of the vinyl polymer is 200,000 or more, the melt tension is excellent, and if it is 20,000,000 or less. Easy to melt knead engineering plastic and vinyl polymer.
- the mass average molecular weight of the vinyl polymer is preferably 200,000 to 20,000,000, more preferably 200,000 to 10,000,000, and even more preferably 500,000 to 5,000,000. preferable.
- the mass average molecular weight can be measured by gel permeation chromatography in terms of polystyrene.
- the vinyl polymer powder in the first aspect of the present invention is produced, for example, by polymerizing a vinyl monomer capable of radical polymerization and recovering the obtained latex of the vinyl polymer as a powder.
- a polymerization method of the vinyl polymer emulsion polymerization, miniemulsion polymerization, and fine suspension polymerization are preferable, and emulsion polymerization is more preferable because the composition distribution and particle morphology of the polymer can be easily controlled.
- the polymerization method is not particularly limited, and one-stage polymerization, two-stage polymerization, multistage polymerization, or the like can be employed.
- the first-stage vinyl monomer is emulsion-polymerized to obtain a pre-copolymer.
- the first-stage vinyl monomer may be emulsion polymerized in the presence of the pre-copolymer.
- the vinyl polymer can be obtained by polymerizing a vinyl monomer.
- the vinyl polymer is an engineering plastic of the resulting vinyl polymer powder, particularly polyester and polycarbonate.
- the ester moiety contains a (meth) acrylic acid ester unit containing an alkyl group having 1 to 4 carbon atoms or an aromatic group.
- (meth) acrylic acid means one or both of acrylic acid having a hydrogen atom bonded to the ⁇ -position and methacrylic acid having a methyl group bonded to the ⁇ -position.
- (Meth) acrylic acid ester means one or both of an acrylic acid ester having a hydrogen atom bonded to the ⁇ -position and a methacrylic acid ester having a methyl group bonded to the ⁇ -position.
- (Meth) acrylate means one or both of an acrylate having a hydrogen atom bonded to the ⁇ -position and a methacrylate having a methyl group bonded to the ⁇ -position.
- Examples of the monomer that is a raw material for the (meth) acrylic acid ester unit containing an alkyl group having 1 to 4 carbon atoms at the ester site include the following. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate.
- the alkyl group may be linear or branched. These monomers may be used independently and may use 2 or more types together.
- an alkyl group having 1 to 2 carbon atoms (methyl group, ethyl group) as an alkyl group at the ester site it is preferable to have an alkyl group having 1 carbon atom (methyl group).
- Examples of the (meth) acrylic acid ester having an aromatic group at the ester site include the following. Phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate, monochlorophenyl (meth) Acrylate, dichlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate, benzyl (meth) acrylate, naphthyl (meth) acrylate.
- phenyl (meth) acrylate, benzyl (meth) acrylate, and naphthyl (meth) acrylate are preferred from the viewpoint of dispersibility of the obtained vinyl polymer powder in engineering plastics, particularly polyester and polycarbonate.
- (Meth) acrylate and naphthyl (meth) acrylate are more preferred.
- a methacrylic ester since it is easy to raise the glass transition temperature of the vinyl polymer obtained, it is preferable to use a methacrylic ester.
- the number of carbons constituting the aromatic ring contained in the aromatic group of the ester moiety is 6-10. Is preferred.
- the ester moiety contains an alkyl group or aromatic group having 1 to 4 carbon atoms in the total mass of all monomer units constituting the vinyl polymer (meta )
- the content of acrylate units is preferably 0.5 to 99.5% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 50% by mass.
- the resulting vinyl polymer powder is an engineering plastic, particularly The dispersibility in polyester and polycarbonate is excellent, and as a result, the appearance of the resulting molded article is excellent. Moreover, it is excellent in melt fluidity as this content rate is 99.5 mass% or less.
- the ester moiety contains an alkyl group or aromatic group having 1 to 4 carbon atoms in the total mass of all monomer units constituting the vinyl polymer (meta )
- the content of acrylate units is preferably 0.5 to 100% by mass, more preferably 50 to 100% by mass.
- the resulting vinyl polymer powder is an engineering plastic, particularly It is excellent in dispersibility in polyester and polycarbonate, and as a result, is excellent in the effect of improving the melt tension and the appearance of the molded body.
- the vinyl polymer When using vinyl polymer powder as a fluidity improver, the vinyl polymer preferably contains an aromatic vinyl monomer unit.
- Examples of the monomer that is a raw material for the aromatic vinyl monomer unit include the following. Styrene, ⁇ -methylstyrene, p-methylstyrene, pt- butylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, chlorostyrene, bromostyrene, vinyltoluene, vinylnaphthalene, vinylanthracene , Divinylbenzene. These monomers may be used individually by 1 type, and may use 2 or more types together.
- styrene, ⁇ -methyl styrene, p-methyl styrene, and pt-butyl styrene are preferable, and styrene and ⁇ -methyl styrene are more preferable because the polymerization rate of the vinyl polymer and the glass transition temperature are easily increased.
- the content of aromatic vinyl monomer units is 0.5 to 99.5 mass in the total mass of all monomer units constituting the vinyl polymer. % Is preferable, 30 to 95% by mass is more preferable, and 50 to 90% by mass is more preferable.
- the content of the aromatic vinyl monomer unit is 0.5% by mass or more, the resin composition obtained by blending the obtained vinyl polymer powder with engineering plastics, particularly polyester and polycarbonate, has excellent melt fluidity, and When it is 99.5% by mass or less, the appearance of the obtained molded article is excellent.
- the content of the aromatic vinyl monomer unit is 0 to 99.5% by mass in the total mass of all monomer units constituting the vinyl polymer. Preferably, 0 to 50% by mass is more preferable. More than 0 mass% and 99.5 mass% or less are more preferable, and more than 0 mass% and 50 mass% or less are especially preferable.
- the content of the aromatic vinyl monomer unit exceeds 0%, the resulting vinyl polymer powder is excellent in thermal stability at the time of molding when blended with engineering plastic, and this content is 99.99%.
- the content is 5% by mass or less, the dispersibility in engineering plastics, particularly polyester and polycarbonate is excellent, and as a result, the melt tension improving effect and the appearance of the molded product are excellent.
- the vinyl polymer may contain other monomer units as necessary.
- the monomer used as a raw material for other monomer units is not particularly limited as long as it is a vinyl monomer capable of radical polymerization, and examples thereof include the following.
- Esters such as n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, etc.
- the content of other monomer units in the total mass of all monomer units constituting the vinyl polymer is preferably 0 to 20% by mass.
- the content of other monomer units is 0 to 20% by mass, the resulting vinyl polymer powder is unlikely to hinder the object of the present invention.
- a combination of styrene and phenyl methacrylate As a vinyl monomer, a combination of styrene and phenyl methacrylate; a combination of styrene, ⁇ -methyl styrene, phenyl methacrylate, methyl methacrylate, and allyl methacrylate; a combination of styrene, ⁇ -methyl styrene, methyl methacrylate, and allyl methacrylate; Combinations of styrene, ⁇ -methylstyrene, phenyl methacrylate, methyl methacrylate, n-butyl acrylate, and allyl methacrylate; and combinations of methyl methacrylate and n-butyl acrylate are preferred.
- the first-stage vinyl monomer is preferably a combination of styrene, ⁇ -methyl styrene, and phenyl methacrylate; a combination of styrene, ⁇ -methyl styrene, and methyl methacrylate.
- the second stage vinyl monomer is a combination of styrene, phenyl methacrylate, methyl methacrylate, and allyl methacrylate; a combination of styrene, methyl methacrylate, and allyl methacrylate; and styrene, phenyl methacrylate, methyl methacrylate, n-butyl acrylate, and allyl.
- a combination of methacrylates is preferred.
- the polymerization initiator used for the polymerization of the vinyl monomer is not particularly limited, and a known polymerization initiator can be used. Examples thereof include persulfates, organic peroxides, azo initiators, redox initiators in which persulfates and reducing agents are combined, and redox initiators in which organic peroxides and reducing agents are combined. These polymerization initiators may be used alone or in combination of two or more. Moreover, there is no restriction
- Chain transfer agents include mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan, n-butyl mercaptan; carbon tetrachloride, odor Halogen compounds such as ethylene fluoride; ⁇ -styrene dimer.
- chain transfer agents may be used individually by 1 type, and may use 2 or more types together.
- emulsifier examples of the emulsifier used for the emulsion polymerization of the vinyl monomer include an anionic emulsifier, a nonionic emulsifier, a nonionic anionic emulsifier, and a polymer emulsifier. Of these, nonionic anionic emulsifiers are preferably used. In the present invention, “nonionic anionic emulsifier” refers to an emulsifier having a nonionic hydrophilic portion and an anionic hydrophilic portion (ionic hydrophilic portion) in the same molecule.
- the latex containing the vinyl polymer When the latex containing the vinyl polymer is coagulated, a slight amount of the emulsifier remains in the vinyl polymer powder in an acid or salt state, and when the vinyl polymer powder is blended with engineering plastic, particularly polyester and polycarbonate, There is a risk of decomposing the resin.
- the acid value of the vinyl polymer powder increases.
- the metal ions in the vinyl polymer powder increase.
- Nonionic anionic emulsifiers can be easily washed at the time of coagulation because they can maintain water solubility to some extent by the nonionic hydrophilic part even if the hydrophilicity of the anionic hydrophilic part is reduced by coagulation of the vinyl polymer latex. It is difficult to remain in the polymer powder.
