WO2020137842A1 - スチレン系樹脂組成物シート及び成形体 - Google Patents

スチレン系樹脂組成物シート及び成形体 Download PDF

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Publication number
WO2020137842A1
WO2020137842A1 PCT/JP2019/049982 JP2019049982W WO2020137842A1 WO 2020137842 A1 WO2020137842 A1 WO 2020137842A1 JP 2019049982 W JP2019049982 W JP 2019049982W WO 2020137842 A1 WO2020137842 A1 WO 2020137842A1
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WIPO (PCT)
Prior art keywords
sheet
resin composition
styrene resin
styrene
mass
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2019/049982
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English (en)
French (fr)
Japanese (ja)
Inventor
利春 蔵田
井上　修治
宝晃 岡田
雅史 塚田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyo Styrene Co Ltd
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Toyo Styrene Co Ltd
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Filing date
Publication date
Application filed by Toyo Styrene Co Ltd filed Critical Toyo Styrene Co Ltd
Priority to CN201980068703.9A priority Critical patent/CN112888740B/zh
Priority to JP2020563183A priority patent/JPWO2020137842A1/ja
Publication of WO2020137842A1 publication Critical patent/WO2020137842A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a sheet made of a styrene resin composition, and a molded product obtained by molding the styrene resin composition sheet.
  • Styrene-based resins are used in many fields such as sheets, foams, and housings because they are easy to mold and are lightweight.
  • polyester resins are widely used in various industrial applications such as films, sheets, tableware, and packaging containers because of their excellent mechanical properties.
  • carbon neutral materials that apparently emit no carbon dioxide. Attention has been paid.
  • polylactic acid has low impact resistance and poor practicality
  • polymer alloys with petroleum-based resins, particularly alloys with styrene-based resins having excellent practical physical properties such as moldability and impact resistance are being investigated. .. (Patent Document 1).
  • the above-mentioned polymer alloy of styrene resin and polylactic acid may reduce the gloss and oil resistance of the sheet obtained by sheet molding, and further improvement is required.
  • the object of the present invention is to improve the balance between gloss, oil resistance and sheet strength in a sheet made of a styrene resin composition containing a styrene resin and a polyester resin.
  • the styrene resin composition further contains (C) a copolymer of butadiene and an ethylenically unsaturated carboxylic acid ester.
  • a molded product comprising the styrene resin composition sheet according to any one of (1) to (4) above.
  • the styrene-based resin composition sheet of the present invention (hereinafter referred to as “sheet”) comprises a styrene-based resin composition containing at least (A) styrene-based resin and (B) polyester-based resin.
  • the (A) styrene-based resin used in the present invention is obtained by polymerizing an aromatic vinyl compound, and if necessary, a conjugated diene-based rubbery polymer may be added for rubber modification.
  • a known method for example, a bulk polymerization method, a bulk/suspension two-step polymerization method, a solution polymerization method or the like can be used.
  • the aromatic vinyl compound-based monomer known ones such as styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene and p-methylstyrene can be used, but styrene is preferable.
  • monomers such as acrylonitrile, (meth)acrylic acid, (meth)acrylic acid ester, and maleic anhydride that are copolymerizable with these aromatic vinyl compound-based monomers also have the performance of (A) styrene-based resin.
  • a polymer obtained by adding and polymerizing may be used as long as it does not damage
  • a crosslinking agent such as divinylbenzene may be added to the styrene-based monomer and polymerized.
  • conjugated diene rubbery polymer used for rubber modification of the styrene resin (A) of the present invention examples include polybutadiene, styrene-butadiene random or block copolymer, polyisoprene, polychloroprene, styrene-isoprene random, block. Further, a graft copolymer, ethylene-propylene rubber, ethylene-propylene-diene rubber and the like can be mentioned, but polybutadiene, styrene-butadiene random, block or graft copolymer is particularly preferable. Further, these may be partially hydrogenated.
  • styrene resin examples include polystyrene (GPPS), high impact polystyrene (HIPS), ABS resin (acrylonitrile-butadiene-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), MS resin (methyl methacrylate-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethylene propylene-styrene copolymer), MBS resin (methyl methacrylate-butadiene-styrene copolymer) Polymer) and the like.
  • HIPS is particularly preferable because it can increase the impact resistance of the styrene resin composition.
  • the content of the rubber-like polymer in HIPS is not particularly limited, but is preferably 3% by mass or more and 10% by mass or less.
  • the (B) polyester resin used in the present invention is a general term for polymers having an ester bond obtained by polymerizing a polyvalent carboxylic acid and a polyalcohol.
  • the (B) polyester-based resin can be obtained, for example, by polymerization from a dicarboxylic acid and a diol.
  • Examples of such (B) polyester-based resin include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate.
  • Examples of the phthalate include polyhexamethylene terephthalate and polyhexamethylene naphthalate, but the present invention is not limited thereto.
  • dicarboxylic acid component examples include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid.
  • aromatic dicarboxylic acids such as 4,4′-diphenyl ether dicarboxylic acid and 4,4′-diphenyl sulfone dicarboxylic acid.
  • aliphatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, dimer acid, dodecanedioic acid, cyclohexanedicarboxylic acid, and ester derivatives thereof can be mentioned.
  • carboxylic acid components may be used alone or in combination of two or more, and further, an oxy acid such as hydroxybenzoic acid may be partially copolymerized.
  • diol component examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane.
  • Diol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2-bis(4 -Hydroxyethoxyphenyl)propane, isosorbate, spiroglycol and the like can be mentioned.
  • the (B) polyester-based resin can be obtained by polymerizing a monomer having both a carboxylic acid and an alcohol as a single compound, and such a (B) polyester-based resin includes polylactic acid.
  • polylactic acid is preferred from the viewpoint of carbon neutrality.
  • the polylactic acid used as the (B) polyester resin is preferably a plant-derived raw material from the viewpoint of reducing carbon dioxide emissions.
  • non-edible plant-derived raw materials that do not compete with food problems are preferable.
  • the weight average molecular weight (Mw) of polylactic acid is preferably 50,000 or more and 400,000 or less, and particularly preferably 100,000 or more and 300,000 or less.
