WO2019009389A1 - Composition solide de résine à base de polypropylène - Google Patents

Composition solide de résine à base de polypropylène Download PDF

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Publication number
WO2019009389A1
WO2019009389A1 PCT/JP2018/025621 JP2018025621W WO2019009389A1 WO 2019009389 A1 WO2019009389 A1 WO 2019009389A1 JP 2018025621 W JP2018025621 W JP 2018025621W WO 2019009389 A1 WO2019009389 A1 WO 2019009389A1
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Prior art keywords
resin composition
polypropylene resin
agents
additive
mass
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PCT/JP2018/025621
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English (en)
Japanese (ja)
Inventor
岡本　卓治
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出光興産株式会社
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Publication of WO2019009389A1 publication Critical patent/WO2019009389A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08L23/10—Homopolymers or copolymers of propene

Definitions

  • the present invention relates to solid polypropylene-based resin compositions, preferably to polypropylene-based masterbatch pellets.
  • the thermoplastic resin contains various additives for plastics.
  • additives for plastics are often in the form of powder or liquid, and their handling is poor.
  • the resin component and the oil component which is a plasticizer are mixed in a hot melt adhesive or an elastomer compound product, if there is a deficiency in the addition order and the addition amount in which a liquid additive such as oil is mixed, kneading is performed.
  • the oil component may stick to the screw, the shear force is not transmitted to the resin, and the resin component may not be mixed because of a so-called "slip phenomenon".
  • special considerations need to be taken when formulating additives that are liquid at ambient temperature.
  • Patent Document 1 discloses a masterbatch containing 10 to 95% by mass of a plastic additive, 1 to 50% by mass of an olefin polymer satisfying specific conditions, and 1 to 89% by mass of a polyolefin resin for a carrier. A composition is disclosed. The masterbatch composition disclosed in Patent Document 1 can improve the handling property when adding the additive for plastic.
  • a dyeable polyolefin composition is disclosed that contains an olefin polymer having a melting endotherm ⁇ H-D of 0 to 80 J / g.
  • Masterbatch compositions are generally manufactured by melt-kneading.
  • the manufacturing method in particular is not limited, the melt-kneading by a twin screw extruder etc. is illustrated.
  • the additive for plastics is a liquid additive at normal temperature
  • the masterbatch containing an additive since it is the above-mentioned "slip phenomenon", it is with an olefin polymer etc.
  • it has been found that there is a problem that it is difficult to knead uniformly and difficult to produce a master batch.
  • Patent Document 1 since the polyolefin resin for the carrier is blended, the kneading temperature must be increased.
  • the inventors of the present invention are susceptible to reaction and volatilization of additives in liquid form at normal temperature under high temperature, and therefore, when preparing a masterbatch containing such liquid additives, the kneading temperature at the time of producing the masterbatch It has been found that the additives for plastic may react and deteriorate or volatilize and not be blended in a predetermined amount.
  • Patent Document 2 does not disclose a solid resin composition excellent in handleability containing a liquid additive and a master batch pellet using the same.
  • the problem to be solved by the present invention is to provide a solid resin composition (preferably, a masterbatch pellet) excellent in handleability containing an additive which is liquid at room temperature.
  • the present disclosure relates to the following.
  • a sample is held at -10 ° C for 5 minutes in a nitrogen atmosphere using a ⁇ 1> differential scanning calorimeter (DSC), and then the melting endotherm obtained from the melting endothermic curve obtained by raising the temperature at 10 ° C / min 10 mass% or more and 99.6 mass% or less of a polypropylene resin (A) having a heat amount ( ⁇ H-D) of 0 J / g or more and 80 J / g or less, and an additive (B) 0.4 which is liquid at 23 ° C.
  • Solid polypropylene resin composition containing mass% or more and 90 mass% or less.
  • DSC differential scanning calorimeter
  • the melting point (Tm-D) defined as the observed peak top is not observed or is 0 ° C. or more and 120 ° C. or less.
