WO2015166939A1 - Polyoléfine modifiée par un acide, composition de résine thermoplastique, adhésif, et corps stratifié - Google Patents

Polyoléfine modifiée par un acide, composition de résine thermoplastique, adhésif, et corps stratifié Download PDF

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Publication number
WO2015166939A1
WO2015166939A1 PCT/JP2015/062780 JP2015062780W WO2015166939A1 WO 2015166939 A1 WO2015166939 A1 WO 2015166939A1 JP 2015062780 W JP2015062780 W JP 2015062780W WO 2015166939 A1 WO2015166939 A1 WO 2015166939A1
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acid
modified polyolefin
polyolefin
ppm
adhesive
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PCT/JP2015/062780
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English (en)
Japanese (ja)
Inventor
綾平 志賀
圭一 池田
和人 杉山
伊崎　健晴
恭子 小林
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三井化学株式会社
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Publication of WO2015166939A1 publication Critical patent/WO2015166939A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment

Definitions

  • the present invention relates to an acid-modified polyolefin.
  • Polyolefin resins have many excellent features such as chemical resistance and mechanical properties, but have the disadvantage of low affinity with polar substances because they are nonpolar resins.
  • a polar group derived from an organic carboxylic acid having a carbon-carbon double bond in a polyolefin (hereinafter simply referred to as “organic acid”) is used as an initiator.
  • organic acid a polar group derived from an organic carboxylic acid having a carbon-carbon double bond in a polyolefin
  • a method of modifying a polyolefin by imparting by a graft reaction is used.
  • Patent Document 1 discloses a polypropylene adhesive in which an unsaturated carboxylic acid such as maleic anhydride and / or a derivative thereof is grafted onto a polypropylene resin with respect to a specific polyolefin polymer composition. ing.
  • an object of the present invention is to provide an acid-modified polyolefin and a resin composition using the same, which can be used as an adhesive capable of bonding a polyolefin resin and a polar resin with a sufficient force.
  • the present invention relates to the following ⁇ 1> to ⁇ 7>.
  • the ratio (X / Y) of the integral value (X) of the signal in the range of 3.5 ppm to 4.0 ppm and the integral value (Y) of the signal in the range of 2.6 ppm to 3.5 ppm is 0.
  • Acid-modified polyolefin (C) having a signal maximum value in a range of 3.6 ppm or more and 3.8 ppm or less in a 1 H-NMR spectrum.
  • ⁇ 2> The acid-modified polyolefin according to ⁇ 1>, wherein a graft amount of the unsaturated carboxylic acid and / or derivative (B) per 100% by weight of the acid-modified polyolefin (C) is 0.5% by weight or more.
  • C ⁇ 3>
  • ⁇ 4> The acid-modified polyolefin (C) according to any one of ⁇ 1> to ⁇ 3>, wherein the unsaturated carboxylic acid and / or derivative (B) thereof is maleic anhydride.
  • a thermoplastic resin composition comprising the acid-modified polyolefin (C) according to any one of ⁇ 1> to ⁇ 4> and an unmodified polyolefin (D).
  • An adhesive comprising the thermoplastic resin composition according to ⁇ 5>.
  • ⁇ 7> A laminate comprising a polyolefin resin layer, an adhesive layer, and a polar resin layer in this order, wherein the adhesive layer contains the adhesive according to ⁇ 6>.
  • an acid-modified polyolefin excellent in adhesive strength between a polyolefin resin and a polar resin and a resin composition using the same are provided.
  • the acid-modified polyolefin (C) of the present invention is an acid-modified polyolefin (C) obtained by grafting an unsaturated carboxylic acid and / or its derivative (B) onto the polyolefin (A), and the acid-modified polyolefin (C)
  • the ratio of the integral value (X) of the signal in the range of 3.5 ppm to 4.0 ppm and the integral value (Y) of the signal in the range of 2.6 ppm to 3.5 ppm in the 1 H-NMR spectrum of (X / Y) is 0.01 or more and less than 1.