- a latex obtained by polymerizing a vinyl monomer in the presence of a nonionic anionic emulsifier is preferable because it easily coagulates and easily increases the bulk density and free flow property of the powder.
- anionic hydrophilic part (ionic hydrophilic part) of the nonionic anionic emulsifier tends to lower the acid value of the resulting vinyl polymer powder, phosphoric acid (phosphoric acid group) or a salt thereof or carboxylic acid (carboxyl group) Or it is preferable that it is its salt.
- nonionic anionic emulsifier in which the anionic hydrophilic portion is a carboxylic acid or a salt thereof include polyoxyethylene alkyl ether acetic acid.
- the alkyl group preferably has 4 to 20 carbon atoms, more preferably 8 to 20 carbon atoms.
- the average added mole number of ethylene oxide is preferably 1 to 12, and more preferably 3 to 12.
- These emulsifiers may use an acid form, or may use a salt form such as a sodium salt or a potassium salt. Specific examples include sodium polyoxyethylene (4.5) lauryl ether acetate.
- X represents the average addition mole number of ethylene oxide.
- nonionic anionic emulsifier in which the anionic hydrophilic portion is phosphoric acid or a salt thereof include polyoxyethylene phenyl ether phosphoric acid, polyoxyethylene alkyl phenyl ether phosphoric acid, polyoxyethylene alkyl ether phosphoric acid and the like.
- the alkyl group preferably has 4 to 20 carbon atoms, more preferably 8 to 20 carbon atoms.
- the average added mole number of ethylene oxide is preferably 1 to 12, and more preferably 3 to 12.
- These emulsifiers may be used in an acid form, or a salt form such as a sodium salt or a potassium salt. Specific examples include sodium polyoxyethylene (6) alkyl ether phosphate.
- nonionic anionic emulsifiers whose anionic hydrophilic portion is phosphoric acid or a salt thereof, or carboxylic acid or a salt thereof include polyoxyethylene alkyl ether sulfate.
- anionic emulsifier examples include sulfonates such as sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and sodium dialkylsulfosuccinate; fatty acid salts such as potassium oleate and sodium stearate; and alkyl phosphate esters.
- Nonionic emulsifiers include, for example, polyoxyalkylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Oxyethylene fatty acid ester is mentioned.
- polymer emulsifier examples include a polymer carboxylate.
- the above emulsifiers may be used alone or in combination of two or more.
- the amount of the emulsifier used is not particularly limited, but is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and 0.1 to 5 parts by weight with respect to 100 parts by weight of the vinyl monomer. Further preferred. When the amount of the emulsifier used is 0.1 part by mass or more, the emulsion stability is excellent, and when it is 20 parts by mass or less, coagulation becomes easy.
- the vinyl polymer powder in the first aspect of the present invention can be obtained, for example, by collecting vinyl polymer latex as a powder.
- a known pulverization method can be used as a method for pulverizing the vinyl polymer latex. Examples thereof include a coagulation method and a spray drying method. Of these, the coagulation method is preferable because the emulsifier hardly remains in the vinyl polymer powder as compared with the spray drying method.
- the latex is brought into contact with hot water in which a coagulant is dissolved, and coagulated with stirring to form a slurry, and the generated precipitate is dehydrated and dried.
- a coagulant include acids and salts.
- the temperature of the hot water is preferably from the glass transition temperature of the vinyl polymer ⁇ 25 ° C. to the glass transition temperature of the vinyl polymer + 25 ° C. If the glass transition temperature of the vinyl polymer is ⁇ 25 ° C. or higher, the fine powder hardly increases in the vinyl polymer powder. If the glass transition temperature of the vinyl polymer is 25 ° C. or less, it is difficult to form coarse particles in which the vinyl polymer particles are excessively fused.
- the coagulant is calcium salt, magnesium salt, aluminum salt, barium salt, or zinc salt, it forms a hardly soluble salt with the emulsifier, and the salt derived from the coagulant remains in the vinyl polymer powder. It becomes easy to do. As a result, when the obtained vinyl polymer powder is blended with engineering plastics, particularly polyester and polycarbonate, decomposition of the resin is easily promoted, which is not preferable. Further, when the coagulant is a calcium salt, magnesium salt, aluminum salt, barium salt, or zinc salt, the coagulation force is weak and the powder characteristics of the resulting vinyl polymer powder are liable to deteriorate. Therefore, it is preferable to use an acid as the coagulant.
- Examples of the acid used for the coagulant include inorganic acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid and nitric acid; and organic acids such as formic acid, acetic acid and benzenesulfonic acid. Of these, sulfuric acid and hydrochloric acid are preferred because of their strong acidity.
- the amount of the coagulant used is not particularly limited as long as it sufficiently coagulates the latex, but it is 0 with respect to 100 parts by mass of the resin solid content (100 parts by mass of the vinyl polymer) in the vinyl polymer latex. 0.1 to 20 parts by mass is preferable, 0.1 to 10 parts by mass is more preferable, and 0.1 to 5 parts by mass is even more preferable. When the amount of the coagulant used is 0.1 part by mass or more, the powder recoverability of the vinyl polymer is good. When the amount of the coagulant used is 20 parts by mass or less, the resin composition obtained by blending the obtained vinyl polymer powder with engineering plastic, particularly polyester and polycarbonate, is excellent in thermal stability during high temperature molding.
- the pH of the slurry obtained by coagulating the vinyl polymer latex is preferably 6 or less, more preferably 4 or less, and even more preferably 1 to 4. If the pH of the slurry is 6 or less, the anionic hydrophilic portion of the emulsifier is unlikely to be in a metal salt state, and the metal salt of the emulsifier is unlikely to remain in the resulting vinyl polymer powder. As a result, when the vinyl polymer powder is blended with engineering plastics, particularly polyester and polycarbonate, it is difficult to promote the decomposition of the resin.
- the pH of the slurry may be adjusted by the type and amount of the coagulant, and may be adjusted by adding an acid or base to the slurry after coagulation.
- Solidification is a process for reducing the voids of the precipitated particles and making them difficult to be crushed.
- the temperature at the time of solidification is preferably higher than the coagulation temperature to the coagulation temperature + 40 ° C. because the fine powder in the vinyl polymer powder hardly increases.
- After separating the vinyl polymer powder from the slurry it may be washed with ion exchange water or the like, dehydrated, and dried. By performing the cleaning, the amount of impurities can be controlled.
- thermoplastic resin composition in the second aspect of the present invention includes the vinyl polymer in the first aspect of the present invention and an engineering plastic.
- the engineering plastic used for the thermoplastic resin composition in the second correspondence of the present invention is not particularly limited, and a known engineering plastic can be used. Examples of engineering plastics include the following.
- Polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as 6-nylon, 6,6-nylon and polyphenylene terephthalamide; polycarbonate, syndiotactic polystyrene, polyarylate, polyphenylene ether, polyphenylene sulfide, polyether ketone, polyether ether Ketone, polysulfone, polyethersulfone, polyamideimide, polyetherimide, polyacetal.
- polyamide, polyester, and polycarbonate are preferable, polyester and polycarbonate are more preferable, and polycarbonate is more preferable because of high molding processability improving effect.
- the engineering plastic a commercially available one or a synthesized one may be used.
- aromatic polycarbonate resin (trade name: “Iupilon S-2000F”, manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight: 22,000), and aromatic polycarbonate resin (trade name: “Iupilon S”). -3000F ", manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight: 21,000).
- thermoplastic resin composition the range that does not impair the excellent heat resistance, impact resistance, flame retardancy, etc. inherent to the engineering plastic, specifically, 100% by mass of the resin composition.
- the following resin can be mix
- Styrenic resins such as ABS, HIPS, PS, and PAS; Acrylic resins such as polymethyl methacrylate; Polyolefin resins such as polyethylene and polypropylene. Specifically, 0 to 40% by mass is preferable with respect to 100% by mass of the resin composition, and 0 to 30% by mass is more preferable.
- the blending ratio of the vinyl polymer powder and the engineering plastic in the first aspect of the present invention may be appropriately determined according to the desired physical properties and the like, and is not particularly limited.
- the blending amount of the vinyl polymer powder is 0.1% by mass or more, a sufficient effect of improving moldability can be obtained.
- the compounding quantity of vinyl polymer powder is 30 mass% or less, it is hard to impair the mechanical characteristics of engineering plastics. It is preferable to blend 70 to 99.9% by mass of engineering plastic with respect to 100% by mass of the resin composition, more preferably 80 to 99% by mass, and still more preferably 85 to 99% by mass.
- thermoplastic resin composition according to the second aspect of the present invention can be blended with known additives for imparting various functions and improving properties to the molded body, if necessary.
- additives include antioxidants, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, sliding agents, coloring agents (pigments and dyes such as carbon black and titanium oxide), fluorescent whitening agents, Examples include phosphorescent pigments, fluorescent dyes, and antistatic agents.
- fillers such as a talc, a mica, a calcium carbonate, a glass fiber, a carbon fiber, a potassium titanate fiber, can be contained.
- a rubber-like elastic body having a core-shell two-layer structure can be blended.
- a preferred combination of vinyl polymer powder and engineering plastic is a vinyl polymer powder containing units derived from styrene and phenyl methacrylate; styrene, ⁇ -methylstyrene, phenyl methacrylate, methyl methacrylate, and allyl methacrylate.
