WO2020188963A1 - Composition de résine, article moulé, film, et procédé de production de composition de résine - Google Patents

Composition de résine, article moulé, film, et procédé de production de composition de résine Download PDF

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Publication number
WO2020188963A1
WO2020188963A1 PCT/JP2020/000576 JP2020000576W WO2020188963A1 WO 2020188963 A1 WO2020188963 A1 WO 2020188963A1 JP 2020000576 W JP2020000576 W JP 2020000576W WO 2020188963 A1 WO2020188963 A1 WO 2020188963A1
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Prior art keywords
polyamide resin
derived
mol
resin
diamine
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PCT/JP2020/000576
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English (en)
Japanese (ja)
Inventor
桃子 山下
佐藤　和哉
尚史 小田
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三菱瓦斯化学株式会社
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Priority to JP2020518824A priority Critical patent/JP6741190B1/ja
Publication of WO2020188963A1 publication Critical patent/WO2020188963A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a resin composition, a molded product and a film using the resin composition.
  • the present invention also relates to a method for producing a resin composition.
  • Polystyrene (PS) resin using styrene as a raw material monomer has excellent transparency and is widely used in cassette cases, food containers, household products and the like. Blending with other resins is being considered in order to improve its physical properties or to improve its manufacturing suitability.
  • Patent Document 1 a stretched body of a thermoplastic resin composition composed of polystyrene resin A 10 to 98% by weight and polyamide resin B 2 to 90% by weight, measured by the depolarization strength method of the polyamide fat. It has been proposed that the semi-crystallization time is specified in a specific range.
  • An object of the present invention is to solve such a problem, which is a resin composition obtained by blending a polystyrene resin with a xylylene diamine-based polyamide resin, and having a resin composition capable of maintaining excellent transparency.
  • An object of the present invention is to provide a method for producing a product, a molded product, a film and a resin composition.
  • the present inventor has found that the above problems can be solved by using an isophthalic acid-modified xylylenediamine-based polyamide resin to be blended with the polystyrene resin at a specific ratio. Specifically, the above problems have been solved by the following means ⁇ 1> to ⁇ 10>.
  • a total of 85 to 15 parts by mass of the polyamide resin (B) and the polyamide resin (C) is contained in an amount of 15 to 85 parts by mass of the polystyrene resin (A), and the polyamide resin (B) is a constituent unit derived from a diamine.
  • the polyamide resin (B) is a constituent unit derived from a diamine.
  • 70 mol% or more of the constituent unit derived from dicarboxylic acid is derived from xylylene diamine, and more than 90 mol% of the constituent unit derived from dicarboxylic acid is derived from adipic acid.
  • the polyamide resin (C) is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylene diamine, and the dicarboxylic acid-derived constitution. 40-60 mol% of the unit is derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and 60-40 mol% is derived from isophthalic acid (however, the total exceeds 100 mol%).
  • ⁇ 2> The resin composition according to ⁇ 1>, wherein 70 mol% or more of the diamine-derived structural unit in the polyamide resin (B) is derived from m-xylylenediamine.
  • ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein 70 mol% or more of the diamine-derived structural unit in the polyamide resin (C) is derived from m-xylylenediamine.
  • ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein 60 to 40 mol% of the dicarboxylic acid-derived structural unit in the polyamide resin (C) is derived from adipic acid.
  • the polyamide resin (B) is a crystalline polyamide resin
  • the polyamide resin (C) is an amorphous polyamide resin
  • the structural units constituting the polyamide resin (B) and the polyamide resin are common.
  • ⁇ 6> 70 mol% or more of the diamine-derived structural unit in the polyamide resin (B) is derived from metaxylylene diamine, and 70 mol% or more of the diamine-derived structural unit in the polyamide resin (C) is metaxylylene.
  • the polyamide resin (B) is a crystalline polyamide resin
  • the polyamide resin (C) ) Is an amorphous polyamide resin, and 60 mol% or more of the constituent unit constituting the polyamide resin (B) and the constituent unit constituting the polyamide resin (C) are common, according to ⁇ 1>.
  • Resin composition. ⁇ 7> Any one of ⁇ 1> to ⁇ 6>, wherein the mass ratio ((B): (C)) of the polyamide resin (B) to the polyamide resin (C) is 90:10 to 70:30.
  • ⁇ 8> A molded product formed from the resin composition according to any one of ⁇ 1> to ⁇ 7>.
