WO2007034789A1 - Composition contenant une résine de copolymère composé vinylique aromatique/acide (méth)acrylique et procédé servant à produire celle-ci - Google Patents

Composition contenant une résine de copolymère composé vinylique aromatique/acide (méth)acrylique et procédé servant à produire celle-ci Download PDF

Info

Publication number
WO2007034789A1
WO2007034789A1 PCT/JP2006/318528 JP2006318528W WO2007034789A1 WO 2007034789 A1 WO2007034789 A1 WO 2007034789A1 JP 2006318528 W JP2006318528 W JP 2006318528W WO 2007034789 A1 WO2007034789 A1 WO 2007034789A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolymer resin
containing composition
acrylic acid
mass
meth
Prior art date
Application number
PCT/JP2006/318528
Other languages
English (en)
Japanese (ja)
Inventor
Kohhei Nishino
Tetsuya Takahashi
Original Assignee
Toyo Styrene Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Styrene Co., Ltd. filed Critical Toyo Styrene Co., Ltd.
Priority to KR1020087006029A priority Critical patent/KR101292963B1/ko
Priority to CN2006800340257A priority patent/CN101263194B/zh
Priority to JP2007536494A priority patent/JP5237640B2/ja
Publication of WO2007034789A1 publication Critical patent/WO2007034789A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/06—Treatment of polymer solutions
    • C08F6/10—Removal of volatile materials, e.g. solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • Aromatic vinyl compound mono (meth) acrylic acid copolymer resin-containing composition and method for producing the same are aromatic vinyl compound mono (meth) acrylic acid copolymer resin-containing composition and method for producing the same
  • the present invention is an aromatic vinyl compound mono (meth) acrylic acid copolymer resin-containing composition that is excellent in heat resistance, suppresses gelation due to an intermolecular condensation reaction, and does not contain a gel-like substance. It relates to the manufacturing method.
  • Aromatic vinyl compound mono (meth) acrylic acid copolymer resins have superior heat resistance compared to general polystyrene and are mainly used as food packaging materials for microwave heating. Has been. Specifically, after being formed into an extruded foam sheet or biaxially stretched sheet, it is used after being shaped into a food container or lid. In addition, since it has an excellent balance between transparency and heat resistance, it is also suitable for a light diffusing resin plate containing a light diffusing agent such as a light cover or a light diffusing plate for a transmissive display.
  • a drawback of aromatic vinyl compound mono (meth) acrylic acid copolymer resins is that the carboxyl group in the polymer undergoes a condensation reaction between polymer molecules due to thermal history during processing into a sheet or the like. It has been pointed out that gel-like substances may be produced, and that gel-like substances may be produced by the same reaction in the production process of copolymer resins.
  • Patent Document 1 JP-A 56-161409
  • Patent Document 2 JP 59-230043
  • the present invention provides an aromatic bur compound (meth) acrylic acid copolymer resin-containing composition in which gellich is suppressed particularly at high temperature and high vacuum, and does not contain a gel-like substance, and a method for producing the same The purpose is that.
  • the present invention has been intensively studied.
  • a specific polyoxyethylene alkyl ether is contained in the aromatic vinyl compound- (meth) acrylic acid copolymer resin-containing composition. It has been found that the gelation described above is remarkably suppressed by containing a specific amount of.
  • the present invention is based on such knowledge and has the following gist.
  • a composition comprising, as a main component, a copolymer resin of an aromatic bur compound monomer and (meth) acrylic acid, the following general formula (1) with respect to the mass of the copolymer resin
  • a poly (ethylene) alkyl ether represented by () is contained in 0.05 to 0.5% by mass, and a (meth) acrylic acid copolymer resin-containing composition.
  • R represents an alkyl group having 8 to 18 carbon atoms
  • X represents an integer representing the number of ethylene oxide units added, and the average number of additions is:! To 15
  • copolymer resin-containing composition according to any one of 1 to 3 above, containing 0.05 to 0.5% by mass of an ultraviolet absorber.
  • copolymer resin-containing composition according to any one of the above:! To 5, which contains 0 to 05-0. 5% by mass of a hindered amine light stabilizer.
  • a light diffusing resin plate obtained by adding a light diffusing agent to the copolymer resin-containing composition according to any one of 1 to 7 above and extrusion molding or injection molding.
  • a process for producing an aromatic vinyl compound- (meth) acrylic acid copolymer resin-containing composition according to any one of 1 to 7, wherein the aromatic vinyl compound monomer and (meta ) Acrylic acid is copolymerized in the polymerization step, and the unreacted product and / or polymerization solvent is removed from the reaction product after the polymerization reaction in the devolatilization step in the next step, and an aromatic vinyl compound— (meth) A copolymer characterized by adding the polyoxyethylene alkyl ether represented by the above general formula (1) before or during the devolatilization step of the process for producing an acrylic copolymer resin.
  • a method for producing a resin-containing composition A method for producing a resin-containing composition.
  • an aromatic vinyl imide compound (meth) acrylic acid copolymer resin-containing composition that can produce a molded article having excellent heat resistance and containing almost no gel-like substance that significantly deteriorates the appearance.