  • ⁇ 3> The content of at least one structural unit selected from the group consisting of propylene homopolymers or ethylene and ⁇ -olefins having 4 to 30 carbon atoms in an amount of more than 0 mol%
  • the additive (B) is a viscosity modifier, a plasticizer, a crystal nucleating agent, a crystallization rate modifier, a lubricant, a release agent, a strength improver, a crosslinking agent, a decomposition agent, a softening agent, a flame retardant Flame retardant aid, slip agent, antifogging agent, conductive agent, antistatic agent, heat conductive agent, foaming agent, coloring agent, fluorescent agent, fragrance, surfactant, insect repellent, antioxidant, anti-aging agent,
  • the solid polypropylene resin according to any one of the above ⁇ 1> to ⁇ 3>, which is at least one selected from the group consisting of a weathering agent, an ultraviolet light absorber, an antidegradant, a fungicide and an antibacterial agent.
  • composition Composition.
  • a pellet comprising the solid polypropylene resin composition according to any one of the above ⁇ 1> to ⁇ 4>.
  • ⁇ 6> A step of immersing pellets or flakes of the polypropylene resin (A) in the additive (B) to impregnate the additives (B) in the pellets or flakes of the polypropylene resin (A) The manufacturing method of the solid-state polypropylene resin composition as described in any one of said ⁇ 1>- ⁇ 4> which it has.
  • a solid resin composition preferably, a masterbatch pellet
  • an additive which is liquid at room temperature
  • the term “A to B” relating to the description of numerical values means “A or more and B or less” (for A ⁇ B) or “A or less B or more” (for A> B). . Moreover, in the present invention, a combination of preferred embodiments is a more preferred embodiment.
  • the solid polypropylene-based resin composition of the present invention comprises 10% by mass to 99.6% by mass of a specific polypropylene-based resin (A) and 0.4% by mass or more of an additive (B) which is liquid at 23 ° C. 90 mass% or less is included.
  • the polypropylene-based resin (A) used in the present embodiment is obtained by using a differential scanning calorimeter (DSC) and keeping the sample at -10 ° C for 5 minutes in a nitrogen atmosphere, and then raising the temperature at 10 ° C / min.
  • the melting endotherm ( ⁇ H-D) obtained from the melting endothermic curve is from 0 J / g to 80 J / g. When the melting endotherm ( ⁇ H-D) exceeds 80 J / g, the impregnation of the liquid additive becomes insufficient.
  • the melting endotherm ( ⁇ H-D) is preferably 70 J / g or less, more preferably 60 J / g or less, still more preferably 50 J / g or less, and from the viewpoint of further suppressing stickiness
  • it is 10 J / g or more, More preferably, it is 20 J / g or more, More preferably, it is 30 J / g or more.
  • the melting endotherm ( ⁇ H-D) is the highest temperature of the melting endothermic curve obtained by DSC measurement, with the line connecting the point on the low temperature side without change in calorific value and the point on the high temperature side without change in calorific value as a baseline It is calculated by obtaining an area surrounded by a line portion including a peak observed on the side and the baseline.
  • the melting endotherm ( ⁇ H-D) can be controlled by appropriately adjusting the monomer concentration and the reaction pressure.
  • the polypropylene resin (A) may be a propylene homopolymer or a copolymer.
  • the copolymerization ratio of propylene units is more than 50 mol%, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% It is above.
  • the copolymerizable monomer is at least one selected from the group consisting of ethylene and an ⁇ -olefin having 4 to 30 carbon atoms, and specific examples thereof include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene and the like.
  • the polypropylene resin (A) is a copolymer
  • the polypropylene resin (A) contains 0 mol% of at least one structural unit selected from the group consisting of ethylene and ⁇ -olefins having 4 to 30 carbon atoms. It is preferable to include more than 20 mol% or less.
  • the polypropylene resin (A) preferably satisfies the following (1).
  • (1) Using a differential scanning calorimeter (DSC), hold the sample at -10 ° C for 5 minutes in a nitrogen atmosphere and then raise the temperature at 10 ° C / min to the highest temperature side of the melting endothermic curve
  • the melting point (Tm-D) defined as the observed peak top is not observed or is 0 ° C. or more and 120 ° C. or less.