  • ⁇ 9> A film formed from the resin composition according to any one of ⁇ 1> to ⁇ 7>.
  • ⁇ 10> The method for producing a resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the polyamide resin (B) and the polyamide resin (C) are melt-kneaded, and then further.
  • a method for producing a resin composition which comprises adding a polystyrene resin (A) and melt-kneading.
  • the xylylenediamine-based polyamide resin in the present specification means a polyamide resin in which 70 mol% or more of the constituent units derived from diamine are derived from xylylenediamine.
  • the resin composition of the present invention contains a total of 85 to 15 parts by mass of the polyamide resin (B) and the polyamide resin (C) with respect to 15 to 85 parts by mass of the polystyrene resin (A), and the polyamide resin (B) is It is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit. More than 70 mol% of the diamine-derived structural unit is derived from xylylene diamine, and more than 90 mol% of the dicarboxylic acid-derived structural unit is adipine.
  • the polyamide resin (C) is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylene diamine.
  • 40 to 60 mol% of the constituent units derived from dicarboxylic acid are derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and 60 to 40 mol% are derived from isophthalic acid (however, the total is It does not exceed 100 mol%), and the mass ratio ((B) :( C)) of the polyamide resin (B) to the polyamide resin (C) is 95: 5 to 65:35. ..
  • a polystyrene resin and a xylylenediamine-based polyamide resin have been successfully blended by using a high-refractive-index xylylenediamine-based polyamide resin obtained by modifying a xylylenediamine-based polyamide resin with isophthalate. Even if there is an interface between the xylylenediamine-based polyamide resin that has not been modified with isophthalic acid and the polystyrene resin, the presence of the xylylenediamine-based polyamide resin that has been modified with isophthalic acid makes it difficult for light to be diffusely reflected at that interface, making it transparent. It has become possible to improve the sex. Furthermore, it has been found that good chemical resistance, hardness and oxygen barrier property can be obtained. In the present specification, transparent means colorless and transparent unless otherwise specified, but it also means that it may be in a colored translucent state within a range suitable for various uses.
  • Polystyrene resin (A) used in the resin composition of the present invention those generally used as this type of resin can be widely adopted.
  • Polystyrene resin is usually an amorphous resin.
  • Specific examples of the polystyrene resin include a polymer of a styrene-based monomer or a copolymer of a styrene-based monomer and another monomer copolymerizable therewith.
  • styrene-based monomer examples include alkyl-substituted styrenes such as styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-t-butylstyrene, and 2,4-dimethylstyrene, and ⁇ -methyl.
  • ⁇ -alkyl substituted styrene such as styrene and ⁇ -methyl-4-methylstyrene
  • halogenated styrene such as chlorostyrene and bromostyrene
  • halogen substituted alkylstyrene such as chlorostyrene and bromostyrene
  • alkylstyrene polyalkoxystyrene
  • polycarboxyalkylstyrene polyalkyletherstyrene
  • polyalkyl Cyril styrene can be mentioned.
  • styrene-based monomers include acrylic acid or methacrylic acid, methyl acrylate or methyl methacrylate, ethyl acrylate or ethyl methacrylate, butyl acrylate or butyl methacrylate, -2-ethylhexyl acrylate.
  • acrylic acid such as -2-ethylhexyl methacrylate, methacrylic acid ester, unsaturated nitriles such as acrylonitrile and methacrylic acid, maleic anhydride, maleimide, N-methylmaleimide, N-substituted maleimide such as N-ethylmaleimide and the like.
  • polystyrene resin (A) includes impact-resistant polystyrene, styrene-conjugated diene block copolymer, hydrogenated product of styrene-conjugated diene block copolymer, ABS (rubber graft styrene-acrylonitrile copolymer), MBS. (Rubber graft styrene-methyl methacrylate copolymer), rubber graft styrene- (meth) acrylic acid ester copolymer and the like can also be used.
  • the polystyrene resin (A) used in the present invention is not a so-called elastomer (impact resistance improver).
  • the resin composition of the present invention may be a copolymer of styrene with another monomer copolymerizable with styrene or a derivative thereof as long as the effects of the invention are not impaired.
  • the styrene homopolymer in the present invention means that 80% by mass or more of the monomers constituting the polymer are styrene-based monomers.
  • the method for synthesizing the polystyrene resin is not particularly limited, and a general method can be adopted.