  • the aromatic vinyl compound / metatalic acid copolymer resin-containing composition obtained by the present invention can prevent the formation of a gel-like substance at the time of molding processing having a high gelation suppressing effect.
  • the present invention is a composition mainly comprising a copolymer resin of an aromatic vinyl monomer compound monomer and (meth) acrylic acid (in the present invention, also referred to as a copolymer resin-containing composition). ). And 0.5 to 0.5 to 0.5% by mass of a polyoxyethylene alkyl ether represented by the following general formula (1) as an anti-gelling agent with respect to the mass of the copolymer resin It is characterized by that.
  • R represents an alkyl group having 8 to 18 carbon atoms, preferably 12 to 18 carbon atoms, and X is an integer.
  • the addition number of ethylene oxide units is represented by a number, and the average addition number is 1 to 15).
  • Content of polyoxyethylene alkyl ether represented by the general formula (1) used in the present invention is the mass of the copolymer resin, 0.5 05-0 5 wt%, preferably from 0.1:.! ⁇ 0. a 4 mass 0/0.
  • the content of polyoxyethylene alkyl ether is less than 0.05% by mass with respect to the mass of the copolymer resin, the effect of suppressing Gelich in the devolatilization step when producing the copolymer is insufficient. In addition, the effect of suppressing gelation during molding is insufficient.
  • the content power S of polyoxyethylene alkyl ether exceeds 0.5% by mass relative to the resin mass, the heat resistance is lowered, which is not preferable.
  • the polyoxyethylene alkyl ether used in the present invention is generally synthesized by attaching ethylene oxide to an alcohol having an alkyl group represented by R in the general formula (1). Is done.
  • the polyoxyethylene alkyl ether thus obtained usually has a distribution in the number of added alkylene oxide units.
  • the average addition number of ethylene oxide units is from 1 to: 15, preferably from 4 to: 12.
  • propylene oxide may be added together with ethylene oxide within the range of the average number of additions of the present invention.
  • the average addition power of the ethylene oxide unit is less, the content of alcohol not added with ethylene oxide increases, which is preferable. If the average number of calories with ethylene oxide units exceeds 15, the gelling effect is insufficient.
  • Examples of the aromatic bur compound monomer used in the present invention include styrene, ⁇ -methylstyrene, 0-methylstyrene, ⁇ -methylstyrene and the like, and particularly preferable is styrene.
  • the (meth) acrylic acid used in the present invention is attalinoleic acid or methacrylic acid. These may be used alone or in combination.
  • monomers that can be copolymerized other than (meth) acrylic acid for example, monomers such as acrylonitrile, methacrylic acid ester, and acrylic acid ester are also effective for the present invention.
  • One or two or more types can be copolymerized as long as they do not impair the properties.
  • the content of the (meth) acrylic acid unit in the copolymer resin-containing composition of the present invention is preferably 3 to 15 mass%, more preferably 6 to 10 mass%.
  • (Meth) acrylic acid alone If the content is less than 3% by mass, the heat resistance of the microwave oven container is insufficient, and if it exceeds 15% by mass, the fluidity at the time of melting is significantly reduced and the molding processability is deteriorated. .
  • the residual amount of the aromatic vinyl compound monomer in the copolymer resin-containing composition of the present invention is preferably lOOOppm or less, more preferably 500ppm or less.
  • the residual amount of the aromatic vinyl compound monomer exceeds lOOOOppm, the heat resistance of the resulting copolymer resin composition decreases.
  • points, such as an odor it is not preferable also from points, such as an odor.
  • the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of an aromatic vinyl compound- (meth) acrylic acid copolymer resin is
  • the weight average molecular weight (Mw) in the present invention can be measured, for example, under the following conditions using gel permeation chromatography (GPC).
  • GPC model Showa Denko Shodex GPC- 101
  • the molecular weight of the aromatic bur compound (meth) acrylic acid copolymer resin in the present invention is a value in terms of polystyrene.
  • the molecular weight at each elution time is calculated from the elution curve of monodisperse polystyrene, and is calculated as the molecular weight in terms of polystyrene. It is.
  • an aromatic vinyl compound monomer and (meth) acrylic acid are copolymerized in a polymerization step, and the next step is a devolatilization step.
  • the unreacted product and / or polymerization solvent is removed from the reaction product after the polymerization reaction, and before the devolatilization step of the process for producing the aromatic vinyl compound mono (meth) acrylic acid copolymer resin, or the devolatilization step. It is preferable to add polyoxyethylene alkyl ether.
  • Examples of the polymerization method that can be used in the method for producing a copolymer resin-containing composition of the present invention include known styrene polymerization methods such as a bulk polymerization method, a solution polymerization method, and a suspension polymerization method.
  • Examples of solvents that can be used include alkylbenzenes such as benzene, toluene, ethylbenzene, and xylene; ketones such as acetone and methylethylketone; and aliphatic hydrocarbons such as hexane and cyclohexane.
  • a polymerization initiator and a chain transfer agent can be used as necessary.