  • the polylactic acid (B) is preferably polylactic acid consisting of either D-lactic acid or L-lactic acid. When both are mixed, the smaller the ratio of one component is, the more the polylactic acid is crystallized. Progress quickly. Considering the moldability of the styrene resin composition according to the present invention, it is preferable that the ratio of the component having the smaller ratio is 5 mol% or less. It is particularly preferably 4 mol% or less.
  • a copolymer of (C) butadiene and an ethylenically unsaturated carboxylic acid ester may be added to the styrene resin composition according to the present invention.
  • the copolymer (C) of butadiene and an ethylenically unsaturated carboxylic acid ester is a thermoplastic elastomer having butadiene and an ethylenically unsaturated carboxylic acid as monomer units.
  • Examples of the ethylenically unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, Examples thereof include n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and the like, and two or more kinds may be used in combination.
  • (C) a copolymer of butadiene and an ethylenically unsaturated carboxylic acid ester is obtained by graft-copolymerizing a monomer containing an ethylenically unsaturated carboxylic acid ester on its surface as a polymer particle core containing butadiene.
  • a multilayer structure particle having a shell is preferable because it can further improve the impact strength.
  • Examples of such a copolymer of butadiene and an ethylenically unsaturated carboxylic acid ester include "Metablene (registered trademark) C-223A" (manufactured by Mitsubishi Chemical Corporation) and "Kaneace (registered trademark) M-511" (stock). Company Kaneka) and the like.
  • the addition amount of the copolymer of (C) butadiene and ethylenically unsaturated carboxylic acid ester is not particularly limited, but is 1 part by mass with respect to 100 parts by mass of the total of (A) styrene resin and (B) polyester resin. It is preferably not less than 15 parts and not more than 15 parts by mass.
  • the co-continuous structure in the polymer alloy means the phase state described in JP 2010-6910 A.
  • phase states in the polymer alloy are roughly classified into (1) complete compatibility (single phase), (2) sea-island structure (multiphase), (3) co-continuous structure (multiphase), (4) layered structure ( It is divided into four. Most polymer alloys are not completely compatible and are known to form morphologies (2), (3) and (4).
  • Z/Q kWh/kg was found to be important. Therefore, a sheet having a bicontinuous structure can be obtained by adjusting the resin composition and Z/Q.
  • the ATR (attended total reflection) method is a surface measurement method of infrared spectroscopy (IR).
  • KRS-5 thallium bromide + thallium iodide: refractive index 2.37
  • ZnSe zinc selenide: refractive index 2.4
  • Ge germanium: refractive index 4.0
  • a medium having a high refractive index is brought into close contact with the sample, and infrared light is incident on the high refractive index medium at an incident angle larger than the critical angle. In the region where the sample has absorption, the energy of the reflected light decreases in accordance with the intensity of the absorption, and therefore the ATR spectrum can be obtained by measuring this reflected light.
  • the penetration depth dp the depth at which the amplitude of the light soaked into the high refractive index medium drops to 1/e (e is the base of the natural logarithm) is defined as the penetration depth dp, and the penetration depth dp is expressed by the following equation. ..
  • ⁇ is the wavelength of light
  • ⁇ is the incident angle
  • n1 is the refractive index of the high refractive medium
  • n2 is the refractive index of the sample.
  • the penetration angle dp is smaller and the information closer to the sample surface is reflected in the spectrum as the incident angle ⁇ is larger and the refractive index n1 of the high refractive index medium is larger.
  • Ge is used as the high refractive index medium and the infrared absorption spectrum is measured at an incident angle of 60°.
  • the infrared absorption spectrum of the sheet is measured by the ATR-FTIR method, which uses FTIR (Fourier transform infrared spectrophotometer).
  • the sheet of the present invention has ⁇ / ⁇ of 2 or more and 10 or less, preferably 2 or more and 8 or less, and more preferably 2 or more, calculated from the infrared absorption spectra of the outermost surface and the interior measured by the ATR-FTIR method. It is 6 or less. Note that ⁇ and ⁇ are as follows.
  • the present inventors can adjust the ratio ( ⁇ / ⁇ ) of the absorbance ratio between the outermost surface and the inside of the sheet of the present invention by the production conditions such as the resin composition at the time of melt-kneading and the stretching ratio at the time of extruding the sheet. I found that.
  • thermoforming method examples include vacuum forming, pressure forming, or free drawing forming as these applications, plug and ridge forming, ridge forming, matched mold forming, straight forming, drape forming, reverse draw forming, air forming.
  • Conventionally known general molding methods such as slip molding, plug assist molding, and plug assist reverse load molding can be used.
  • a styrene resin is dissolved in chloroform, a certain amount of iodine monochloride/carbon tetrachloride solution is added, and the mixture is allowed to stand in a dark place for about 1 hour. Then, a 15 mass% potassium iodide solution and 50 ml of pure water are added, and excess. Iodine monochloride was titrated with a 0.1N sodium thiosulfate/ethanol aqueous solution and calculated from the amount of added iodine monochloride.
  • a test piece with the following dimensions was cut out from the sheet to give a constant strain chemical resistance test evaluation test piece.
  • 0.05 ml of the chemical was applied with a dropper to the bent portion of the above-mentioned test piece to which gauze was applied, and the time until the test piece was broken was evaluated.
  • 1 is a test piece
  • 2 is a base made of stainless steel
  • 3 is gauze
  • 4 is a chemical
  • 5 is a dropper.
  • the depth direction of the test piece 1 was arranged in parallel to the depth direction in FIG. 1, and the test piece 1 was bent so that the center thereof protrudes upward and arranged in the recess of the base.
  • a Henschel mixer (“FM20B” manufactured by Nippon Coke Industry Co., Ltd.)
  • twin-screw extruder Toshiba Machinery Co., Ltd.) Manufactured by "TEM26SS”
  • Example 2 A sheet was obtained in the same manner as in Example 1 except that the composition (parts by mass) of the styrene resin composition was changed as shown in Table 1 and the obtained sheet was heated at 130° C. for 10 seconds to obtain a sheet. It evaluated similarly to. The results are shown in Table 1.
  • Comparative Example 1 The composition (parts by mass) of the styrene-based resin composition was changed as shown in Table 2, and when the sheet was obtained, the sheet was stretched 1.5 times in the sheet flow direction (MD) due to the speed difference between roll groups, and the tenter was used. Thus, a sheet was obtained in the same manner as in Example 1 except that the sheet was stretched 1.5 times in the direction (TD) orthogonal to the sheet flow direction, and evaluated in the same manner as in Example 1. The results are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Biological Depolymerization Polymers (AREA)
PCT/JP2019/049982 2018-12-26 2019-12-20 スチレン系樹脂組成物シート及び成形体 Ceased WO2020137842A1 (ja)