  • Atactic polystyrene is a thermoplastic resin, is inexpensive, and can be suitably used because of its advantages such as easy injection molding.
  • a recycled polystyrene resin material may be used.
  • the molecular weight of the polystyrene resin (A) is preferably 80,000 or more, more preferably 100,000 or more, and further preferably 120,000 or more in terms of weight average molecular weight.
  • the upper limit is preferably 1,000,000 or less, more preferably 800,000 or less, and even more preferably 500,000 or less.
  • the content of the polystyrene resin (A) may be appropriately determined, but it is preferably 15% by mass or more, more preferably 25% by mass or more, and 40% by mass or more in the resin composition. Is even more preferable.
  • the upper limit value is preferably 85% by mass or less, more preferably 80% by mass or less, and preferably 70% by mass or less.
  • the polyamide resin (B) used in the present invention is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylenediamine and is derived from dicarboxylic acid. Over 90 mol% of the building blocks are derived from adipic acid.
  • the polyamide resin (B) is preferably derived from a diamine-derived structural unit in an amount of preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, still more preferably 99 mol% or more, and derived from xylylenediamine. To do.
  • xylylenediamine metaxylylenediamine and paraxylylenediamine are preferable, and metaxylylenediamine is more preferable.
  • An example of a preferred embodiment of the polyamide resin (B) in the present invention is a polyamide resin in which 70 mol% or more of the diamine-derived constituent units are derived from m-xylylenediamine.
  • Diamines other than ximethylenediamine that can be used as the raw material diamine component of the polyamide resin (B) are tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and nonamethylene.
  • Aliamine diamines such as diamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1 , 4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminomethyl) ) Decalin, alicyclic diamine such as bis (aminomethyl) tricyclodecane, diamine having an aromatic ring such as bis (4-aminophenyl) ether, paraphenylenediamine, bis (aminomethyl) naphthalene and the like can be exemplified.
  • diamine other than xylylenediamine is used as the diamine component, it is used in an amount of 30 mol% or less, more preferably 1 to 25 mol%, and particularly preferably 5 to 20 mol% of the constituent unit derived from diamine.
  • the polyamide resin (B) is derived from adipic acid in an amount of 90 mol% or more, preferably 95 mol% or more, more preferably 99 mol% or more of the constituent unit derived from the dicarboxylic acid.
  • Examples of the dicarboxylic acid other than the adipic acid preferable to be used as the raw material dicarboxylic acid component of the polyamide resin (B) include succinic acid, glutaric acid, pimelliic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and the like.
  • phthalic acid compounds such as aliphatic dicarboxylic acid, terephthalic acid, orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1 , 6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, etc.
  • An acid can be exemplified, and one kind or a mixture of two or more kinds can be used.
  • a dicarboxylic acid other than adipic acid is used as the dicarboxylic acid component, it is less than 10 mol% of the constituent unit derived from the dicarboxylic acid, preferably 5 mol% or less.
  • the other dicarboxylic acid is preferably an aliphatic dicarboxylic acid.
  • the polyamide resin (B) used in the present invention is composed of a dicarboxylic acid-derived structural unit and a diamine-derived structural unit, but the structural units other than the dicarboxylic acid-derived structural unit and the diamine-derived structural unit, and the terminal. It may include parts of other structures such as groups. Examples of other constituent units include lactams such as ⁇ -caprolactam, valerolactam, laurolactam, and undecalactam, and aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid. It is not limited to these. Further, the polyamide resin (B) used in the present invention may contain trace components such as additives used in the synthesis. The polyamide resin (B) is usually composed of 95% by mass or more, preferably 98% by mass or more, of a dicarboxylic acid-derived structural unit or a diamine-derived structural unit.
  • the number average molecular weight (Mn) of the polyamide resin (B) is preferably 10,000 or more, and more preferably 15,000 or more.
  • the upper limit of the number average molecular weight of the polyamide resin (B) is not particularly defined, but may be, for example, 100,000 or less, further 50,000 or less, and 40,000 or less.
  • the number average molecular weight in the present invention is measured according to the method described in paragraph 0016 of WO 2017/090556, the contents of which are incorporated herein.
  • the polyamide resin (B) is usually a crystalline polyamide resin, and its melting point is preferably 190 to 300 ° C., more preferably 200 to 270 ° C., and further preferably 210 to 250 ° C. preferable.
  • the melting point in the present invention is measured according to the description in paragraph 0017 of JP2016-216661, and the contents thereof are incorporated in the present specification.