  • the melting point (Tm-D) of the polypropylene resin (A) is preferably not observed or is 0 ° C. or more and 120 ° C. or less from the viewpoint of impregnation of the liquid additive.
  • a melting point is observed, from the same viewpoint, more preferably 30 ° C. or more, further preferably 35 ° C. or more, still more preferably 40 ° C. or more, and more preferably 90 ° C. or less, more preferably 85 ° C. or less.
  • the melting point can be controlled by appropriately adjusting the monomer concentration and the reaction pressure.
  • the intrinsic viscosity [ ⁇ ] of the polypropylene resin (A) is preferably 0.01 dL / g or more, more preferably 0.10 dL / g or more, still more preferably 0. 30 dL / g or more, still more preferably 0.40 dL / g or more, and preferably 1.80 dL / g or less, more preferably 1.50 dL / g or less, still more preferably 1.30 dL / g or less, more preferably More preferably, it is 1.20 dL / g or less, still more preferably 1.00 dL / g or less.
  • the intrinsic viscosity [ ⁇ ] is calculated by using a Ubbelohde viscometer to measure the reduced viscosity ( ⁇ SP / c) in tetralin at 135 ° C., and using the following equation (Hagins' equation).
  • ⁇ SP / c [ ⁇ ] + K [ ⁇ ] 2 c SP SP / c (dL / g):
  • Intrinsic viscosity c (g / dL): Polymer viscosity K 0.35 (Huggins constant)
  • the weight average molecular weight (Mw) of the polypropylene resin (A) is preferably 30,000 or more, more preferably 50,000 or more, still more preferably 70,000 or more, from the viewpoint of impregnation of the liquid additive. And preferably it is 200,000 or less, more preferably 180,000 or less, further preferably 150,000 or less.
  • the molecular weight distribution (Mw / Mn) of the polypropylene resin (A) is preferably 3.0 or less, more preferably 2.8 or less, still more preferably 2.6 or less, from the viewpoint of impregnation of the liquid additive. It is more preferably 2.5 or less, and preferably 1.5 or more, more preferably 1.6 or more, still more preferably 1.7 or more, and still more preferably 1.8 or more.
  • the above weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) are determined by gel permeation chromatography (GPC) measurement.
  • the weight average molecular weight is a polystyrene equivalent weight average molecular weight measured under the following apparatus and conditions, and the molecular weight distribution is a value calculated from the number average molecular weight (Mn) and the weight average molecular weight similarly measured.
  • ⁇ GPC measuring device Column: "TOSO GMHHR-H (S) HT” manufactured by Tosoh Corporation Detector: RI detector for liquid chromatography Waters Corporation "WATERS 150C” ⁇ Measurement conditions> Solvent: 1,2,4-Trichlorobenzene Measurement temperature: 145 ° C Flow rate: 1.0 mL / min Sample concentration: 2.2 mg / mL Injection volume: 160 ⁇ L Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver. 1.0)
  • the melt flow rate (MFR) of the polypropylene resin (A) is preferably 1 g / 10 min or more, more preferably 7 g / 10 min or more, still more preferably 10 g / 10 min or more from the viewpoint of impregnation of the liquid additive And preferably 5000 g / 10 min or less, more preferably 4000 g / 10 min or less, and still more preferably 3000 g / 10 min or less.
  • the measuring method of MFR of a polypropylene resin (A) is based on ISO1133: 1997, and is measured on temperature 230 degreeC, and the conditions of load 21.18N.
  • a commercial item can be used as polypropylene resin (A). Specific examples thereof include “S400”, “S600” and “S901” of "L-MODU” (registered trademark) (made by Idemitsu Kosan Co., Ltd.). Commercially available products of amorphous poly- ⁇ -olefin include “APAO” manufactured by REXtac, LLC, “Vestoplast” manufactured by Evonik, etc. (all are trade names).