Priority Applications (2)

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CN201980068703.9A CN112888740B (zh) 2018-12-26 2019-12-20 苯乙烯系树脂组合物片和成形体
JP2020563183A JPWO2020137842A1 (ja) 2018-12-26 2019-12-20 スチレン系樹脂組成物シート及び成形体

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JP2018-242389 2018-12-26
JP2018242389 2018-12-26

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023042753A1 (ja) * 2021-09-17 2023-03-23 デンカ株式会社 樹脂シート及び成形容器

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008274191A (ja) * 2007-05-07 2008-11-13 Daicel Pack Systems Ltd 脂肪族ポリエステル系樹脂組成物
JP2013095847A (ja) * 2011-11-01 2013-05-20 Unitika Ltd 熱可塑性樹脂組成物
JP2014189748A (ja) * 2013-03-28 2014-10-06 Dic Corp スチレン系延伸シート及びその成形品
JP2016199654A (ja) * 2015-04-09 2016-12-01 東洋スチレン株式会社 スチレン系樹脂組成物及び成形体
JP2018048248A (ja) * 2016-09-21 2018-03-29 東洋スチレン株式会社 樹脂組成物、樹脂組成物の製造方法、樹脂組成物から得られる成形体および成形体の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008274191A (ja) * 2007-05-07 2008-11-13 Daicel Pack Systems Ltd 脂肪族ポリエステル系樹脂組成物
JP2013095847A (ja) * 2011-11-01 2013-05-20 Unitika Ltd 熱可塑性樹脂組成物
JP2014189748A (ja) * 2013-03-28 2014-10-06 Dic Corp スチレン系延伸シート及びその成形品
JP2016199654A (ja) * 2015-04-09 2016-12-01 東洋スチレン株式会社 スチレン系樹脂組成物及び成形体
JP2018048248A (ja) * 2016-09-21 2018-03-29 東洋スチレン株式会社 樹脂組成物、樹脂組成物の製造方法、樹脂組成物から得られる成形体および成形体の製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023042753A1 (ja) * 2021-09-17 2023-03-23 デンカ株式会社 樹脂シート及び成形容器
JPWO2023042753A1 (https=) * 2021-09-17 2023-03-23
JP7803956B2 (ja) 2021-09-17 2026-01-21 デンカ株式会社 樹脂シート及び成形容器

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JPWO2020137842A1 (ja) 2021-11-11
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