  • the resin composition of the present invention preferably contains the polyamide resin (B) in an amount of 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and preferably 25% by mass or more. It is more preferable, and it is even more preferable to contain 30% by mass or more. Further, the resin composition of the present invention preferably contains the polyamide resin (B) in an amount of 70% by mass or less, may be 55% by mass or less, may be less than 50% by mass, and even more. It may be 48% by mass or less.
  • the polyamide resin (C) used in the resin composition of the present invention is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylene diamine.
  • 40 to 60 mol% of the constituent unit derived from the dicarboxylic acid is derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and 60 to 40 mol% is derived from isophthalic acid (however, , The total does not exceed 100 mol%).
  • 70 mol% or more of the diamine-derived structural unit is derived from xylylenediamine, preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably. 95 mol% or more, more preferably 99 mol% or more, is derived from xylylenediamine.
  • the xylylenediamine is preferably metaxylylenediamine.
  • Diamines other than xylylenediamine include aromatic diamines such as paraphenylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. , Octamethylenediamine, nonamethylenediamine and other aliphatic diamines are exemplified. These other diamines may be only one kind or two or more kinds.
  • the polyamide resin (C) used in the present invention is derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 40 to 60 mol% of carbon atoms of 4 to 20.
  • the lower limit of the proportion of ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is preferably 42 mol% or more, more preferably 45 mol% or more.
  • the upper limit is preferably 58 mol% or less, more preferably 55 mol% or less.
  • Examples of ⁇ , ⁇ -linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms include succinic acid, glutaric acid, pimeric acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid.
  • An aliphatic dicarboxylic acid is exemplified, and adipic acid and sebacic acid are preferable, and adipic acid is more preferable.
  • the ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms may be one kind or two or more kinds.
  • the ratio of the constituent units derived from isophthalic acid is 60 to 40 mol% among all the dicarboxylic acids constituting the constituent units derived from dicarboxylic acid.
  • the lower limit of the ratio of the constituent units derived from isophthalic acid is preferably 42 mol% or more, more preferably 45 mol% or more.
  • the upper limit of the ratio of the constituent units derived from isophthalic acid is preferably 58 mol% or less, more preferably 55 mol% or less.
  • the constituent unit derived from the dicarboxylic acid may contain isophthalic acid and other dicarboxylic acids other than ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
  • dicarboxylic acids include phthalic acid compounds such as terephthalic acid and orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid.
  • Naphthalenedicarboxylic acids such as 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid.
  • An acid compound and the like can be exemplified, and one or a mixture of two or more can be used.
  • the total of the constituent units derived from isophthalic acid and the constituent units derived from ⁇ , ⁇ -linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is 90 mol% or more of the constituent units derived from dicarboxylic acid. It is preferably occupied, more preferably 95 mol% or more, further preferably 98 mol% or more, and even more preferably 99 mol% or more. The upper limit is 100 mol%.
  • the polyamide resin (C) used in the present invention is composed of a dicarboxylic acid-derived structural unit and a diamine-derived structural unit, but the structural units other than the dicarboxylic acid-derived structural unit and the diamine-derived structural unit, and the terminal. It may include parts of other structures such as groups. Examples of other constituent units include lactams such as ⁇ -caprolactam, valerolactam, laurolactam, and undecalactam, and aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid. It is not limited to these. Further, the polyamide resin (C) used in the present invention may contain trace components such as additives used in the synthesis.
  • the polyamide resin (C) is usually composed of 95% by mass or more, preferably 98% by mass or more, of a dicarboxylic acid-derived structural unit or a diamine-derived structural unit.
  • the polyamide resin (C) is preferably an amorphous polyamide resin. Transparency can be further improved by using an amorphous polyamide resin.
  • the amorphous resin means a resin having a crystal melting enthalpy ⁇ Hm of less than 10 J / g.
  • the number average molecular weight (Mn) of the polyamide resin (C) used in the present invention preferably has a lower limit of 6,000 or more, more preferably 10,000 or more, and more preferably 12,000 or more. May be good.
  • the upper limit of the number average molecular weight (Mn) is preferably 50,000 or less, more preferably 30,000 or less, and 25,000 or less, 18,000 or less, or 15,000 or less. There may be.
  • the number average molecular weight in the present invention is measured according to the method described in paragraph 0016 of WO 2017/090556, the contents of which are incorporated herein.