  • the ratio (X / Y) is preferably in the range of 0.02 to 0.35, more preferably 0.05 to 0.30.
  • a numerical range of “n1 or more and n2 or less” is also simply referred to as “n1 to n2”.
  • Acid-modified polyolefins in which the ratio (X / Y) in the 1 H-NMR spectrum takes the above values are superior in adhesion performance to polar substances compared to acid-modified polyolefins in which the ratio (X / Y) does not take this value. Excellent.
  • a signal in the range of 3.5 ppm to 4.0 ppm in the 1 H-NMR spectrum is considered to correspond to a structure in which unsaturated carboxylic acids and / or derivatives thereof are grafted in a chain.
  • the polarity of the graft portion is increased, and as a result, the affinity between the acid-modified polyolefin and the polar substance is improved, thereby improving the adhesiveness.
  • the acid-modified polyolefin (C) of the present invention has a signal maximum value in the range of 3.6 ppm to 3.8 ppm in the 1 H-NMR spectrum, and 3.6 ppm to 3. It is preferable that it exists in the range of 75 ppm or less.
  • the graft amount of the unsaturated carboxylic acid and / or derivative (B) grafted in the acid-modified polyolefin (C) is preferably 0.5% by weight or more, more preferably 1.0% by weight or more. In order for the graft amount to satisfy this range, it is necessary that the (B) is present at a high concentration in the course of the graft reaction, and at the same time, during the graft reaction, the (B) has a chain shape.
  • the present invention is also suitable because it is easy to form a structure grafted on the substrate.
  • the “graft amount of unsaturated carboxylic acid and / or its derivative (B)” means that when unsaturated carboxylic acid and its derivative are used together, the graft amount of unsaturated carboxylic acid and the derivative of unsaturated carboxylic acid Refers to the total amount of grafts.
  • the intrinsic viscosity [ ⁇ ] of the acid-modified polyolefin (C) measured in decalin at 135 ° C. is preferably 0.2 dl / g or more, more preferably 0.3 dl / g or more, still more preferably 0.4 dl / g. That's it.
  • the intrinsic viscosity [ ⁇ ] of the acid-modified polyolefin (C) is less than 0.2 dl / g, it may be difficult to handle as a polyolefin resin due to the occurrence of stickiness or a significant decrease in melt viscosity.
  • the acid-modified polyolefin (C) of the present invention may be used for adhesion to a polar substance as a composition further containing an unmodified polyolefin (D), as described later.
  • the upper limit of the intrinsic viscosity [ ⁇ ] of the acid-modified polyolefin (C) is not particularly limited, but may be, for example, 20 dl / g.
  • the unmodified polyolefin (A) as a raw material for the acid-modified polyolefin (C) of the present invention is not particularly limited, but a polymer composed only of ⁇ -olefin, a polymer composed only of a cyclic olefin, or Mention may be made of a copolymer having two or more selected from ⁇ -olefins and cyclic olefins as raw material monomers.
  • ⁇ -olefin examples include ethylene, propylene, butene-1, pentene-1, 2-methylbutene-1, 3-methylbutene-1, hexene-1, 3-methylpentene-1, 4-methylpentene-1, 3,3-dimethylbutene-1, heptene-1, methylhexene-1, dimethylpentene-1, trimethylbutene-1, ethylpentene-1, octene-1, methylpentene-1, dimethylhexene-1, trimethylpentene- 1, ethylhexene-1, methylethylpentene-1, diethylbutene-1, propylpentene-1, decene-1, methylnonene-1, dimethyloctene-1, trimethylheptene-1, ethyloctene-1, methylethylhept Ten-1, diethylhexene-1, dodecene-1, hexadecen
  • cyclic olefin examples include norbornene, tetracyclododecene, dicyclopentadiene, ethylidene norbornene, and vinyl norbornene.
  • the main component monomer means a monomer that forms the constituent unit species having the maximum content among the constituent unit species constituting the polymer.