  • organic peroxides such as benzoyl peroxide, t-butyl peroxybenzoate, 1,1-di (t-butylperoxy) cyclohexane, 1,1 bis (t-butylperoxy) 3, 3, 5 —Trimethylcyclohexane, t-butylperoxyisopropyl carbonate, dicumyl peroxide, t-butyltamyl peroxide, t-butylperoxyacetate, t-butylperoxy 2-ethyl hexanoate, 2, 2 bis (4,4 t-butylperoxycyclohexyl) propane, polyether tetrakis (t-butylperoxycarbonate), ethyl 3,3-di (tert-butylperoxy) butyrate, t-butylper
  • organic peroxides such as benzoyl peroxide
  • a rubber-reinforced aromatic vinyl-based resin such as HI-PS resin or MBS resin, or an aromatic such as SBS is used as a component containing rubber as necessary.
  • Vinyl-based thermoplastic elastomers can be blended.
  • the copolymer resin-containing composition of the present invention is blended with various additives as necessary. That power S.
  • the type of additive is not particularly limited as long as it is generally used for plastics, but is not limited to antioxidants, flame retardants, lubricants, processing aids, antiblocking agents, antistatic agents, antifogging agents, and light resistance. Examples include improvers, softeners, plasticizers, inorganic reinforcing agents, cross-linking agents, pigments, dyes, and the like, or mixtures thereof.
  • higher fatty acids such as stearic acid, zinc stearate, calcium stearate, and magnesium stearate or salts thereof, lubricants such as ethylenebisstearylamide, and plasticizers such as liquid paraffin may be included.
  • a benzotriazole ultraviolet absorber or a hindered amine light stabilizer can be preferably used as the light fastness improver.
  • the content in the copolymer resin-containing composition of light resistance improvers such as ultraviolet absorbers and light stabilizers is preferably 0.05 to 0.5% by mass, more preferably 0.:! ⁇ 0.4% by weight.
  • the heating rate was 50 ° C / hr and the test load was 50N.
  • 0.2 g of the copolymer resin-containing composition was dissolved in 10 ml of dimethylformamide containing cyclopentanol as an internal standard substance, and measured using a gas chromatography FID-GC-12A manufactured by Shimadzu Corporation.
  • the column was PEG-20MPT manufactured by GL Sciences, the detector was FID, and the carrier gas was nitrogen.
  • HPLC model alliance system 2695 separation module manufactured by Japan Waters
  • a flat plate (gate shape: 3 mm ⁇ 7 mm side gate) having a length of 75 mm, a width of 50 mm, and a thickness of 4 mm was molded at a temperature of 220 ° C. with an injection molding machine.
  • the number of gelled material flow marks (appearing as streaks along the direction of resin flow) appearing on the molded flat plate was measured to confirm the occurrence of the gel.
  • the gel substance can be confirmed by not dissolving in methyl ethyl ketone.
  • the copolymer resin-containing composition was heated and kneaded using the following plastic coder, and the geliness was evaluated by increasing the torque. Since moisture in the copolymer resin-containing composition affects the gelling reaction, it is necessary to sufficiently dry it before measurement.
  • the test was conducted under a nitrogen atmosphere at a setting temperature of 300 ° C, a sample input amount of 47 g, a rotation speed of 50 rpm, and a kneading time of 25 minutes. The sample was dried at 100 ° C for 4 hours. The ratio between the tone after 25 minutes and the minimum tonolek at the beginning of the measurement (after about 6 minutes) was defined as the gel strength, which was used as a guide for ease of gelling. If the degree of gelation is large, gelling is likely to occur.
  • a flat plate with a length of 40 mm, a width of 90 mm, and a thickness of 2 mm was prepared by injection molding, and an accelerated light resistance test was performed using an ATLAS Xenon Weatherometer Ci65 A. Irradiation intensity at a wavelength of 340nm 0.35W / m 2 , black panel temperature 63 ° C, humidity 50% irradiation for 500 hours, and color difference ⁇ ⁇ of the flat plate before and after the test Measured with a Sigma 80 manufactured by the company. Care was taken that there was no gel-like material at the hue measurement point.
  • a polymerization reactor was configured by connecting in series a first reactor, which was a 39-liter fully mixed stirring tank, and a second reactor, which was a 39-liter fully mixed stirring tank.
  • Styrene 77.1 wt 0/0, methacrylic acid 5.9 weight 0/0 have created a mixed solution of Echirubenzen 17.0 mass 0/0.
  • This raw material solution was continuously supplied to the first reactor at a rate of 12.6 kg per hour, and each reactor was circulated in a full state.
  • 1, 1 bis (t butylperoxy) cyclohexane (Perhexa C manufactured by NOF Co., Ltd.) on a mass basis is used for the total amount of styrene and methacrylic acid in the raw material solution. 250 PP m mixed.
  • polyoxyethylene lauryl ether [P_ 1] is continuously added as a gelling habit inhibitor at the first reactor inlet, and the polyoxyethylene laurylol relative to the mass of the copolymer resin at the second reactor outlet is added.
  • the content of ether [P-1] was adjusted to 0.20% by mass.
  • Emulgen 109P manufactured by Kao Corporation was used as polyoxyethylene lauryl ether [P-1] (alkyl group R in formula (1) has 12 carbon atoms).
  • the reaction temperature of each reactor was adjusted to be 130 ° C in the first reactor and 140 ° C in the second reactor.
  • the solution containing the copolymer resin continuously taken out from the second reactor was introduced into a vacuum devolatilization tank with a preheater installed in two stages in series, and the unreacted monomer and ethylbenzene were separated, and then a strand. After being extruded and cooled, it was cut into pellets.
  • the preheater temperature was set to 175 ° C
  • the vacuum devolatilizer pressure was set to 500 mmHg
  • the vacuum devolatilizer jacket temperature was set to 185 ° C.
  • the preheater temperature is 240 ° C
  • the vacuum devolatilizer pressure is 8 mmHg
  • the jacket temperature of the vacuum devolatilization tank was set to 240 ° C.