  • the content of the polyamide resin (C) may be appropriately determined, but it is preferably 1% by mass or more, and more preferably 4% by mass or more in the resin composition.
  • the upper limit value is preferably 20% by mass or less, may be 15% by mass or less, or may be 12% by mass or less.
  • the polyamide resins (B) and (C) can be produced by a production method comprising polycondensing diamine and a dicarboxylic acid in the presence of a catalyst.
  • the diamine and dicarboxylic acid here are synonymous with those described above, and the preferred ranges are also the same.
  • Known catalysts can be used, and examples of the catalyst containing sodium include sodium hypophosphite, sodium phosphite, sodium hydrogen phosphite and the like.
  • Examples of the catalyst containing calcium include calcium hypophosphite, calcium phosphite and the like.
  • Polycondensation is usually a melt polycondensation method, and examples thereof include a method in which a raw material diamine is dropped onto a melted raw material dicarboxylic acid and the temperature is raised under pressure to remove condensed water for polymerization.
  • a method in which a salt composed of a raw material diamine and a raw material dicarboxylic acid is heated in the presence of water under pressure and polymerized in a molten state while removing the added water and condensed water can be mentioned.
  • the resin composition of the present invention contains a total of 85 to 15 parts by mass of the polyamide resin (B) and the polyamide resin (C) with respect to 15 to 85 parts by mass of the polystyrene resin (A).
  • the total amount of the polystyrene resin (A), the polyamide resin (B) and the polyamide resin (C) may exceed 100 parts by mass, but 100 parts by mass is preferable.
  • the lower limit of the proportion of the polystyrene resin (A) is 18.
  • the upper limit of the proportion of the polystyrene resin (A) is preferably 82 parts by mass or less. , 80 parts by mass or less, and further, 70 parts by mass or less, 65 parts by mass or less, 55 parts by mass or less may be used depending on the application and the like.
  • the mass ratio ((B): (C)) of the polyamide resin (B) to the polyamide resin (C) is 95: 5 to 65:35, preferably 90:10. It is ⁇ 70:30, more preferably 85:15 ⁇ 75:25.
  • the total of the polyamide resin (B) and the polyamide resin (C) and the ratio of the polystyrene resin (A) and the ratio of the polyamide resin (B) and the polyamide resin (C) may be within the above ranges. It is important that the high transparency of the molded product can be maintained and further excellent chemical resistance, hardness and oxygen barrier property can be imparted.
  • the polyamide resin (B) and the polyamide resin (C) preferably have 60 mol% or more of their constituent units in common, more preferably 65 mol% or more in common, and 70 mol% or more in common. Is even more preferable.
  • the upper limit is preferably 80 mol% or less, more preferably 75 mol% or less.
  • the common structural unit here means that, for example, the total ratio of metaxylylene diamine and adipic acid among the raw material monomers constituting the polyamide resin (B) contained in the resin composition is 95 mol% of the total raw material monomers.
  • the amount of isophthalic acid in the resin composition of the present invention is the amount of the isophthalic acid-derived constituent units when the total amount of the dicarboxylic acid-derived constituent units in the polyamide resin (B) and the polyamide resin (C) is 100 mol%. It can be evaluated by the ratio (mol%).
  • the ratio of the constituent units derived from isophthalic acid is preferably 1 mol% or more, more preferably 3 mol% or more, and further preferably 5 mol% or more.
  • the upper limit is preferably 25 mol% or less, more preferably 22.5 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less.
  • the resin composition of the present invention may consist only of polystyrene resin (A), polyamide resin (B) and polyamide resin (C), or may contain other components.
  • polystyrene resin (A), the polyamide resin (B) and the polyamide resin (C) one type may be used for each, or two or more types may be contained. When two or more types are included, it is preferable that the total satisfies the above range.
  • the components other than the polystyrene resin (A), the polyamide resin (B) and the polyamide resin (C) in the resin composition of the present invention include other components other than the polyamide resins (B) and (C) shown above.
  • lubricant include higher fatty acid metal salts, and calcium stearate is preferable.
  • polyamide resins examples include polyamide 6, polyamide 66, polyamide 46, polyamide 6/66 (a copolymer composed of polyamide 6 component and polyamide 66 component), polyamide 610, polyamide 612, polyamide 11, polyamide 12, and MPXD6 (poly). Metaparaxylylene adipamide), MXD10 (polymethaxylylene sevasamide), MPXD10 (polymetaxylylene sevasamide) and PXD10 (polyparaxylylene sevasamide), polyamide 6I, polyamide 6T, polyamide 9I , Polyamide 9T, Polyamide 10T, Polyamide 6I / 6T, Polyamide 9I / 9T and the like are exemplified. Each of these other polyamide resins may be one kind or two or more kinds.