  • the unsaturated carboxylic acid and / or its derivative (B) grafted to the polyolefin (A) are, for example, an unsaturated compound having one or more carboxylic acid groups, an unsaturated carboxylic acid compound having a carboxylic acid group and an alkyl alcohol.
  • An unsaturated compound having at least one ester or carboxylic anhydride group for example, an anhydride of an unsaturated dicarboxylic acid.
  • the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group. it can.
  • the unsaturated carboxylic acid and / or its derivative (B) can be used alone or in combination of two or more.
  • component (B) is also referred to as “component (B)”.
  • unsaturated carboxylic acid examples include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, nadic acid, and endocis-bicyclo [2. 2.1] Unsaturated dicarboxylic acids such as hept-5-ene-2,3-dicarboxylic acid are preferred.
  • the component (B) used for the graft is not limited to the unsaturated carboxylic acid in the form of the free carboxylic acid as described above, but in the form of a derivative corresponding to the unsaturated carboxylic acid. It may be.
  • it may be in the form of an acid anhydride corresponding to an unsaturated dicarboxylic acid, such as maleic anhydride, citraconic anhydride, or nadic anhydride.
  • it may be in the form of acid halide, amide, imide, ester and the like, and specific examples of such unsaturated carboxylic acid derivatives include maleenyl chloride, maleenylimide, monomethyl maleate, dimethyl maleate and the like. .
  • the component (B) is preferably an unsaturated dicarboxylic acid or an acid anhydride thereof, particularly preferably maleic acid, nadic acid or an acid anhydride thereof, and particularly preferably maleic anhydride.
  • the acid-modified polyolefin (C) of the present invention is usually obtained by graft-reacting an unsaturated carboxylic acid and / or its derivative (B) to a polyolefin (A) in the presence of an organic peroxide as a radical initiator. can get.
  • the organic peroxide used in the graft reaction is any organic peroxide as long as the unsaturated carboxylic acid and / or derivative (B) thereof is grafted on the polyolefin (A) and satisfies the above requirements.
  • An oxide may be used as a radical initiator.
  • organic peroxides include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, t-hexylperoxyneodecanoate, t-butylperoxy Neodecanoate, t-amylperoxyneodecanoate, t-butylperoxyneoheptanoate, t-hexylperoxypivalate, t-butylperoxypivalate, t-amylperoxypivalate, t -Hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, 1,1 -Di (t-butylperoxy) -2-methylcyclohexane, 1,1-
  • organic peroxides can be used singly or in combination of two or more.
  • Preferred organic peroxides are 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, di-t-butyl peroxide, t-butylperoxyisopropyl monocarbonate, t-butylperoxy Benzoate.
  • the amount of the organic peroxide used is usually 0.01 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the polyolefin (A). Parts by weight.
  • a method in which a graft reaction is performed at a temperature not higher than the melting point (hereinafter sometimes referred to as “solid phase method”) is preferred.
  • a more preferable means includes performing the reaction in a sealed container.
  • Examples of the apparatus for carrying out the graft reaction include pressure-resistant and sealed containers such as autoclaves, paddle dryers, planetary mixers, V mixers, nauter mixers, Henschel mixers, ribbon mixers, rotary drum mixers, and kneaders. Examples include body mixers and microwave heating devices.
  • the amount of component (B) used is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, and particularly preferably 10 to 10 parts by weight with respect to 100 parts by weight of the polyolefin (A). 40 parts by weight.
  • grafting methods such as a solution method and a melt-kneading method may be adopted as long as it is possible to satisfy the requirement that the component (B) exist at a high concentration that causes self-polymerization in the reaction system. it can. That is, a polymer is melted, a graft monomer is added thereto, and a graft reaction is carried out in the presence of an organic peroxide. Alternatively, a polymer is dissolved in a solvent to form a solution, and the graft monomer is added thereto.
  • a solution method in which a graft reaction is performed in the presence of an organic peroxide can also be used without limitation.