  • the resin temperature in the first-stage vacuum devolatilization tank was 168 ° C
  • the resin temperature in the second-stage vacuum devolatilization tank was 231 ° C. Table 1 shows the characteristics of the copolymer resin composition of the pellets obtained.
  • Example 2 The procedure was the same as Example 1 except that the addition amount of the gelation inhibitor was 0.10% by mass.
  • Example 2 The same procedure as in Example 1 was conducted except that polyoxyethylene lauryl ether [P-2] was used as a gelling habit inhibitor.
  • the polyoxyethylene lauryl ether [P-2] used was Emulgen 104P manufactured by Kao Corporation (the carbon number of the alkyl group R in the formula (1) is 12).
  • Example 2 The same procedure as in Example 1 was conducted except that polyoxyethylene C 16 —C 18 alkyl ether [P-3] was used as the gelation inhibitor.
  • the polyoxyethylene C16-C18 alkyl ether [P-3] used was Emulgen 210P manufactured by Kao Corporation (the carbon number of the alkyl group R in the formula (1) is 16-18).
  • Example 1 The same procedure as in Example 1 was conducted except that polyoxyethylene lauryl ether [P-4] was used as a Gelich inhibitor.
  • polyoxyethylene lauryl ether [P-4] Emulgen 120 manufactured by Kao Corporation was used (the carbon number of the alkyl group R in the formula (1) is 12).
  • Example 5 The procedure was the same as Example 5 except that the addition amount of the gelation inhibitor was 0.40% by mass.
  • Example 2 The same procedure as in Example 1 was conducted, except that polyoxyethylene polyoxypropylene alkyl ether [P_5] was used as the gelling habit inhibitor.
  • polyoxyethylene polyoxypropylene alkyl ether [P-5] Emulgen LSI 10 manufactured by Kao Corporation was used (the carbon number of the alkyl group R in the formula (1) is 12 to 15).
  • Comparative Example 2 The same procedure as in Example 1 was conducted except that octyl alcohol [A-1] was used as the gelling habit inhibitor and the addition amount was 2.0% by mass. As octyl alcohol [A-1], Calco 0898 manufactured by Kao Corporation was used.
  • Example 2 The procedure was the same as Example 1 except that stearyl alcohol [A-2] was used as a gelling habit inhibitor. In addition, stearyl alcohol [A-2] used a calo 8098 manufactured by Kao Corporation
  • Example 2 The procedure was the same as Example 1 except that the amount of the gelation inhibitor added was 0.70% by mass.
  • Example 2 The procedure was the same as Example 1 except that polyoxyethylene lauryl ether [P-6] was used as a gelling habit inhibitor.
  • the polyoxyethylene lauryl ether [P-6] used was Emalgen 130K manufactured by Kao Corporation.
  • TINUVIN 329 (2-(2H-benzotriazole-2-ynole) 1 4_ (1, manufactured by Ciba Specialty Chemicals) was used as an ultraviolet absorber.
  • 3 _ tetramethylolmethane Norev Chino Les) Fuenonore was 0.25 mass 0/0 added Caro and 40 in mm phi single screw extruder, 230 ° C, pelletized performed extruded blend at lOOrpm A copolymer resin-containing composition was obtained.
  • Example 2 To the copolymer resin-containing composition obtained in Example 1, as a hindered amine light stabilizer, Sanol LS-770 (bis (2, 2, 6, 6-tetramethyl-4-piperidyl) manufactured by Sankyo Lifetech Co., Ltd. was used. ) Sebacate) is added in an amount of 0.25% by mass, and it is 230 ° C in a 40mm ⁇ single screw extruder. Extrusion blending was performed at lOOrpm to obtain a pellet-shaped copolymer resin-containing composition.
  • Sanol LS-770 bis (2, 2, 6, 6-tetramethyl-4-piperidyl) manufactured by Sankyo Lifetech Co., Ltd.
  • Sebacate is added in an amount of 0.25% by mass, and it is 230 ° C in a 40mm ⁇ single screw extruder. Extrusion blending was performed at lOOrpm to obtain a pellet-shaped copolymer resin-containing composition.
  • TINUVIN 329 (2- (2H-benzotriazole-2-ynole) _4_ (1, 1) manufactured by Ciba Specialty Chemicals was used as an ultraviolet absorber. , 3, 3-tetra-methylbutyl) phenol) 0.13 weight 0/0 was added, Hin Dadoamin based light Sankyo as stabilizers Lifetech Co.
  • TINUVIN 329 (2- (2H-benzotriazole-2-ino)) 1- (1) (1) , 1, 3, 3-tetra-methylbutyl) phenol) 0 - 25 wt. 0/0 was added, Hin Dadoamin based light stabilizer as a Sankyo Lifetech Co. Sanol LS- 770 (bis (2, 2, 6, 6 - tetramethyl - 4 over) sebacate) 0 - 25 wt. 0/0 was added, by a single-screw extruder 40 ⁇ ⁇ , 230 ° C, performed extruded blend at lOOrpm a pelletized copolymer ⁇ fat-containing composition Obtained.
  • the copolymer resin-containing composition of the present invention has an excellent Vicat softening temperature and appearance that indicate its heat resistance, and an increase in torque in the heat-kneading test (gelation degree) ) Is small and excellent in stability during heating and kneading.
  • the appearance was poor due to the generation of a gel that was not sufficiently effective in suppressing gelation, and the increase in tonolec (degree of gelation) in the heating and kneading test was also large. Easily gelled by kneading.
  • Comparative Example 4 and Comparative Example 6 although the gelling suppression effect is high, the Vicat softening temperature is low and the heat resistance is poor.
  • the copolymer resin-containing composition of the present invention is excellent in light resistance. Furthermore, as shown in Examples 8 to 11, light resistance can be improved by blending an ultraviolet absorber and a hindered amine light stabilizer.
  • a containing composition was obtained.
  • the copolymer resin-containing composition is a microwave oven.
  • a light diffusing resin plate containing a light diffusing agent such as an illumination cover and a light diffusing plate for a transmissive display, preferably after being formed into a food packaging material for heating, or an extruded foam sheet or a biaxially stretched sheet. Furthermore, it can be used by shaping it into food containers or lids.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