- the resin composition containing the vinyl polymer powder and the engineering plastic in the first aspect of the present invention is prepared as a powder mixture or a melt-kneaded product.
- a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a two-roll, a kneader, a Brabender, or the like is used.
- a master batch in which a vinyl polymer powder having a large vinyl polymer content and engineering plastic is mixed in advance is prepared, and then the master batch and engineering plastic are mixed again to obtain a resin composition having a desired composition. You can also.
- the temperature for mixing and / or kneading is not particularly limited, but may be appropriately selected and determined usually in the range of 240 to 350 ° C.
- the molded object in the 3rd aspect of this invention shape
- the molding method include compression molding, transfer molding, injection molding, blow molding, extrusion molding, laminate molding, and calendar molding.
- the molding temperature of the resin composition (the temperature of the resin composition) is not particularly limited. The higher the molding temperature is, the better the melt flowability of the resin composition is, but if it is too high, the decomposition of the resin composition is promoted, so 240-350 ° C is preferred.
- the molded body in the third aspect of the present invention can be used in a wide range of fields including the OA equipment field, the electrical / electronic equipment field, and the building materials field.
- Glass-transition temperature Using a differential scanning calorimetry (DSC) apparatus (model name “DSC6200”, manufactured by Seiko Instruments Inc.), the glass transition temperature of the vinyl polymer was measured according to JIS K7121. The numerical value of the extrapolation glass transition start temperature was used as the glass transition temperature.
- DSC differential scanning calorimetry
- FIG. 1 shows a measuring instrument used for evaluation of free flow property.
- This measuring instrument includes a pedestal 41 on which a tray 40 is set, a funnel 43 having a shutter 42 provided at the tube opening, a support tool 44 that holds the funnel 43 above the pedestal 41, and a support post on which the support tool 44 is fixed. 45. Evaluation of the free flow property using this measuring device was performed as follows. First, the measuring instrument was installed in a horizontal place, the shutter 42 of the funnel 43 was closed, and 120 cm 3 of powder was uniformly placed in the funnel 43. Next, the shutter was opened to drop the powder, and immediately, a tray 40 whose tare was measured in advance was set on the pedestal 41.
- Initial YI Pellets are supplied to a 100-ton injection molding machine (model name “SE-100DU”, manufactured by Sumitomo Heavy Industries, Ltd.) set at a cylinder temperature of 320 ° C. and injection molded, and the length is 100 mm, the width is 50 mm, and the thickness is 2 mm. A flat plate was obtained. Next, the YI value of the flat plate was measured, and the value was taken as the initial YI.
- the YI value of the flat plate is in accordance with JIS K7105, using a spectral color difference meter (model name “SE2000” manufactured by Nippon Denshoku Industries Co., Ltd.), under conditions of C light source and 2 degree visual field, and Examples 13 to 22 and Comparative Examples 5 to 8 were measured by the transmitted light measurement method, and Examples 23 to 25 were measured by the reflected light measurement method.
- a spectral color difference meter model name “SE2000” manufactured by Nippon Denshoku Industries Co., Ltd.
- melt fluidity is evaluated by the spiral flow length of the resin composition, and was measured using an injection molding machine (model name “SE-100DU”, manufactured by Sumitomo Heavy Industries, Ltd.). The longer the spiral flow length, the better the melt fluidity.
- the molding temperature was 320 ° C.
- the mold temperature was 80 ° C.
- the thickness of the resulting molded body was 2 mm and the width was 15 mm.
- Example 1 Charge polyoxyethylene (6) alkyl ether sodium phosphate (1.0 part) and ion exchange water (294 parts) as an emulsifier into a 5 liter separable flask equipped with a stirring blade, condenser, thermocouple, and nitrogen inlet. The mixture was stirred for 30 minutes at room temperature under a room air flow. In addition, the said polyoxyethylene (6) alkyl ether sodium phosphate was used in the state previously dissolved in a part of said ion-exchange water.
- the temperature of the liquid in the flask was raised to 60 ° C., and a mixture comprising 0.0001 part of ferrous sulfate, 0.0003 part of disodium ethylenediaminetetraacetate and 0.3 part of Rongalite was added to 4 parts of ion-exchanged water. The solution dissolved in was added to the flask. Further, a mixture of 87.5 parts of styrene, 12.5 parts of phenyl methacrylate, 0.5 part of n-octyl mercaptan, and 0.2 part of t-butyl hydroperoxide was dropped into the flask over 4 hours and 30 minutes. Radical polymerization was performed.
- the temperature of the liquid in the flask was raised to 80 ° C., and then stirred for 1 hour while maintaining the temperature at 80 ° C. to obtain a vinyl polymer latex.
- the content of vinyl polymer in this latex was 25%.
- Example 2 Polymerization was performed in the same manner as in Example 1 except that the emulsifier was changed to 1.0 part of polyoxyethylene (4.5) sodium lauryl ether acetate to obtain a vinyl polymer latex. Subsequently, the latex was coagulated in the same manner as in Example 1 except that the coagulant was changed to 0.5 part of sulfuric acid to obtain 100 parts of a vinyl polymer powder (A-2). At this time, the pH of the slurry after solidification was 2.2.
- Example 3 Polyoxyethylene (4.5) sodium lauryl ether acetate as an emulsifier (2.0 parts) and ion-exchanged water (293 parts) were placed in a separable flask having a capacity of 5 liters equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet. The mixture was stirred and stirred at room temperature for 30 minutes under a room air flow. In addition, the said polyoxyethylene (4.5) sodium lauryl ether acetate was used in the state dissolved beforehand in a part of said ion exchange water.
- the temperature of the liquid in the flask was raised to 60 ° C., and a mixture comprising 0.0001 part of ferrous sulfate, 0.0003 part of disodium ethylenediaminetetraacetate and 0.3 part of Rongalite was added to 4 parts of ion-exchanged water.
- the solution dissolved in was added to the flask.
- a mixture of 30 parts of styrene, 10 parts of ⁇ -methylstyrene, 10 parts of phenyl methacrylate, 0.23 part of n-octyl mercaptan and 0.1 part of t-butyl hydroperoxide was dropped into the flask over 4 hours.
- the first stage radical polymerization was performed.
- the mixture was stirred for 1 hour while maintaining the temperature of the liquid in the flask at 60 ° C., and further 20 parts of styrene, 14.88 parts of phenyl methacrylate, 14.88 parts of methyl methacrylate, allyl methacrylate.
- a mixture consisting of 0.25 parts, 0.34 parts of n-octyl mercaptan, and 0.1 parts of t-butyl hydroperoxide was dropped into the flask over 4 hours to carry out the second-stage radical polymerization.
- the temperature of the liquid in the flask was raised to 80 ° C. and then stirred for 1 hour while maintaining the temperature at 80 ° C. to obtain a vinyl polymer latex.
- the content of vinyl polymer in this latex was 25%.
- the latex was coagulated in the same manner as in Example 2 to obtain 100 parts of a vinyl polymer powder (A-3).
- the pH of the slurry after solidification at this time was 2.0.
- Example 4 The emulsifier was changed to 1.0 part of sodium polyoxyethylene (4.5) lauryl ether acetate, and the first-stage mixture was mixed with 30 parts of styrene, 10 parts of ⁇ -methylstyrene, 10 parts of methyl methacrylate, and 0 parts of n-octyl mercaptan. The mixture in the second stage was changed to 20 parts of styrene, 29.75 parts of methyl methacrylate, 0.25 parts of allyl methacrylate, and 0 parts of n-octyl mercaptan.
- Example 3 Polymerization was carried out in the same manner as in Example 3 except that the mixture was changed to a mixture comprising .34 parts and t-butyl hydroperoxide 0.1 part to obtain a vinyl polymer latex. Subsequently, the latex was coagulated in the same manner as in Example 2 to obtain 100 parts of a vinyl polymer powder (A-4). At this time, the pH of the slurry after solidification was 2.1.
- Example 5 Polymerization was carried out in the same manner as in Example 3 to obtain a vinyl polymer latex. Subsequently, 280 parts of a sulfuric acid aqueous solution containing 0.5 part of sulfuric acid as a coagulant was charged into a reactor having a capacity of 40 liters equipped with a stirrer, and the aqueous solution was heated to 90 ° C. while stirring. The latex was gradually dropped into the aqueous solution to coagulate the polymer to obtain a slurry. Then, after raising the temperature of this slurry to 90 degreeC, it stirred for 5 minutes and solidified. Further, a 10% aqueous sodium hydroxide solution was added to the solidified slurry until the pH reached 3.7. Next, the obtained precipitate was separated from the slurry, washed with 3000 parts of ion exchange water, dehydrated and dried to obtain 100 parts of vinyl polymer powder (A-5).
- Example 6 Polymerization was carried out in the same manner as in Example 2 to obtain a vinyl polymer latex. Subsequently, 100 parts of a vinyl polymer powder (A-6) was obtained in the same manner as in Example 5 except that a 10% aqueous sodium hydroxide solution was added to the solidified slurry until the pH reached 5.8. It was.
- the second mixture is 20 parts of styrene, 14.88 parts of phenyl methacrylate, 12.88 parts of methyl methacrylate, 2 parts of n-butyl acrylate, 0.25 part of allyl methacrylate, 0.34 part of n-octyl mercaptan, t- Polymerization was carried out in the same manner as in Example 3 except that the mixture was changed to a mixture comprising 0.1 part of butyl hydroperoxide to obtain a vinyl polymer latex. Subsequently, the latex was coagulated in the same manner as in Example 2 to obtain 100 parts of a vinyl polymer powder (A-7). The pH of the slurry after solidification at this time was 2.0.