  • the reaction time for the graft reaction as described above can be appropriately set in consideration of conditions such as the reaction temperature and the half-life of the decomposition reaction of the organic peroxide used.
  • the reaction time is usually 3 to 10 times, preferably 4 to 6 times the decomposition half-life of the organic peroxide at the reaction temperature.
  • the reaction time is usually 1/60 hours to 20 hours, preferably 0.5 hours to 15 hours.
  • thermoplastic resin composition contains the acid-modified polyolefin (C) and the unmodified polyolefin (D).
  • the thermoplastic resin composition of the present invention is a resin composition having an excellent balance of adhesion, printability, insulation / conductivity, compatibility, affinity with fillers, etc. Can be used for various purposes.
  • thermoplastic resin composition of the present invention when used as an adhesive resin composition (adhesive), a polyolefin resin such as polyethylene and polypropylene and a polar resin such as ethylene / vinyl alcohol copolymer and polyamide are sufficient. Since it can adhere
  • thermoplastic resin composition of the present invention includes (1) polystyrene, ethylene / vinyl alcohol copolymer, ionomer resin, polyurethane, polyamide, polyester, polyphenylene ether, polycarbonate, polyacetal, polyphenylene sulfide, polysulfone, polyether ketone, Various engineering plastics such as polyetheretherketone and polyimide; (2) Various polyolefins described in the section of polyolefin (A); and (3) Nitrile rubber, butadiene rubber, chloroprene rubber, butyl rubber, isoprene rubber, styrene-isoprene.
  • thermoplastic resin composition of the present invention is suitably used as a compatibilizing agent in a reinforced resin comprising at least one selected from (1) to (3) and a filler such as glass fiber or carbon fiber. It is done.
  • a raw material monomer is a polymer composed only of an ⁇ -olefin, a polymer composed only of a cyclic olefin, or any two or more selected from an ⁇ -olefin and a cyclic olefin. Mention may be made of copolymers.
  • ⁇ -olefin examples include ethylene, propylene, butene-1, pentene-1, 2-methylbutene-1, 3-methylbutene-1, hexene-1, 3-methylpentene-1, 4-methylpentene-1, 3,3-dimethylbutene-1, heptene-1, methylhexene-1, dimethylpentene-1, trimethylbutene-1, ethylpentene-1, octene-1, methylpentene-1, dimethylhexene-1, trimethylpentene- 1, ethylhexene-1, methylethylpentene-1, diethylbutene-1, propylpentene-1, decene-1, methylnonene-1, dimethyloctene-1, trimethylheptene-1, ethyloctene-1, methylethylhept Ten-1, diethylhexene-1, dodecene-1, hexadecen
  • cyclic olefin examples include norbornene, tetracyclododecene, dicyclopentadiene, ethylidene norbornene, and vinyl norbornene.
  • Preferred polyolefins are polymers having ethylene as the main monomer, polymers having 4-methylpentene-1 as the main monomer, polymers having propylene as the main monomer, and polymers having butene-1 as the main monomer.
  • the method for producing the thermoplastic resin composition of the present invention is a known method, for example, after dry blending an acid-modified polyolefin (C) and an unmodified polyolefin (D), using an apparatus such as an extruder or a mixer. And can be obtained by melt kneading.
  • the adhesive of the present invention contains the thermoplastic resin composition of the present invention.
  • the adhesive of the present invention includes polystyrene, ethylene / vinyl alcohol copolymer, ionomer resin, polyurethane, polyamide, polyester, polyphenylene ether, polycarbonate, polyacetal, polyphenylene sulfide, polysulfone, polyether ketone, polyether ether ketone, polyimide, Various engineering plastics, nitrile rubber, butadiene rubber, chloroprene rubber, butyl rubber, isoprene rubber, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer Various substances such as resins such as coalesced elastomers, metals such as aluminum, iron, nickel and copper, fabrics such as paper, cotton and chemical fibers Because it has a high adhesion for, with the use
  • the adhesive of the present invention may contain known additives such as antioxidants, weathering stabilizers, antistatic agents, ultraviolet absorbers, crystal nucleating agents, flame retardants and foaming agents as other components.