On empêche une composition de résine de copolymère composé vinylique aromatique/acide (méth)acrylique qui a une excellente résistance à la chaleur de gélifier par condensation intramoléculaire et celle-ci ne contient pas de substances sous forme de gel. La composition contenant une résine de copolymère composé vinylique aromatique/acide (méth)acrylique contient, comme composant principal, une résine qui est un copolymère d'un monomère de type composé vinylique aromatique et de l'acide (méth)acrylique et elle est caractérisée en ce qu'elle contient un éther de polyoxyéthylène et d'alkyle représenté par la formule générale (1) suivante en quantité de 0,05-0,5 % en poids sur la base de la résine du copolymère. R-O-(CH2-CH2-O)X-H (1) (Dans la formule, R représente un alkyle en C8-18 et X est un nombre entier indiquant le nombre d'unités oxyde d'éthylène additionnées et vaut 1-15 en termes de nombre moyen d'unités additionnées.)
PCT/JP2006/318528 2005-09-20 2006-09-19 Composition contenant une résine de copolymère composé vinylique aromatique/acide (méth)acrylique et procédé servant à produire celle-ci WO2007034789A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020087006029A KR101292963B1 (ko) 2005-09-20 2006-09-19 방향족 비닐 화합물 - (메트)아크릴산계 공중합체 수지함유 조성물 및 그 제조 방법
CN2006800340257A CN101263194B (zh) 2005-09-20 2006-09-19 含有芳香族乙烯化合物-(甲基)丙烯酸类共聚物树脂的组合物及其制造方法
JP2007536494A JP5237640B2 (ja) 2005-09-20 2006-09-19 芳香族ビニル化合物−（メタ）アクリル酸系共重合体樹脂含有組成物及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-271824 2005-09-20
JP2005271824 2005-09-20