- Example 8 The second-stage mixture was mixed with 18.4 parts of styrene, 13.69 parts of phenyl methacrylate, 13.69 parts of methyl methacrylate, 4 parts of n-butyl acrylate, 0.25 part of allyl methacrylate, 0.34 part of n-octyl mercaptan, Polymerization was carried out in the same manner as in Example 3 except that the mixture was changed to a mixture comprising 0.1 part of t-butyl hydroperoxide to obtain a vinyl polymer latex. Subsequently, the latex was coagulated in the same manner as in Example 2 except that the coagulation temperature was changed to 85 ° C. and the solidification temperature was changed to 95 ° C. to obtain 100 parts of a vinyl polymer powder (A-8). It was. The pH of the slurry after solidification at this time was 2.0.
- Example 9 The second-stage mixture was mixed with 15.2 parts of styrene, 11.3 parts of phenyl methacrylate, 11.3 parts of methyl methacrylate, 12 parts of n-butyl acrylate, 0.25 part of allyl methacrylate, 0.34 part of n-octyl mercaptan, Polymerization was carried out in the same manner as in Example 3 except that the mixture was changed to a mixture comprising 0.1 part of t-butyl hydroperoxide to obtain a vinyl polymer latex. Subsequently, the latex was coagulated in the same manner as in Example 2 except that the coagulation temperature was changed to 65 ° C. and the solidification temperature was changed to 75 ° C. to obtain 100 parts of a vinyl polymer powder (A-9). It was. The pH of the slurry after solidification at this time was 2.0.
- Example 10 Polyoxyethylene (4.5) sodium lauryl acetate 1.0 part as an emulsifier, 48 parts of methyl methacrylate, 2 parts of n-butyl acrylate, 0.004 part of n-octyl mercaptan, 223 parts of ion-exchanged water, a stirring blade , A 3 liter separable flask equipped with a condenser, thermocouple, and nitrogen inlet, and stirred at room temperature for 30 minutes under a nitrogen stream.
- the said polyoxyethylene (4.5) sodium lauryl ether acetate was used in the state dissolved beforehand in a part of said ion exchange water.
- the temperature of the liquid in the flask was raised to 45 ° C., and 0.15 part of potassium persulfate dissolved in 6 parts of ion-exchanged water was added to initiate radical polymerization.
- a mixture of 44 parts of methyl methacrylate and 6 parts of n-butyl acrylate was dropped into the flask over 2 hours to carry out radical polymerization.
- the mixture was stirred for 1 hour while maintaining the temperature at 70 ° C. to obtain a vinyl polymer latex.
- the content of vinyl polymer in this latex was 30%.
- Example 11 Polyoxyethylene (4.5) sodium lauryl acetate as an emulsifier 1.0 part, 85 parts of methyl methacrylate, 15 parts of n-butyl acrylate, 223 parts of ion-exchanged water, stirring blade, condenser, thermocouple, nitrogen inlet Were charged in a separable flask having a capacity of 3 liters and stirred at room temperature for 30 minutes under a nitrogen stream.
- the said polyoxyethylene (4.5) sodium lauryl ether acetate was used in the state dissolved beforehand in a part of said ion exchange water.
- the temperature of the liquid in the flask was raised to 45 ° C., and 0.15 part of potassium persulfate dissolved in 6 parts of ion-exchanged water was added to initiate radical polymerization. After completion of the polymerization exotherm, the polymer was stirred for 1 hour while maintaining the temperature at 70 ° C. to obtain a vinyl polymer latex. The content of vinyl polymer in this latex was 30%.
- the latex was coagulated in the same manner as in Example 10 to obtain 100 parts of a vinyl polymer powder (A-11).
- the pH of the slurry after solidification at this time was 2.0.
- Example 12 Polymerization was carried out in the same manner as in Example 11 except that the vinyl monomer mixture was changed to a mixture comprising 85 parts of methyl methacrylate, 15 parts of n-butyl acrylate, and 0.03 part of n-octyl mercaptan. Got. Subsequently, the latex was coagulated in the same manner as in Example 10 to obtain a vinyl polymer powder (A-12). The pH of the slurry after solidification at this time was 2.0.
- Example 1 Polymerization was carried out in the same manner as in Example 3 to obtain a vinyl polymer latex. Subsequently, the latex was coagulated in the same manner as in Example 3 except that the coagulant was changed to 5.0 parts of calcium acetate to obtain 100 parts of a vinyl polymer powder (A-13). At this time, the pH of the slurry after solidification was 6.5.
- Example 2 Polymerization was performed in the same manner as in Example 1 except that the emulsifier was changed to 1.0 part of dipotassium alkenyl succinate to obtain a vinyl polymer latex. Subsequently, the latex was coagulated in the same manner as in Example 2 to obtain 100 parts of a vinyl polymer powder (A-14). At this time, the pH of the slurry after solidification was 2.3.
- Comparative Example 3 Polymerization was performed in the same manner as in Comparative Example 2 to obtain a vinyl polymer latex. Subsequently, the latex was coagulated in the same manner as in Comparative Example 1 to obtain 100 parts of a vinyl polymer powder (A-15). At this time, the pH of the slurry after solidification was 6.5.
- Example 4 Polymerization was carried out in the same manner as in Example 1 except that the emulsifier was changed to 1.0 part of sodium alkyldiphenyl ether disulfonate to obtain a vinyl polymer latex.
- a vinyl polymer latex 1.5 parts (as an active ingredient) of a hindered phenol-based antioxidant aqueous dispersion (product name Irgastab MBS43EM (manufactured by Ciba Japan Co., Ltd.)) was added and stirred at room temperature.
- the latex was coagulated in the same manner as in Comparative Example 1 to obtain 100 parts of a vinyl polymer powder (A-16). At this time, the pH of the slurry after solidification was 6.9.
- the vinyl polymer powders produced in Examples 1 to 12 and Comparative Examples 1 to 4 are summarized in Tables 2A, 2B, 3A, and 3B.
- the symbol described in Table 2A, Table 2B, Table 3A, Table 3B means the compound described in Table 4.
- the mass part of the emulsifier in Table 2A and Table 2B is the quantity with respect to 100 mass parts of vinyl monomers.
- the mass part of a coagulant is the quantity with respect to 100 mass parts of polymers in latex.
- Examples 13 to 25, Comparative Examples 5 to 8 Each material was mix
- the vinyl polymer powder of the present invention was excellent in powder characteristics. Further, as is apparent from Examples 13 to 25, the resin composition containing the vinyl polymer powder of the present invention is excellent in molding processability and is difficult to be colored even when molded under high temperature retention. Excellent thermal stability at the time.
- the vinyl polymer powders of Comparative Examples 1, 3, and 4 since calcium salt is used for coagulation of the vinyl polymer latex, the calcium ion content exceeds 350 ppm, resulting in poor powder characteristics. It was. Further, the vinyl polymer powder of Comparative Example 2 was polymerized in the presence of an emulsifier other than the nonionic anion emulsifier and coagulated with sulfuric acid, so that the acid value was high and the powder characteristics were inferior. In addition, the resin compositions of Comparative Examples 5, 7, and 8 were inferior in thermal stability because they contained vinyl polymer powder containing calcium ions exceeding 350 ppm. The resin composition of Comparative Example 6 was inferior in thermal stability because it contained a vinyl polymer powder having a high acid value.
- a vinyl polymer powder that can be mixed with an engineering plastic to obtain a resin composition having excellent molding processability and high thermal stability during high-temperature molding, and having excellent powder characteristics.
- a thermoplastic resin composition excellent in molding processability and having high thermal stability during high-temperature molding and a molded body using the same.
- the molded body of the present invention is useful in a wide range of fields including the OA equipment field, the electrical / electronic equipment field, and the building materials field.