  • thermoplastic resin other than the polyamide resin examples include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate, polystyrene resins, and acrylic resins.
  • the thermoplastic resin other than these polyamide resins may be one kind or two or more kinds, respectively.
  • the total content of the polystyrene resin (A), the polyamide resin (B) and the polyamide resin (C) can be 98% by mass or more of the resin component contained in the resin composition. It may be 99% by mass or more.
  • the resin composition of the present invention also has a total content of polystyrene resin (A), polyamide resin (B) and polyamide resin (C) of 90% by mass or more (preferably 95% by mass or more) of the resin composition. It can be preferably 99% by mass or more).
  • the resin composition of the present invention can be produced by a known method. For example, it is obtained by melt-kneading polystyrene resin (A), polyamide resin (B), and polyamide resin (C).
  • polystyrene resin (A) polystyrene resin (B)
  • polyamide resin (C) polyamide resin (C)
  • the oxygen permeation coefficient of the resin composition of the present invention is 11 cc ⁇ mm / day ⁇ m 2 ⁇ atm or less when molded into a film having a thickness of 100 ⁇ m and measured under the conditions of a measurement temperature of 25 ° C. and a relative humidity of 60%. It is preferably 5 cc ⁇ mm / day ⁇ m 2 ⁇ atm or less, more preferably 1 cc ⁇ mm / day ⁇ m 2 ⁇ atm or less, and 0.5 cc ⁇ mm / day ⁇ m 2 -Atm or less is more preferable, and 0.3 cc ⁇ mm / day ⁇ m 2 ⁇ atm or less is even more preferable.
  • the ideal lower limit is 0 cc ⁇ mm / day ⁇ m 2 ⁇ atm, but even if it is 0.001 cc ⁇ mm / day ⁇ m 2 ⁇ atm or more, the required performance is satisfied.
  • the details of the method for measuring the oxygen barrier property follow the method described in Examples described later.
  • the molded article of the present invention is formed from the resin composition of the present invention.
  • the specific method for producing a molded product using the resin composition of the present invention is not particularly limited, and a molding method generally used for thermoplastic resins can be adopted. Specifically, molding methods such as injection molding, hollow molding, extrusion molding, and press molding can be applied.
  • Molded products include single-layer films (including single-layer sheets), multilayer films (including multilayer sheets), fibers, threads, monofilaments, multifilaments, ropes, tubes, hoses, various molding materials, containers, various parts, and completed products. Examples include products, housings, and the like. Further, the molded product (particularly, film, monofilament, multifilament) may be stretched. The molded product may be a thin-walled molded product, a hollow molded product, or the like. Among them, in the present invention, a film (including a sheet) product is preferable from the viewpoint of utilizing the advantage of high transparency.
  • the thickness of the film is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 60 ⁇ m or less. It is practical that the lower limit is 0.1 ⁇ m or more. As the thick sheet, the thickness is preferably 100 ⁇ m or more, more preferably 500 ⁇ m or more, and further preferably 1 mm or more. It is practical that the upper limit value is 10 mm or less. Specific examples of the molded product are not particularly limited, but are daily necessities such as food packaging films such as wraps and shrink films, pouches of various shapes, container lids, bottles, cups, trays, tubes, and electronic devices.
  • Transparent members for display screens of equipment transparent members for lighting equipment, surface members for recording media, packaging members for pharmaceuticals, transport machine parts such as automobiles, general machine parts, precision machine parts, OA equipment parts, building materials / housing related parts , Medical equipment, leisure sports equipment, play equipment, medical products, etc.
  • molded products are not particularly limited, but are related to transportation equipment parts such as automobiles, automobile interior parts, general mechanical parts, precision mechanical parts, electronic / electrical equipment parts, OA equipment parts, building materials / housing equipment. These include parts, medical equipment, leisure and sporting goods, play equipment, medical supplies, food packaging films, ornaments, paint and oil containers, defense and aerospace products, etc.
  • the internal temperature was continuously raised to 245 ° C.
  • the water produced by polycondensation was removed from the system through a condenser and a cooler.