Publications (1)

Publication Number Publication Date
WO2007034789A1 true WO2007034789A1 (fr) 2007-03-29

Family

ID=37888832

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/318528 WO2007034789A1 (fr) 2005-09-20 2006-09-19 Composition contenant une résine de copolymère composé vinylique aromatique/acide (méth)acrylique et procédé servant à produire celle-ci

Country Status (5)

Country Link
JP (1) JP5237640B2 (fr)
KR (1) KR101292963B1 (fr)
CN (1) CN101263194B (fr)
TW (1) TWI401288B (fr)
WO (1) WO2007034789A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009082047A1 (fr) * 2007-12-21 2009-07-02 Dongbu Hitek Co., Ltd. Composition à base d'un copolymère styrénique, son procédé de polymérisation et copolymère styrénique obtenu avec ce procédé
JP2012102190A (ja) * 2010-11-08 2012-05-31 Sumitomo Chemical Co Ltd 連続重合装置および重合体組成物の製造方法
WO2013094642A1 (fr) * 2011-12-20 2013-06-27 東洋スチレン株式会社 Composition optique à base de styrène, produit moulé et plaque guide de lumière
WO2013094641A1 (fr) * 2011-12-20 2013-06-27 東洋スチレン株式会社 Composition de résine optique à base de styrène
WO2016056319A1 (fr) * 2014-10-09 2016-04-14 コニカミノルタ株式会社 Couche de protection contre le rayonnement infrarouge et film de protection contre le rayonnement infrarouge
JP2018145309A (ja) * 2017-03-06 2018-09-20 東洋スチレン株式会社 光学用スチレン系樹脂組成物、成形品および導光体
JP2020023650A (ja) * 2018-08-08 2020-02-13 東洋スチレン株式会社 スチレン系樹脂組成物及び成形品