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Abstract
Description
本願は、2014年3月20日に、日本に出願された特願2014-058378号に基づき優先権を主張し、その内容をここに援用する。
本発明の他の目的は、成形加工性に優れかつ高温成形時の熱安定性の高い熱可塑性樹脂組成物及びこれを用いた成形体を提供することにある。
[1]ビニル重合体を含むビニル重合体粉体であって、前記ビニル重合体のガラス転移温度が0℃以上(ただし、ガラス転移点を複数持つ場合はすべてのガラス転移温度が0℃以上)であり、ビニル重合体粉体の総質量に対するマグネシウムイオン、カルシウムイオン、アルミニウムイオン、バリウムイオン、及び亜鉛イオンの含有量の合計が350ppm以下であり、ビニル重合体粉体の総質量に対するアンモニウムイオンの含有量が100ppm以下であり、酸価が2.5mgKOH/g以下であり、嵩密度が0.10~0.60g/cm3であるビニル重合体粉体。
[2]下記方法にて測定されるフリーフロー性が15g/10秒以上である[1]に記載のビニル重合体粉体。
[フリーフロー性の測定方法]
受け皿がセットされる台座と、筒口にシャッターが設けられたロートと、台座の上方にロートを保持する支持具と、支持具が固定された支柱とから構成される測定器を水平な場所に設置する。ロートのシャッターを閉じ、ロートに120cm3の粉体を均一に入れる。ついで、シャッターを開けて粉体を落下させ、すぐに台座上に受け皿をセットする。受け皿のセットと同時に、ストップウォッチで時間の計測を始め、10秒後に受け皿を測定器から外す。粉体の入った受け皿を計量し、10秒間に落下した粉体の量を求める。以上の測定を2回行い、10秒間に落下した粉体の量の平均値を求め、これをフリーフロー性(g/10秒)とする。
[3]ビニル重合体粉体の総質量に対するナトリウムイオン及びカリウムイオンの含有量の合計が100ppm以下である[1]又は[2]に記載のビニル重合体粉体。
[4]前記ビニル重合体が、エステル部位に炭素数1~4のアルキル基又は芳香族基を含む(メタ)アクリル酸エステル単位を含む[1]~[3]のいずれか1項に記載のビニル重合体粉体。
[5]前記ビニル重合体を構成する単量体単位の総質量中、芳香族ビニル単量体単位0.5~99.5質量%を含む[1]~[4]のいずれか1項に記載のビニル重合体粉体。
[6]前記ビニル重合体の質量平均分子量が5,000~20,000,000である[1]~[5]のいずれか1項に記載のビニル重合体粉体。
[7]前記ビニル重合体の質量平均分子量が5,000~200,000である[1]~[6]のいずれか1項に記載のビニル重合体粉体。
[8]エンジニアリングプラスチック70~99.9質量%、及び[1]~[7]のいずれか1項に記載のビニル重合体粉体を0.1~30質量%を含有する熱可塑性樹脂組成物。
[9]前記エンジニアリングプラスチックがポリアミド、ポリエステル及びポリカーボネートから選ばれる少なくとも1種類の樹脂である[8]に記載の熱可塑性樹脂組成物。
[10][8]又は[9]に記載の熱可塑性樹脂組成物を成形してなる成形体。
[11]エステル部位に炭素数1~4のアルキル基又は芳香族基を含む(メタ)アクリル酸エステル単位0.5~99.5質量%と、芳香族ビニル単量体単位0.5~99.5質量%とを含み、ガラス転移温度が0℃以上(ただし、ガラス転移点を複数持つ場合はすべてのガラス転移温度が0℃以上)であるビニル重合体を含み、下記条件[1]及び[2]を満足するビニル重合体粉体。
条件[1]
JIS K6720に準拠して測定される嵩密度が0.30~0.60g/cm3。
条件[2]
下記方法にて測定されるフリーフロー性が15g/10秒以上。
[フリーフロー性の測定方法]
受け皿がセットされる台座と、筒口にシャッターが設けられたロートと、台座の上方にロートを保持する支持具と、支持具が固定された支柱とから構成される測定器を水平な場所に設置する。ロートのシャッターを閉じ、ロートに120cm3の粉体を均一に入れる。ついで、シャッターを開けて粉体を落下させ、すぐに台座上に受け皿をセットする。受け皿のセットと同時に、ストップウォッチで時間の計測を始め、10秒後に受け皿を測定器から外す。粉体の入った受け皿を計量し、10秒間に落下した粉体の量を求める。以上の測定を2回行い、10秒間に落下した粉体の量の平均値を求め、これをフリーフロー性(g/10秒)とする。
[12]ビニル重合体粉体の製造方法であって、下記工程(1)及び工程(2)を含む方法。
工程(1):ノニオンアニオン乳化剤の存在下でビニル単量体を乳化重合して、ガラス転移温度が0℃以上(ただし、ガラス転移点を複数持つ場合はすべてのガラス転移温度が0℃以上)のビニル重合体ラテックスを得る工程。
工程(2):前記ビニル重合体ラテックスを凝析してpH6以下のスラリーを作り析出物を生成させ、前記析出物をビニル重合体粉体として回収する工程。
[13]前記ノニオンアニオン乳化剤のイオン性親水部がカルボン酸若しくはその塩、又はリン酸若しくはその塩である[12]に記載のビニル重合体粉体の製造方法。
[14]工程(2)において、酸を用いてビニル重合体ラテックスを凝析する[12]に記載のビニル重合体粉体の製造方法。
[15]工程(2)において、スラリーのpHが4以下である[12]に記載のビニル重合体粉体の製造方法。
[ビニル重合体粉体]
本発明の第一の態様におけるビニル重合体粉体は、ビニル重合体を含み、ビニル重合体のガラス転移温度が0℃以上であり、ビニル重合体粉体の総質量に対して、マグネシウムイオン、カルシウムイオン、アルミニウムイオン、バリウムイオン、及び亜鉛イオンの含有量の合計が350ppm以下であり、ビニル重合体粉体の総質量に対して、アンモニウムイオンの含有量が100ppm以下であり、酸価が2.5mgKOH/g以下であり、嵩密度が0.10~0.60g/cm3であるビニル重合体粉体である。
本発明の第一の態様におけるビニル重合体は、ガラス転移温度が0℃以上である。ビニル重合体のガラス転移温度が0℃以上であれば、エンジニアリングプラスチックと混合した樹脂組成物の熱変形温度を下げにくい。上記の観点から、ビニル重合体のガラス転移温度は30℃以上が好ましく、60℃以上がより好ましく、70℃以上がさらに好ましく、80℃以上が特に好ましく、90℃以上が最も好ましい。また、ビニル重合体のガラス転移温度は、粉体回収の行いやすさから、200℃以下が好ましく、150℃以下がより好ましく、120℃以下がさらに好ましい。具体的には、ビニル重合体のガラス転移温度は、30~150℃が好ましく、60~120℃がより好ましい。
示差走査熱量測定(DSC)装置(機種名「DSC6200」セイコーインスツル(株)社製)を用い、重合体のガラス転移温度をJIS K7121に準じて測定する。補外ガラス転移開始温度の数値をガラス転移温度として用いる。
本発明の第一の態様におけるビニル重合体粉体中に含まれるマグネシウムイオン、カルシウムイオン、アルミニウムイオン、バリウムイオン、及び亜鉛イオンの含有量の合計は、ビニル重合体粉体の総質量に対し、350ppm以下である。ビニル重合体粉体中に含まれる金属イオンの含有量の合計が高いと、エンジニアリングプラスチック、特にポリエステル及びポリカーボネートに配合した際、押出し、成形時の熱及び/又は水分等により、前記樹脂を触媒的に分解するため、高温成形時の熱安定性が悪化する。
本発明の第一の態様におけるビニル重合体粉体に含まれるアンモニウムイオンの含有量は、ビニル重合体粉体の総質量に対し、100ppm以下である。ビニル重合体粉体中に含まれるアンモニウムイオンの含有量の合計が高いと、エンジニアリングプラスチック、特にポリエステル及びポリカーボネートに配合した際、押出し、成形時の熱及び/又は水分等により、前記樹脂を触媒的に分解するため、高温成形時の熱安定性が悪化する。
試料を粉砕した後、メスフラスコに秤量する。蒸留水を加えて超音波処理を行い、アンモニウムイオンを抽出する。抽出したアンモニウムイオンをイオンクロマトグラフ分析装置(機種名「IC-2010」東ソー(株))により定量する。
本発明の第一の態様におけるビニル重合体粉体の酸価は2.5mgKOH/g以下である。ビニル重合体粉体の酸価が規定量より高いとエンジニアリングプラスチック、特にポリエステル及びポリカーボネートに配合した際、熱及び/又は水分等により、前記樹脂を触媒的に分解するため、高温成形時の熱安定性が悪化する。上記の観点から、ビニル重合体粉体の酸価は、2.0mgKOH/g以下であることが好ましい。より具体的には、0~2.5mgKOH/gであることが好ましく、0~2.0mgKOH/gであることがより好ましい。
ビニル重合体粉体試料10gをトルエン30mlに加えて室温撹拌し、完全溶解させる。溶解後、トルエン/エタノール=50/50体積%混合溶液を40ml入れ希釈する。得られたビニル重合体溶液をエタノール性水酸化カリウム溶液でpH12まで滴定する。溶媒はビニル重合体粉体を溶解可能であれば、特に限定されないが、例えば、ジメチルホルムアミド、ジメチルスルホキシド、ジメチルアセトアミド、N-メチルピロリドン、アセトン、メチルエチルケトン、シクロヘキサノン、キシレン、トルエン、クロロベンゼン、ベンゼン、クレゾール、クロロホルム、ジクロロメタン、ジエチルエーテル、テトラヒドロフラン、ジオキサン、エタノール、ブタノール、イソプロパノール、ヘキサン、ヘプタン、シクロヘキサン、酢酸エチル、アセトニトリル、水が挙げられる。また、これらの溶媒は1種を単独で用いてもよく、2種以上を併用してもよい。