  • the laminate of the present invention comprises a layer composed of a polyolefin resin (hereinafter also referred to as “base material”), an adhesive layer, and a layer composed of a polar resin in this order, and the adhesive layer includes the adhesive of the present invention. is there.
  • polyethylene polyethylene, polypropylene, or the like can be used, but polypropylene having excellent moldability, mechanical strength, chemical resistance, and the like is more preferable.
  • the substrate is usually in the form of a sheet or film.
  • the thickness of the substrate can be appropriately selected depending on the material, shape, application, etc. of the substrate, but is preferably 0.01 mm or more, more preferably 0.03 mm or more in order to maintain the rigidity as the substrate. .
  • the thickness of the base material is preferably 10 mm or less, more preferably 2 mm or less from the viewpoint of ease of handling.
  • the thickness of the adhesive layer containing the adhesive of the present invention is preferably 0.001 mm or more, more preferably 0.003 mm or more in order to obtain a sufficient adhesive function. However, even if it is too thick, the effect is not changed and the cost is increased. Therefore, the thickness of the adhesive layer is preferably 0.3 mm or less, more preferably 0.1 mm or less.
  • examples of the polar resin include ethylene / vinyl alcohol copolymer (EVOH), polyamide such as polyamide-6, polyamide-66, and polyamide 6T, and polyester such as polyethylene terephthalate and polybutylene terephthalate. It is done.
  • EVOH ethylene / vinyl alcohol copolymer
  • polyamide such as polyamide-6, polyamide-66, and polyamide 6T
  • polyester such as polyethylene terephthalate and polybutylene terephthalate. It is done.
  • the thickness of the layer made of polar resin is preferably 0.001 mm or more, more preferably 0.003 mm or more.
  • the thickness of the layer made of a polar resin is preferably 0.3 mm or less, more preferably 0.1 mm or less.
  • the manufacturing method of such a laminate can be a conventionally known one, and is not particularly limited.
  • the laminate is obtained, for example, by a coextrusion injection method or a thermal lamination method.
  • the shape of the obtained laminated body is not specifically limited, For example, shapes, such as a bottle, a cup, a tube, a sheet
  • melt flow rate According to ASTM D1238, measurement of melt flow rate (MFR) was performed at 230 ° C. under a load of 2.16 kg.
  • Measurement mode Single pulse ⁇ Pulse width 45 ° (5.12 ⁇ s) ⁇ Number of points 32k ⁇ Repetition time 7.0 seconds ⁇ Number of integrations 512 times ⁇ Measurement solvent 1,1,2,2-tetrachloroethane-d2 ⁇ Sample concentration about 20mg / 0.6mL ⁇ Measurement temperature 120 °C ⁇ Chemical shift standard 1,1,2,2-tetrachloroethane: 5.91 ppm (5) Graft amount of unsaturated carboxylic acid Acid-modified polyolefin from which ungrafted unsaturated carboxylic acid was removed according to the method described in (3) above was hot-pressed at 250 ° C. to prepare a film having a thickness of 300 ⁇ m.
  • the external absorption spectrum was measured, and the amount of unsaturated carboxylic acid grafted was quantified from the absorption near 1790 cm ⁇ 1 .
  • This value was converted into a measured value by 1 H-NMR by a calibration curve based on a correlation between a previously measured value by 1 H-NMR and a value by infrared absorption spectrum.
  • Tm melting point
  • a sample in a particle shape is packed in an aluminum pan, heated up to 200 ° C. at 10 ° C./min, and the melting point is the temperature at the peak of the melting peak when ⁇ H is 1 J / g or more. It was.
  • the peel test was performed under the following conditions. Measurement temperature 23 ° C., test speed 300 mm / min, test section 10.0 mm to 70.0 mm, test piece width 15.0 mm.