  • the internal temperature was further raised to 260 ° C., the reaction was continued for 1 hour, the polymer was taken out as a strand from the nozzle at the bottom of the reaction can, cooled with water, and pelletized to obtain the polymer (MXD6). Obtained.
  • the sheet obtained from the resin composition was highly transparent and had an excellent appearance ( Examples 1 to 6). Further, by increasing the content of the polyamide resin (C), those having high chemical resistance, pencil hardness, and oxygen barrier property were obtained. On the other hand, even in the blend of the polystyrene resin and the polyamide resin, those which do not contain the isophthalic acid-modified polyamide resin (C) (Comparative Example 2) and those which contain a large amount of the isophthalic acid-modified polyamide resin (C) (Comparative Example 3). ), When a polyamide resin having a low isophthalic acid modification rate was used (Comparative Examples 4 to 6), the transparency of the sheet was low and the appearance was inferior to that of the polystyrene resin alone (Comparative Examples). 1).

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

Abstract

La présente invention concerne une composition de résine dans laquelle une résine de polyamide est mélangée avec une résine de polystyrène, un article moulé, un film et un procédé de production d'une composition de résine. La présente composition de résine contient un total de 85 à 15 parties en masse d'une résine de polyamide (B) et d'une résine de polyamide (C) pour 15 à 85 parties en masse d'une résine de polystyrène (A), et est telle que : la résine de polyamide (B) est configurée à partir d'unités structurales dérivées d'une diamine et d'unités structurales dérivées d'un acide dicarboxylique, 70 % en moles ou plus des unités structurales dérivées d'une diamine étant dérivées de xylylènediamine, et plus de 90 % en moles des motifs structuraux dérivés d'un acide dicarboxylique étant dérivés de l'acide adipique ; la résine de polyamide (C) est configurée à partir d'unités structurales dérivées d'une diamine et d'unités structurales dérivées d'un acide dicarboxylique, 70 % en moles ou plus des unités structurales dérivées d'une diamine étant dérivées de xylylènediamine, 40 à 60 % en moles des motifs structuraux dérivés d'un acide dicarboxylique étant dérivés d'un acide dicarboxylique aliphatique en C4-20 α,ω-linéaire, et 60 à 40 % en moles des motifs structuraux dérivés d'un acide dicarboxylique étant dérivés de l'acide isophtalique (cependant, le total n'est pas supérieur à 100 % en moles) ; et le rapport de masse ((B):(C)) de la résine de polyamide (B) et de la résine de polyamide (C) est de 95:5 à 65:35.
PCT/JP2020/000576 2019-03-19 2020-01-10 Composition de résine, article moulé, film, et procédé de production de composition de résine WO2020188963A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009001782A (ja) * 2007-05-21 2009-01-08 Mitsubishi Gas Chem Co Inc ガスバリア性に優れた熱可塑性樹脂組成物延伸体
JP2014047289A (ja) * 2012-08-31 2014-03-17 Mitsubishi Gas Chemical Co Inc ポリアミド樹脂組成物及びその製造方法
WO2017090556A1 (fr) * 2015-11-27 2017-06-01 三菱瓦斯化学株式会社 Résine polyamide, article moulé et procédé de production d'une résine polyamide
WO2019058986A1 (fr) * 2017-09-22 2019-03-28 三菱瓦斯化学株式会社 Composition de résine, article façonné, et film
WO2019208687A1 (fr) * 2018-04-26 2019-10-31 三菱瓦斯化学株式会社 Film étiré, matériau d'emballage et procédé de production d'un film étiré

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009001782A (ja) * 2007-05-21 2009-01-08 Mitsubishi Gas Chem Co Inc ガスバリア性に優れた熱可塑性樹脂組成物延伸体
JP2014047289A (ja) * 2012-08-31 2014-03-17 Mitsubishi Gas Chemical Co Inc ポリアミド樹脂組成物及びその製造方法
WO2017090556A1 (fr) * 2015-11-27 2017-06-01 三菱瓦斯化学株式会社 Résine polyamide, article moulé et procédé de production d'une résine polyamide
WO2019058986A1 (fr) * 2017-09-22 2019-03-28 三菱瓦斯化学株式会社 Composition de résine, article façonné, et film
WO2019208687A1 (fr) * 2018-04-26 2019-10-31 三菱瓦斯化学株式会社 Film étiré, matériau d'emballage et procédé de production d'un film étiré

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