本発明の第一の態様におけるビニル重合体粉体の嵩密度は、0.10~0.60g/cm3である。ビニル重合体粉体の嵩密度が0.10g/cm3以上であると、粉体取扱い性に優れる。上記の観点から、ビニル重合体粉体の嵩密度は0.20g/cm3以上が好ましく、0.30g/cm3以上がより好ましい。具体的には、0.20~0.60g/cm3が好ましく、0.30~0.60g/cm3がより好ましい。
本発明において、ビニル重合体粉体の嵩密度は、試料約120cm3にゼオライト粉末0.1gを混合した後、JIS K6720に準拠して測定されたものをいう。
本発明の第一の態様におけるビニル重合体粉体のフリーフロー性は、15g/10秒以上であることが好ましい。フリーフロー性が15g/10秒以上であると、粉体取扱い性に優れる。上記の観点から、ビニル重合体粉体のフリーフロー性は、20g/10秒以上がより好ましい。
具体的には、15~60g/10秒が好ましく、20~60g/10秒がより好ましい。
まず、測定器を水平な場所に設置し、ロート43のシャッター42を閉じ、ロート43に120cm3の粉体を均一に入れる。ついで、シャッターを開けて粉体を落下させ、すぐに台座41上にあらかじめ風袋(受け皿40の空の重さ)が測定された受け皿40をセットする。受け皿40のセットと同時に、ストップウォッチで時間の計測を始め、10秒後に受け皿40を測定器から外す。粉体の入った受け皿を計量し、10秒間にロートから受け皿の上に落下した粉体の量(単位:g)を求める。以上の測定を2回行い、10秒間に落下した粉体の量の平均値を求め、これをフリーフロー性(g/10秒)とする。
[粉体粒度]
ガラス転移温度が0℃以上(ただし、ガラス転移点を複数持つ場合はすべてのガラス転移温度が0℃以上)であるビニル重合体を含むビニル重合体粉体の嵩密度及びフリーフローを高めるには、ビニル重合体粉体中に含まれる微粉の含有量が少ない方が好ましい。具体的には、ビニル重合体粉体中に含まれる粒子径38μm以下の成分の含有量が、0~15質量%が好ましく、0~10質量%がより好ましい。
なお、粒子径38μm以下の成分の含有量は下記の方法で測定することができる。
試料2gに、ゼオライト粉末10mgを混合した後、連続式音波式篩分け測定器(機種名「ロボットシフターRPS-95」(株)セイシン企業製)を用いて、粒度分布を測定する。このとき、メッシュは#20、#32、#42、#60、#100、#150、#250、#400の合計8枚を使用し、#400メッシュを通過した成分を粒子径38μm以下の成分とする。
ガラス転移温度が0℃以上(ただし、ガラス転移点を複数持つ場合はすべてのガラス転移温度が0℃以上)であるビニル重合体を含むビニル重合体粉体中に含まれる粒子径38μm以下の成分の含有量を減らす方法として、例えば、ノニオンアニオン乳化剤の存在下でビニル単量体を乳化重合した重合体のラテックスを凝析してpH6以下のスラリーを作り、析出したビニル重合体を粉体として回収する方法、ビニル重合体粉体を篩別し、粒子径38μm以下の成分を取り除く方法が挙げられる。これらのうち、工業生産性に優れることから、ノニオンアニオン乳化剤の存在下でビニル単量体を乳化重合した重合体のラテックスを凝析してpH6以下のスラリーを作り、析出したビニル重合体を粉体として回収する方法が好ましい。
本発明の第一の態様におけるビニル重合体の質量平均分子量は5,000~20,000,000であることが好ましい。
ビニル重合体粉体を流動性向上剤としてエンジニアリングプラスチックに配合した際、ビニル重合体の質量平均分子量が5,000以上であれば機械特性を損ないにくく、20,000,000以下であれば溶融流動性に優れる。上記の観点から、ビニル重合体の質量平均分子量は、5,000~200,000が好ましく、10,000~150,000がより好ましく、15,000~100,000がさらに好ましく、20,000~100,000が特に好ましく、30,000~75,000が最も好ましい。
また、ビニル重合体粉体を溶融張力向上剤としてエンジニアリングプラスチックに配合した際、ビニル重合体の質量平均分子量が200,000以上であれば、溶融張力に優れ、20,000,000以下であれば、エンジニアリングプラスチックとビニル重合体を溶融混練しやすい。上記の観点から、ビニル重合体の質量平均分子量は、200,000~20,000,000が好ましく、200,000~10,000,000がより好ましく、500,000~5,000,000がさらに好ましい。
なお、質量平均分子量は、ポリスチレン換算のゲルパーミエーションクロマトグラフィーにより測定することができる。
本発明の第一の態様におけるビニル重合体粉体は、例えば、ラジカル重合可能なビニル単量体を重合し、得られたビニル重合体のラテックスを粉体として回収することにより製造される。
ビニル重合体の重合方法としては、重合体の組成分布や粒子モルフォロジーを制御しやすいことから、乳化重合、ミニエマルション重合、微細懸濁重合が好ましく、乳化重合がより好ましい。
重合方法としては特に限定されず、一段重合、二段重合、又は多段階重合などを採用することができる。例えば、ビニル単量体を、一段目ビニル単量体と、二段目ビニル単量体とに分割し、まず、一段目ビニル単量体を乳化重合して、プレ共重合体を得た後、プレ共重合体の存在下に、一段目ビニル単量体を乳化重合してもよい。
本発明においてビニル重合体はビニル単量体を重合して得ることができる。
ビニル重合体粉体を流動性向上剤として使用する場合、及び溶融張力向上剤として使用する場合、いずれの場合においてもビニル重合体は、得られるビニル重合体粉体のエンジニアリングプラスチック、特にポリエステル及びポリカーボネート中での分散性の観点から、エステル部位に炭素数1~4のアルキル基又は芳香族基を含む(メタ)アクリル酸エステル単位を含むことが好ましい。なお、本明細書中、「(メタ)アクリル酸」とは、α位に水素原子が結合したアクリル酸と、α位にメチル基が結合したメタクリル酸の一方あるいは両方を意味する。「(メタ)アクリル酸エステル」とは、α位に水素原子が結合したアクリル酸エステルと、α位にメチル基が結合したメタクリル酸エステルの一方あるいは両方を意味する。「(メタ)アクリレート」とは、α位に水素原子が結合したアクリレートと、α位にメチル基が結合したメタクリレートの一方あるいは両方を意味する。
ビニル重合体は、必要に応じて、その他の単量体単位を含んでいてもよい。
また、重合反応が二段重合である場合、一段目ビニル単量体がスチレン、α-メチルスチレン、及びフェニルメタクリレートの組み合わせ;スチレン、α-メチルスチレン、及びメチルメタクリレートの組み合わせであることが好ましく、
二段目ビニル単量体がスチレン、フェニルメタクリレート、メチルメタクリレート、及びアリルメタクリレートの組み合わせ;スチレン、メチルメタクリレート、及びアリルメタクリレートの組み合わせ;及びスチレン、フェニルメタクリレート、メチルメタクリレート、n-ブチルアクリレ―ト、及びアリルメタクリレートの組み合わせであることが好ましい。
連鎖移動剤としては、n-ドデシルメルカプタン、t-ドデシルメルカプタン、n-オクチルメルカプタン、t-オクチルメルカプタン、n-テトラデシルメルカプタン、n-ヘキシルメルカプタン、n-ブチルメルカプタン等のメルカプタン;四塩化炭素、臭化エチレン等のハロゲン化合物;α-スチレンダイマーが挙げられる。これらの連鎖移動剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
ビニル単量体の乳化重合に用いる乳化剤として、例えば、アニオン系乳化剤、ノニオン系乳化剤、ノニオンアニオン乳化剤、高分子乳化剤が挙げられる。これらのうち、ノニオンアニオン乳化剤を用いることが好ましい。尚、本発明において、「ノニオンアニオン乳化剤」とは、非イオン性の親水部とアニオン性の親水部(イオン性親水部)を同一分子内に有する乳化剤を示す。
本発明の第一の態様におけるビニル重合体粉体は、例えば、ビニル重合体ラテックスを粉体として回収することで得られる。
ビニル重合体ラテックスを粉体化する方法としては、公知の粉体化方法を用いることができる。例えば、凝析法、噴霧乾燥法が挙げられる。これらのうち、凝析法は、噴霧乾燥法と比較して、乳化剤がビニル重合体粉体中に残存しにくく好ましい。
ビニル重合体粉体をスラリーから分離した後、イオン交換水等で洗浄し、脱水し、乾燥してもよい。洗浄を行うことにより、不純物の量をコントロールすることができる。
本発明の第二の態様における熱可塑性樹脂組成物は、本発明の第一の態様におけるビニル重合体、及びエンジニアリングプラスチックを含む。本発明の第二の対応における熱可塑性樹脂組成物に用いるエンジニアリングプラスチックは、特に限定されず、公知のエンジニアリングプラスチックを使用することができる。エンジニアリングプラスチックとしては、例えば以下のものが挙げられる。ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル;6-ナイロン、6,6-ナイロン、ポリフェニレンテレフタルアミド等のポリアミド;ポリカーボネート、シンジオタクチックポリスチレン、ポリアリレート、ポリフェニレンエーテル、ポリフェニレンスルフィド、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリスルホン、ポリエーテルスルホン、ポリアミドイミド、ポリエーテルイミド、ポリアセタール。これらの中でも、成形加工性改良効果が高いことから、ポリアミド、ポリエステル、ポリカーボネートが好ましく、ポリエステル、ポリカーボネートがより好ましく、ポリカーボネートがさらに好ましい。