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5901361B2 (ja) * 2011-11-18 2016-04-06 住友化学株式会社 連続重合装置および重合体組成物の製造方法
JP6456217B2 (ja) * 2015-03-30 2019-01-23 キヤノン株式会社 撮像制御装置及びその制御方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000355603A (ja) * 1999-06-14 2000-12-26 Nippon Shokubai Co Ltd 水性樹脂分散体の製造方法
JP2003080835A (ja) * 2001-09-13 2003-03-19 Nippon Carbide Ind Co Inc 油性インク受容性マーキングメディア
JP2004050607A (ja) * 2002-07-19 2004-02-19 Sumitomo Chem Co Ltd 光拡散性樹脂積層板
JP2004195744A (ja) * 2002-12-17 2004-07-15 Nippon Carbide Ind Co Inc マーキングメディア
JP2005008790A (ja) * 2003-06-20 2005-01-13 Asahi Kasei Chemicals Corp セメント用水性樹脂分散体及びその組成物
JP2005225108A (ja) * 2004-02-13 2005-08-25 Nippon Zeon Co Ltd ポリカーボネート製光学用成形体

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS624751A (ja) * 1985-06-28 1987-01-10 ロ−ム・アンド・ハ−ス・カンパニ− 界面活性型蒸発抑制剤を含む水性ポリマ−組成物
JPH0517696A (ja) * 1991-07-12 1993-01-26 Kanegafuchi Chem Ind Co Ltd 帯電防止性に優れた透明性熱可塑性樹脂組成物
JPH08170000A (ja) * 1994-12-20 1996-07-02 Dainippon Ink & Chem Inc スチレン系樹脂組成物
CN100427543C (zh) * 2003-01-21 2008-10-22 株式会社可乐丽 丙烯酸类聚合物粉末、丙烯酸溶胶以及成形物
US6811841B1 (en) * 2003-04-15 2004-11-02 3M Innovative Properties Company Light-stable structures
JP4246593B2 (ja) * 2003-10-08 2009-04-02 出光興産株式会社 光反射用ポリカーボネート系樹脂シート及びそれを用いた光反射用積層体

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000355603A (ja) * 1999-06-14 2000-12-26 Nippon Shokubai Co Ltd 水性樹脂分散体の製造方法
JP2003080835A (ja) * 2001-09-13 2003-03-19 Nippon Carbide Ind Co Inc 油性インク受容性マーキングメディア
JP2004050607A (ja) * 2002-07-19 2004-02-19 Sumitomo Chem Co Ltd 光拡散性樹脂積層板
JP2004195744A (ja) * 2002-12-17 2004-07-15 Nippon Carbide Ind Co Inc マーキングメディア
JP2005008790A (ja) * 2003-06-20 2005-01-13 Asahi Kasei Chemicals Corp セメント用水性樹脂分散体及びその組成物
JP2005225108A (ja) * 2004-02-13 2005-08-25 Nippon Zeon Co Ltd ポリカーボネート製光学用成形体