  • propylene-based elastomers Commercial products of propylene-based elastomers include "Tafmer XM”, “Tafmer PN” and “Tafmer SN” manufactured by Mitsui Chemicals, Inc .; “Tuff Selenium” manufactured by Sumitomo Chemical Co., Ltd .; “Prime Polymer” manufactured by Prime Polymer Co., Ltd. TPO ";” Versify "manufactured by Dow Chemical Co., Ltd .;” Vistamaxx ",” Linxar “manufactured by Exxon Mobil,” Licocene “manufactured by Clariant;” Adflex "manufactured by Bacell, etc. Product name).
  • the additive (B) used in the present embodiment is liquid at 23 ° C.
  • the additive (B) is used for the purpose of moldability improvement, physical property improvement, modification, functionalization, stabilization and the like of the thermoplastic resin, and it is not particularly limited as long as it is liquid at 23 ° C.
  • the additive (B) in the present invention may be an additive which is itself liquid at 23 ° C., and the additive dissolved in the solvent (C) described later is used as a liquid additive It can also be used.
  • the additive (B) is preferably impregnated in the polypropylene resin (A).
  • the additive (B) is preferably, for example, at least one selected from the group consisting of a moldability improver, a physical property improver, a functionalizing agent, and a stabilizer.
  • moldability improvers include viscosity modifiers (thickeners, viscosity reducing agents), plasticizers, crystal nucleating agents, crystallization rate modifiers, lubricants, and mold release agents.
  • viscosity modifiers thickeners, viscosity reducing agents
  • plasticizers plasticizers
  • crystal nucleating agents crystallization rate modifiers
  • lubricants lubricants
  • mold release agents examples include viscosity modifiers (thickeners, viscosity reducing agents), plasticizers, crystal nucleating agents, crystallization rate modifiers, lubricants, and mold release agents.
  • thickener a sugar polymer, protein, and its derivative can be illustrated preferably.
  • amylose, cellulose, collagen, derivatives thereof such as amylopectin having glucose in the side chain, xyloglucan having xylose and galactose in the side chain
  • It may be added as starch or gelatin.
  • starch commercially available starch as starch can be
  • polyglycerin or a derivative thereof a water-soluble resin having an amine value, for example, a polyacrylic acid derivative having an amine value, a polyacrylamide derivative, a polyvinyl alcohol derivative having an amine value, and the like can be preferably mentioned.
  • ester compounds such as phthalic acid, aliphatic, phosphoric acid, adipic acid, sebacic acid, azelaic acid, citric acid and the like; mainly polyvinyl chloride such as polyester and epoxy Plasticizers known as plasticizers for use in the present invention; mineral oils such as paraffinic, aromatic and naphthenic oils; vegetable fatty oils; synthetic oils such as silicone oils and esters.
  • the crystal nucleating agent may be a solution type or salt type, and may be a sorbitol type nucleating agent such as nonitol or dibenzylidene sorbitol type, a phosphorus type nucleating agent, a metal carboxylate type nucleating agent, a polymer type nucleating agent, an inorganic type Compounds etc. may be mentioned.
  • the crystallization rate modifier include zinc, cobalt, calcium salt, nigrosine and the like.
  • lubricants examples include wax based lubricants such as liquid paraffin, paraffin wax, microcrystalline wax, vaseline, Fischer-Tropsch wax, mineral oil, polyolefin wax such as polyethylene wax and polypropylene wax, montan wax, beet wax, ceresin wax, plants Waxes, animal waxes; fatty acid-based lubricants such as stearic acid and hydroxystearic acid; fatty acid amides such as oleic acid amide, stearic acid amide, erucic acid amide, lauric acid amide, palmitic acid amide, behenic acid amide, ethylene bis stearoamide, etc.
  • wax based lubricants such as liquid paraffin, paraffin wax, microcrystalline wax, vaseline, Fischer-Tropsch wax, mineral oil, polyolefin wax such as polyethylene wax and polypropylene wax, montan wax, beet wax, ceresin wax, plants Waxes, animal waxes
  • Fatty acid esters such as fatty acid methyl, butyl stearate, butyl oleate, isopropyl myristate, lauryl laurate and neopentyl polyol fatty acid; stearyl Alcohol, alcohol-based lubricants such as cetyl alcohol; metal soaps, and the like.