エンジニアリングプラスチックは市販のものを用いてもよく、合成したものを用いてもよい。市販品としては、芳香族ポリカーボネート樹脂(商品名:「ユーピロンS-2000F」、三菱エンジニアリングプラスチックス(株)製、粘度平均分子量:22,000)や、芳香族ポリカーボネート樹脂(商品名:「ユーピロンS-3000F」、三菱エンジニアリングプラスチックス(株)製、粘度平均分子量:21,000)が挙げられる。
樹脂組成物100質量%に対し、エンジニアリングプラスチック70~99.9質量%を配合することが好ましく、80~99質量%がより好ましく、85 ~99質量%がさらに好ましい。
本発明の第三の態様における成形体は、上記の熱可塑性樹脂組成物を成形したものである。その成形方法としては、例えば、圧縮成形、トランスファー成形、射出成形、ブロー成形、押出成形、積層成形、カレンダー成形が挙げられる。前記樹脂組成物の成形温度(樹脂組成物の温度)は特に限定されない。成形温度が高いほど樹脂組成物は溶融流動性に優れるが、高すぎると樹脂組成物の分解が促進されることから、240~350℃が好ましい。
ゲルパーミエーションクロマトグラフィーを用いて、下記の条件でビニル重合体の質量平均分子量(Mw)及び数平均分子量(Mn)を測定した。
装置 :東ソー(株)製HLC8220
カラム :東ソー(株)製TSKgel SuperMultiporeHZ-H(内径4.6mm×長さ15cm×2本)
温度 :40℃
キャリアー液:テトラヒドロフラン
流量 :0.35ml/分
試料濃度:0.1%
試料注入量:10μl
標準 :ポリスチレン
示差走査熱量測定(DSC)装置(機種名「DSC6200」セイコーインスツル(株)社製)を用い、ビニル重合体のガラス転移温度をJIS K7121に準じて測定した。補外ガラス転移開始温度の数値をガラス転移温度として用いた。
ビニル重合体粉体試料をトルエンに加えて室温撹拌し、完全溶解させた。溶解後、トルエン/エタノール=50/50体積%混合溶液を40ml入れ希釈した。得られたビニル重合体溶液をエタノール性水酸化カリウム溶液でpH12まで滴定した。表1に、ビニル重合体粉体試料の溶解条件及び滴定に用いたエタノール性水酸化カリウム溶液濃度をまとめた。
試料1gを白金皿に量り取り、電熱器により乾式灰化させ塩酸及び蒸留水で溶解し、蒸留水で50mlにメスアップし検液とした。この検液をICP発光分析装置(機種名「IRIS Interpid II XSP」Thermo Scientific社製)を用いて金属イオン量を定量した。
(1)嵩密度
ビニル重合体粉体約120cm3にゼオライト粉末0.1gを混合した後、JIS K6720に準拠して測定した。嵩密度が高いほど粉体取扱い性に優れる。
図1は、フリーフロー性の評価に使用された測定器である。この測定器は、受け皿40がセットされる台座41と、筒口にシャッター42が設けられたロート43と、台座41の上方にロート43を保持する支持具44と、支持具44が固定された支柱45とから構成されるものである。この測定器を用いたフリーフロー性の評価は、以下のようにして行った。
まず、測定器を水平な場所に設置し、ロート43のシャッター42を閉じ、ロート43に120cm3の粉体を均一に入れた。ついで、シャッターを開けて粉体を落下させ、すぐに台座41上にあらかじめ風袋が測定された受け皿40をセットした。受け皿40のセットと同時に、ストップウォッチで時間の計測を始め、10秒後に受け皿40を測定器から外した。粉体の入った受け皿を計量し、10秒間に落下した粉体の量を求めた。以上の測定を2回行い、10秒間に落下した粉体の量の平均値を求め、これをフリーフロー性(g/10秒)とした。フリーフロー性が高いほど、粉体流動性に優れる。
樹脂組成物として、ポリカーボネート樹脂組成物のペレットを用いた。
この評価は樹脂組成物から製造される平板の黄色度(YI)値によって、樹脂組成物の熱安定性を評価するものであり、下記の数式で定義されるΔYIが小さい樹脂組成物は熱安定性が優れると判断される。
ΔYI=滞留後YI-初期YI
シリンダー温度320℃に設定した100t射出成形機(機種名「SE-100DU」、住友重機工業(株)製)にペレットを供給して、射出成形して、長さ100mm、幅50mm、厚さ2mmの平板を得た。次いで、平板のYI値を測定し、その値を初期YIとした。
シリンダー温度320℃に設定した100t射出成形機(機種名「SE-100DU」、住友重機工業(株)製)にペレットを供給して、シリンダー内に30分滞留させた後に射出成形して、長さ100mm、幅50mm、厚さ2mmの平板を得た。次いで平板のYI値を測定し、その値を滞留後YIとした。
平板のYI値は、JIS K7105に準拠し、分光色差計(機種名「SE2000」日本電色工業(株)製)を使用し、C光源、2度視野の条件で、実施例13~22及び比較例5~8は透過光測定法にて測定し、実施例23~25は反射光測定法にて測定した。
樹脂組成物のスパイラルフロー長さによって溶融流動性を評価するものであり、射出成形機(機種名「SE-100DU」、住友重機工業(株)製)を用いて測定した。スパイラルフロー長さが長いほど溶融流動性に優れる。なお、成形条件としては、成形温度を320℃、金型温度を80℃とし、得られる成形体の肉厚を2mm及び幅を15mmとした。
樹脂組成物のペレットをキャピラリー式レオメーター(機種名「ツインキャピラリーレオメーター RH-7型」、ROSAND社製)を用いて、ダイス径=φ1mm、L/D=16、温度280℃の条件で、一定量(1.57cm3/分)で押出し、ストランドを一定速度(10m/分)で引き取り、溶融張力を測定した。
[実施例1]
乳化剤としてのポリオキシエチレン(6)アルキルエーテルリン酸ナトリウム1.0部、イオン交換水294部を、撹拌翼、コンデンサー、熱電対、窒素導入口を備えた容量5リットルのセパラブルフラスコ内に仕込み、室素気流下に室温で30分間撹拌した。尚、前記ポリオキシエチレン(6)アルキルエーテルリン酸ナトリウムは、予め、前記イオン交換水の一部に溶解させた状態で使用した。
乳化剤をポリオキシエチレン(4.5)ラウリルエーテル酢酸ナトリウム1.0部に変更したこと以外は実施例1と同様に重合を行って、ビニル重合体ラテックスを得た。続いて、凝析剤を硫酸0.5部に変更したこと以外は実施例1と同様に前記ラテックスの凝析を行って、ビニル重合体粉体(A-2)100部を得た。尚、このときの固化後のスラリーのpHは2.2であった。
乳化剤としてのポリオキシエチレン(4.5)ラウリルエーテル酢酸ナトリウム2.0部、イオン交換水293部を、撹拌翼、コンデンサー、熱電対、窒素導入口を備えた容量5リットルのセパラブルフラスコ内に仕込み、室素気流下に室温で30分間撹拌した。尚、前記ポリオキシエチレン(4.5)ラウリルエーテル酢酸ナトリウムは、予め、前記イオン交換水の一部に溶解させた状態で使用した。
乳化剤をポリオキシエチレン(4.5)ラウリルエーテル酢酸ナトリウム1.0部に変更し、1段目の混合物を、スチレン30部、α-メチルスチレン10部、メチルメタクリレート10部、n- オクチルメルカプタン0.23部、t-ブチルハイドロパーオキサイド0.1部からなる混合物に変更し、2段目の混合物をスチレン20部、メチルメタクリレート29.75部、アリルメタクリレート0.25部、n- オクチルメルカプタン0.34部、t-ブチルハイドロパーオキサイド0.1部からなる混合物に変更したこと以外は実施例3と同様に重合を行って、ビニル重合体ラテックスを得た。続いて、実施例2と同様に前記ラテックスの凝析を行って、ビニル重合体粉体(A-4)100部を得た。尚、このときの固化後のスラリーのpHは2.1であった。
実施例3と同様に重合を行い、ビニル重合体ラテックスを得た。続いて、凝析剤としての硫酸0.5部を含有する硫酸水溶液280部を、攪拌装置を備えた容量40リットルの反応器に仕込み、この水溶液を温度90℃に加熱して、撹拌しながら、この水溶液中に前記ラテックスを徐々に滴下して、ポリマーを凝析させてスラリーを得た。その後、このスラリーの温度を90℃まで昇温させた後、5分間撹拌し、固化を行った。さらに、pHが3.7になるまで10%水酸化ナトリウム水溶液を固化後のスラリーに加えた。次いで、得られた析出物をスラリーから分離して、3000部のイオン交換水で洗浄し、脱水し、乾燥して、ビニル重合体粉体(A-5)100部を得た。
実施例2と同様に重合を行い、ビニル重合体ラテックスを得た。続いて、pHが5.8になるまで10%水酸化ナトリウム水溶液を固化後のスラリーに加えたこと以外は実施例5と同様にして、ビニル重合体粉体(A-6)100部を得た。
2段目の混合物を、スチレン20部、フェニルメタクリレート14.88部、メチルメタクリレート12.88部、n-ブチルアクリレート2部、アリルメタクリレート0.25部、n- オクチルメルカプタン0.34部、t-ブチルハイドロパーオキサイド0.1部からなる混合物に変更したこと以外は実施例3と同様に重合を行って、ビニル重合体ラテックスを得た。続いて、実施例2と同様に前記ラテックスの凝析を行って、ビニル重合体粉体(A-7)100部を得た。尚、このときの固化後のスラリーのpHは2.0であった。