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009082047A1 (fr) * 2007-12-21 2009-07-02 Dongbu Hitek Co., Ltd. Composition à base d'un copolymère styrénique, son procédé de polymérisation et copolymère styrénique obtenu avec ce procédé
JP2012102190A (ja) * 2010-11-08 2012-05-31 Sumitomo Chemical Co Ltd 連続重合装置および重合体組成物の製造方法
WO2013094642A1 (fr) * 2011-12-20 2013-06-27 東洋スチレン株式会社 Composition optique à base de styrène, produit moulé et plaque guide de lumière
WO2013094641A1 (fr) * 2011-12-20 2013-06-27 東洋スチレン株式会社 Composition de résine optique à base de styrène
JPWO2013094641A1 (ja) * 2011-12-20 2015-04-27 東洋スチレン株式会社 光学用スチレン系樹脂組成物
JP2017061697A (ja) * 2011-12-20 2017-03-30 東洋スチレン株式会社 光学用スチレン系樹脂組成物
JP2017078172A (ja) * 2011-12-20 2017-04-27 東洋スチレン株式会社 光学用スチレン系樹脂組成物
JP2018090813A (ja) * 2011-12-20 2018-06-14 東洋スチレン株式会社 光学用スチレン系樹脂組成物
WO2016056319A1 (fr) * 2014-10-09 2016-04-14 コニカミノルタ株式会社 Couche de protection contre le rayonnement infrarouge et film de protection contre le rayonnement infrarouge
JP2018145309A (ja) * 2017-03-06 2018-09-20 東洋スチレン株式会社 光学用スチレン系樹脂組成物、成形品および導光体
JP7064827B2 (ja) 2017-03-06 2022-05-11 東洋スチレン株式会社 光学用スチレン系樹脂組成物、成形品および導光体
JP2020023650A (ja) * 2018-08-08 2020-02-13 東洋スチレン株式会社 スチレン系樹脂組成物及び成形品

Also Published As

Publication number Publication date
KR20080055818A (ko) 2008-06-19
TWI401288B (zh) 2013-07-11
TW200724595A (en) 2007-07-01
JPWO2007034789A1 (ja) 2009-03-26
JP5237640B2 (ja) 2013-07-17
CN101263194A (zh) 2008-09-10
CN101263194B (zh) 2010-12-29
KR101292963B1 (ko) 2013-08-02

Similar Documents

Publication Publication Date Title
WO2007034789A1 (fr) Composition contenant une résine de copolymère composé vinylique aromatique/acide (méth)acrylique et procédé servant à produire celle-ci
JP6321322B2 (ja) 耐熱スチレン系樹脂組成物、押出シート及び成形品
JP5897311B2 (ja) 耐熱スチレン系樹脂組成物、押出シート及び成形品
JP6104677B2 (ja) 耐熱スチレン系樹脂組成物、押出シート及び成形品
JP6188307B2 (ja) 耐熱スチレン系樹脂組成物、押出シート及び成形品
JP5221941B2 (ja) スチレン−メタクリル酸樹脂組成物の製造方法、及びその樹脂組成物
WO2013069077A1 (fr) Composition de résine à base de styrène comprenant un corps de poids moléculaire très élevé de type très ramifié, et procédé de fabrication de celle-ci
JP6707400B2 (ja) スチレン系樹脂、スチレン系樹脂組成物、そのシート及び成形品、並びにスチレン系樹脂の製造方法
JP2011126996A (ja) スチレン−メタクリル酸−メタクリル酸メチル樹脂、押出シート及び成形品
JP2011225866A (ja) 多分岐型超高分子量体を含有するスチレン系樹脂組成物の製造方法およびその組成物
JP2006282962A (ja) 芳香族ビニル化合物−メタクリル酸系共重合体及びその製造方法
JP2017133040A (ja) 耐熱スチレン系樹脂組成物、押出シート及び成形品
JP2023076738A (ja) 耐熱スチレン系樹脂組成物、押出シート、成形品
JP2005239951A (ja) 芳香族ビニル化合物系重合体の製造方法
EP4317209A1 (fr) Copolymère méthacrylique, composition de résine méthacrylique et procédé pour sa production et corps moulé
JP5468303B2 (ja) スチレン−メタクリル酸−メタクリル酸メチル樹脂の製造方法
KR20080076940A (ko) 무수물-함유 비닐 방향족-비닐 시아니드 공중합체의 제조방법
JP2003049033A (ja) スチレン系樹脂組成物とその発泡シートおよび容器
JP6829103B2 (ja) スチレン系樹脂、シート、成形品及び製造方法
JP4458931B2 (ja) 透明なゴム変性共重合樹脂組成物、それから得られる成形物及び該組成物の製造方法
JP7336840B2 (ja) スチレン系共重合樹脂、樹脂組成物、そのシート及び成形品
JP2017218576A (ja) スチレン系共重合体およびその製造方法
JP2023115374A (ja) スチレン系樹脂組成物及び成形品
JP2021123637A (ja) スチレン系共重合樹脂
JP4470382B2 (ja) 熱可塑性成形材料

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200680034025.7

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2007536494

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020087006029

Country of ref document: KR

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06810270

Country of ref document: EP

Kind code of ref document: A1