  • As the release agent lower alcohol esters of higher fatty acids such as butyl stearate, polyhydric alcohol esters of fatty acids such as castor oil, liquid paraffin, silicone type release agents and the like can be mentioned.
  • the physical property improver examples include a strength improver, a crosslinking agent, a decomposing agent, a softener, a flame retardant, a flame retardant auxiliary, a coupling agent, a photosensitizer, a photopolymerization initiator, a curing agent and the like.
  • a strength improver inorganic fillers and organic fillers may be mentioned, and starch, cellulose and derivatives thereof, glycerins, glycols, polymer fibers and the like may be mentioned.
  • crosslinking agent for example, an organic compound having a plurality of vinyl groups in one molecule is used, and divinylbenzene, trimethylolpropane trimethacrylate, methyl methacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol di Methacrylate, trimellitic acid triallyl ester, triallyl isocyanurate, ethyl vinyl benzene, neopentyl glycol dimethacrylate, 1,2,4-benzenetricarboxylic acid triallyl ester, 1,6-hexanediol dimethacrylate, lauryl methacrylate, stearyl Examples include methacrylate, diallyl phthalate, diallyl terephthalate, and diallyl isophthalate.
  • peroxides can be mentioned, and conventionally, for the purpose of lowering the molecular weight of a polypropylene resin, for the purpose of lightly crosslinking high density polyethylene (HDPE) and low density polyethylene (LDPE), these polyolefin resins Any peroxide can be used as long as it is used for the purpose of grafting saturated acid, etc., and diacyl peroxides, peroxy dicarbonates, peroxy esters, peroxy ketals, dialkyl peroxides And hydroperoxides.
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • olefin elastomers and plastomers comprising ethylene or propylene and a copolymer of ⁇ -olefin, etc., process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, polybutene, asphalt, vaseline, Fatty oil softeners such as coal tar and castor oil, waxes such as beeswax, carnauba wax and lanolin, fatty acids such as palmitic acid and fatty acid salts thereof, ester softeners, microcrystalline wax, Fischer Tropsch wax, liquid polybutadiene and liquid poly Examples include isoprene and its hydrides and derivatives.
  • the flame retardant examples include organic flame retardants such as phosphorus, halogen, chlorine and bromine, and inorganic flame retardants such as aluminum hydroxide, antimony and magnesium hydroxide.
  • a coupling agent coupling agents, such as a silane type, a titanate type, an aluminum type, a zirconium type, are mentioned.
  • the photosensitizer include photosensitizers such as a dichromate type, a bisazide compound type, a naphthoquinone diad type, and a diazoresin type.
  • photopolymerization initiator examples include radical polymerization initiators such as acetophenone type, benzoin type, benzophenone type, thioxanthone type, amine type, phosphorus type and dicarbonyl compound type, and cationic type polymerization initiators.
  • curing agents include linear aliphatic amines such as triethylenetetramine; cyclic aliphatic amines such as isophorone diamine; m-xylylenediamine, polyamidoamine, and aromatic amines such as diaminodiphenylmethane.
  • Amine-based curing agents include acid anhydride-based curing agents such as methyltetrahydrophthalic anhydride; phenol resin-based curing agents such as novolac type phenols; mercaptan-based curing agents and the like.
  • polymerizable monomers may be mentioned. There is no particular limitation, but radically polymerizable monomers are preferable, and monosubstituted ethylene, 1,1-disubstituted ethylene, 1,2-disubstituted ethylene and diene compounds are mentioned.
  • vinyl compounds conjugated monomers such as styrene derivatives, acrylic esters, acrylonitriles and acrylamide derivatives, halogenated vinyls such as vinyl chloride and vinyl esters, vinylamides such as N-vinylpyrrolidone, ⁇ -olefins and vinyl ethers And non-conjugated monomers such as allyl compounds.
  • the vinylidene compound include methacrylic acid esters, methacrylamide derivatives, vinylidene chloride, vinylidene fluoride, ⁇ -methylstyrene, isobutylene and the like.
  • maleimide derivatives such as N-alkyl substituted maleimide, acenaphthylene, vinylene carbonate, maleic anhydride, phthalic anhydride, 1,3-butadiene, isoprene, chloroprene, dimethacrylate, divinylbenzene, dimethacrylamide, diallyl ammonium salt, etc. It can be mentioned.