2段目の混合物を、スチレン18.4部、フェニルメタクリレート13.69部、メチルメタクリレート13.69部、n-ブチルアクリレート4部、アリルメタクリレート0.25部、n- オクチルメルカプタン0.34部、t-ブチルハイドロパーオキサイド0.1部からなる混合物に変更したこと以外は実施例3と同様に重合を行って、ビニル重合体ラテックスを得た。続いて、凝析温度を85℃、固化温度を95℃に変更したこと以外は実施例2と同様に前記ラテックスの凝析を行って、ビニル重合体粉体(A-8)100部を得た。尚、このときの固化後のスラリーのpHは2.0であった。
2段目の混合物を、スチレン15.2部、フェニルメタクリレート11.3部、メチルメタクリレート11.3部、n-ブチルアクリレート12部、アリルメタクリレート0.25部、n- オクチルメルカプタン0.34部、t-ブチルハイドロパーオキサイド0.1部からなる混合物に変更したこと以外は実施例3と同様に重合を行って、ビニル重合体ラテックスを得た。続いて、凝析温度を65℃、固化温度を75℃に変更したこと以外は実施例2と同様に前記ラテックスの凝析を行って、ビニル重合体粉体(A-9)100部を得た。尚、このときの固化後のスラリーのpHは2.0であった。
乳化剤としてのポリオキシエチレン(4.5)ラウリルエーテル酢酸ナトリウム1.0部、メチルメタクリレート48部、n-ブチルアクリレート2部、n-オクチルメルカプタン0.004部、イオン交換水223部を、攪拌翼、コンデンサー、熱電対、窒素導入口を備えた容量3リットルのセパラブルフラスコに仕込み、窒素気流下に室温で30分間攪拌した。尚、前記ポリオキシエチレン(4.5)ラウリルエーテル酢酸ナトリウムは、予め、前記イオン交換水の一部に溶解させた状態で使用した。
乳化剤としてのポリオキシエチレン(4.5)ラウリルエーテル酢酸ナトリウム1.0部、メチルメタクリレート85部、n-ブチルアクリレート15部、イオン交換水223部を、攪拌翼、コンデンサー、熱電対、窒素導入口を備えた容量3リットルのセパラブルフラスコに仕込み、窒素気流下に室温で30分間攪拌した。尚、前記ポリオキシエチレン(4.5)ラウリルエーテル酢酸ナトリウムは、予め、前記イオン交換水の一部に溶解させた状態で使用した。
ビニル単量体混合物をメチルメタクリレート85部、n-ブチルアクリレート15部、n-オクチルメルカプタン0.03部からなる混合物に変更したこと以外は実施例11と同様に重合を行って、ビニル重合体ラテックスを得た。
続いて、実施例10と同様に前記ラテックスの凝析を行って、ビニル重合体粉体(A-12)を得た。尚、このときの固化後のスラリーのpHは2.0であった。
実施例3と同様に重合を行い、ビニル重合体ラテックスを得た。続いて、凝析剤を酢酸カルシウム5.0部に変更したこと以外は実施例3と同様に前記ラテックスの凝析を行って、ビニル重合体粉体(A-13)100部を得た。尚、このときの固化後のスラリーのpHは6.5であった。
乳化剤をアルケニルコハク酸ジカリウム1.0部に変更したこと以外は実施例1と同様に重合を行って、ビニル重合体ラテックスを得た。続いて、実施例2と同様に前記ラテックスの凝析を行って、ビニル重合体粉体(A-14)100部を得た。尚、このときの固化後のスラリーのpHは2.3であった。
比較例2と同様に重合を行い、ビニル重合体ラテックスを得た。続いて、比較例1と同様に前記ラテックスの凝析を行って、ビニル重合体粉体(A-15)100部を得た。尚、このときの固化後のスラリーのpHは6.5であった。
乳化剤をアルキルジフェニルエーテルジスルホン酸ナトリウム1.0部に変更したこと以外は実施例1と同様に重合を行って、ビニル重合体ラテックスを得た。このビニル重合体ラテックスに、ヒンダードフェノール系酸化防止剤水性分散液(製品名Irgastab MBS43EM(チバ・ジャパン(株)製))1.5部(有効成分として)を添加し、常温で撹拌した。比較例1と同様に前記ラテックスの凝析を行って、ビニル重合体粉体(A-16)100部を得た。尚、このときの固化後のスラリーのpHは6.9であった。
表5及び表6に従って各材料を配合して、ポリカーボネート樹脂組成物を得た。これらの各樹脂組成物を、それぞれ、同方向二軸押出機(機種名「PCM-30」、(株)池貝製)に供給し、バレル温度280℃で溶融混練し、ペレットを得た。得られたペレットを用いて樹脂組成物の特性を評価し、評価結果を表5及び表6に示した。尚、表5及び表6中に記載の記号は表4中に記載の化合物を意味する。
本発明の成形体は、OA機器分野、電気・電子機器分野、建材分野をはじめ、その他の広い分野において有用である。
41 台座
42 シャッター
43 ロート
44 支持具
45 支柱
Claims (15)
- ビニル重合体を含むビニル重合体粉体であって、前記ビニル重合体のガラス転移温度が0℃以上(ただし、ガラス転移点を複数持つ場合はすべてのガラス転移温度が0℃以上)であり、ビニル重合体粉体の総質量に対するマグネシウムイオン、カルシウムイオン、アルミニウムイオン、バリウムイオン、及び亜鉛イオンの含有量の合計が350ppm以下であり、ビニル重合体粉体の総質量に対するアンモニウムイオンの含有量が100ppm以下であり、酸価が2.5mgKOH/g以下であり、嵩密度が0.10~0.60g/cm3であるビニル重合体粉体。
- 下記方法にて測定されるフリーフロー性が15g/10秒以上である請求項1に記載のビニル重合体粉体。
[フリーフロー性の測定方法]
受け皿がセットされる台座と、筒口にシャッターが設けられたロートと、台座の上方にロートを保持する支持具と、支持具が固定された支柱とから構成される測定器を水平な場所に設置する。ロートのシャッターを閉じ、ロートに120cm3の粉体を均一に入れる。ついで、シャッターを開けて粉体を落下させ、すぐに台座上に受け皿をセットする。受け皿のセットと同時に、ストップウォッチで時間の計測を始め、10秒後に受け皿を測定器から外す。粉体の入った受け皿を計量し、10秒間に落下した粉体の量を求める。以上の測定を2回行い、10秒間に落下した粉体の量の平均値を求め、これをフリーフロー性(g/10秒)とする。 - ビニル重合体粉体の総質量に対するナトリウムイオン及びカリウムイオンの含有量の合計が100ppm以下である請求項1に記載のビニル重合体粉体。
- 前記ビニル重合体が、エステル部位に炭素数1~4のアルキル基又は芳香族基を含む(メタ)アクリル酸エステル単位を含む請求項1に記載のビニル重合体粉体。
- 前記ビニル重合体を構成する単量体単位の総質量中、芳香族ビニル単量体単位0.5~99.5質量%を含む請求項1に記載のビニル重合体粉体。
- 前記ビニル重合体の質量平均分子量が5,000~20,000,000である請求項1に記載のビニル重合体粉体。
- 前記ビニル重合体の質量平均分子量が5,000~200,000である請求項1に記載のビニル重合体粉体。
- エンジニアリングプラスチック70~99.9質量%、請求項1~7のいずれか1項に記載のビニル重合体粉体を0.1~30質量%を含有する熱可塑性樹脂組成物。
- 前記エンジニアリングプラスチックがポリアミド、ポリエステル及びポリカーボネートから選ばれる少なくとも1種類の樹脂である請求項8に記載の熱可塑性樹脂組成物。
- 請求項8に記載の熱可塑性樹脂組成物を成形してなる成形体。
- エステル部位に炭素数1~4のアルキル基又は芳香族基を含む(メタ)アクリル酸エステル単位0.5~99.5質量%と、芳香族ビニル単量体単位0.5~99.5質量%とを含み、ガラス転移温度が0℃以上(ただし、ガラス転移点を複数持つ場合はすべてのガラス転移温度が0℃以上)であるビニル重合体を含み、下記条件[1]及び[2]を満足するビニル重合体粉体。
条件[1]
JIS K6720に準拠して測定される嵩密度が0.30~0.60g/cm3。
条件[2]
下記方法にて測定されるフリーフロー性が15g/10秒以上。
[フリーフロー性の測定方法]
受け皿がセットされる台座と、筒口にシャッターが設けられたロートと、台座の上方にロートを保持する支持具と、支持具が固定された支柱とから構成される測定器を水平な場所に設置する。ロートのシャッターを閉じ、ロートに120cm3の粉体を均一に入れる。ついで、シャッターを開けて粉体を落下させ、すぐに台座上に受け皿をセットする。受け皿のセットと同時に、ストップウォッチで時間の計測を始め、10秒後に受け皿を測定器から外す。粉体の入った受け皿を計量し、10秒間に落下した粉体の量を求める。以上の測定を2回行い、10秒間に落下した粉体の量の平均値を求め、これをフリーフロー性(g/10秒)とする。 - ビニル重合体粉体の製造方法であって、下記工程(1)及び工程(2)を含む方法。
工程(1):ノニオンアニオン乳化剤の存在下でビニル単量体を乳化重合して、ガラス転移温度が0℃以上(ただし、ガラス転移点を複数持つ場合はすべてのガラス転移温度が0℃以上)のビニル重合体ラテックスを得る工程。
工程(2):前記ビニル重合体ラテックスを凝析してpH6以下のスラリーを作り析出物を生成させ、前記析出物をビニル重合体粉体として回収する工程。 - 前記ノニオンアニオン乳化剤のイオン性親水部がカルボン酸若しくはその塩、又はリン酸若しくはその塩である請求項12に記載のビニル重合体粉体の製造方法。
- 工程(2)において、酸を用いてビニル重合体ラテックスを凝析する請求項12に記載のビニル重合体粉体の製造方法。
- 工程(2)において、スラリーのpHが4以下である請求項12に記載のビニル重合体粉体の製造方法。
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