  • peroxide NOF Corporation, Perbutyl D
  • MFR 5.0 g / 10 min, density 0.9 g / cm 3
  • Use as an adhesive layer to create a laminate of 3 types and 5 layers of polypropylene / adhesive layer / ethylene vinyl alcohol copolymer / adhesive layer / polypropylene 350/50/50/50/350 ⁇ m, and peel test under the above conditions Went.
  • the peel strength was 68 N / 15 mm.
  • a laminate of 3 types and 5 layers was prepared in the same manner as in Example 1 except that this maleic anhydride-modified polypropylene was used as an adhesive layer, and a peel test was conducted.
  • the peel strength of this laminate was 40 N / 15 mm.
  • maleic anhydride-modified polypropylene In order to remove unreacted maleic anhydride from the obtained maleic anhydride-modified polypropylene, it was suspended in 400 ml of methyl ethyl ketone, stirred for 30 minutes, and then filtered. This operation was repeated 4 times, and then vacuum drying was performed at 120 ° C. and 20 mmHg or less for 2 hours to obtain maleic anhydride-modified polypropylene.
  • a three-layer five-layer laminate was prepared in the same manner as in Example 1 except that the maleic anhydride-grafted polypropylene thus obtained was mixed with the above-mentioned commercially available unmodified polypropylene and used as an adhesive layer. Went. The peel strength of this laminate was 50 N / 15 mm.
  • Intrinsic viscosity [ ⁇ ] 3.0 dl / g, average particle diameter 500 ⁇ m, melting point 230 ° C., 100 parts by weight of copolymer particles of 4-methylpentene-1 and decene-1, 5 parts by weight of maleic anhydride, As an oxide, 3.1 parts by weight of t-butyl peroxyisopropyl monocarbonate (NOF Corporation, Perbutyl I) was charged into a 20 ml capacity pressure vessel, the inside was purged with nitrogen, sealed, and heated to 125 ° C. The reaction was conducted by heating in an oil bath for 5 hours. After completion of the reaction, it was cooled and the contents of the pressure vessel were extracted.
  • NOF Corporation Perbutyl I

Abstract

[Problème] L'invention a pour objectif de fournir une polyoléfine modifiée par un acide et une composition de résine utilisant la polyoléfine modifiée par un acide, ladite composition pouvant être utilisée dans un adhésif qui peut coller une polyoléfine et une résine polaire avec une force suffisante. [Solution] Une polyoléfine modifiée par un acide (C) est formée par greffage d'un acide carboxylique insaturé et/ou un dérivé de celui-ci (B) sur une polyoléfine (A), le rapport (X/Y) de la valeur intégrale (X) du signal à spectre 1H NMR de 3,5 et 4,0 ppm de la polyoléfine modifiée par un acide (C) sur la valeur intégrale (Y) du signal de 2,6 à 3,5 ppm étant supérieur ou égal à 0,01 et inférieur à 1, la valeur maximale du signal à spectre 1H NMR de la polyoléfine modifiée par un acide (C) étant comprise entre 3,6 et 3,8 ppm.
PCT/JP2015/062780 2014-04-30 2015-04-28 Polyoléfine modifiée par un acide, composition de résine thermoplastique, adhésif, et corps stratifié WO2015166939A1 (fr)

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JP2017140768A (ja) * 2016-02-10 2017-08-17 三菱エンジニアリングプラスチックス株式会社 成形品
JP2019217701A (ja) * 2018-06-20 2019-12-26 国立大学法人大阪大学 成形用型の製造方法

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JP2017140768A (ja) * 2016-02-10 2017-08-17 三菱エンジニアリングプラスチックス株式会社 成形品
JP2019217701A (ja) * 2018-06-20 2019-12-26 国立大学法人大阪大学 成形用型の製造方法
JP7100846B2 (ja) 2018-06-20 2022-07-14 国立大学法人大阪大学 成形用型の製造方法

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