  • a sliding agent As the functionalizing agent, a sliding agent (slip agent), an antifogging agent, a conductive agent, an antistatic agent, a thermal conductive agent, a foaming agent, a coloring agent (dye, pigment), a fluorescent agent, a fragrance, a deodorant, Surfactants, insect repellents, insecticides, fungicides, fungicides and the like can be mentioned.
  • the antifogging agent include cationic surfactants, anionic surfactants, amphoteric surfactants, nonionic surfactants and the like.
  • the antistatic agent or surfactant include ionic surfactants such as anionic and cationic surfactants, nonionic surfactants and amphoteric surfactants.
  • organic foaming agents such as azo compounds, sulfohydrazides, nitroso type and the like; inorganic foaming agents such as sodium bicarbonate and ammonium vinyl carboxylate; propane, n-butane, iso-butane, n-pentane, Aliphatic hydrocarbons such as iso-pentane, cyclopentane, hexane, heptane, benzene; 1,2-dichlorotetrafluoroethane, 1-chlorotetrafluoroethane, 1,1-difluoroethane, 1,1,1,2-tetra Halogenated hydrocarbon-based gases such as fluoroethane; and halogenated hydrocarbon compounds mainly comprising an alternative fluorocarbon gas such as HFC 152a, HCFC 142b, HFC 134a, and the like.
  • inorganic foaming agents such as sodium bicarbonate and ammonium vinyl carboxylate
  • the dye examples include disperse dyes such as azo dyes, quinophthalone dyes and anthraquinone dyes, direct dyes, acid dyes and cationic dyes.
  • phthalocyanine blue and green pigments diarylide yellow and orange pigments, toluidine red, litho red, azo type red and yellow pigments such as naphthol red, and organic pigments such as brown pigments; iron oxide (yellow (Red, brown or black), ferric ammonium ferrocyanide (blue), manganese violet, ultramarine blue, chromium oxide (green), talc, lecithin modified talc, zeolite, kaolin, lecithin modified kaolin, titanium dioxide (white Inorganic pigments such as zinc oxide and mixtures thereof; and pigments similar to transparent pigments such as barium sulfate and calcium carbonate in which the average particle diameter of primary particles is 1 ⁇ m or less or 0.1 ⁇ m or less.
  • Examples include perfumes and natural perfumes, and various formulated perfumes and the like.
  • Deodorants include, for example, dichloroisocyanurate; extracts of plants such as rice, pine, cypress, persimmon, persimmon, tea, etc .; desalted betaine compounds; modified organic acid compounds; alkanolamines; stabilized chlorine dioxide; Aldehyde compounds; glycol ether compounds; phytoncid-based perfumes; lower aliphatic aldehyde-based perfumes and the like.
  • Examples of insect repellents include pyrethroid compounds, naphthalene compounds, paradichlorobenzene compounds, camphor and the like.
  • insecticides examples include hinokitiol, hiba oil, allyl isothiocyanate, propylene glycol monomethyl ether, ethanol, propanol, 1.8-cineole and the like.
  • Antifungal agents and fungicides include 2- (4-thiazolyl) -benzimidazole, 10,10'-oxybisphenoxacin, N- (fluorodichloromethylthio) -phthalimide, 2-n-octyl-4-isothiazoline
  • Examples include -3-one, bis (2-pyrozylthio-1-oxide) zinc, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine and the like.
  • the stabilizer examples include an antioxidant, an antiaging agent, a weathering agent, a light stabilizer, a decomposition inhibitor such as cleavage of the main chain by heat and hydrolysis, an antibacterial agent, and the like.
  • the antioxidant or anti-aging agent may, for example, be a phosphite-based, lactone-based, phenol-based, sulfur-based, amine-based or thioether-based antioxidant or anti-aging agent.
  • the light stabilizer include ultraviolet absorbers such as salicylate type, benzophenone type, benzotriazole type, cyanoacrylate type and nickel chelate type, and hindered amine type light stabilizer (HALS).
  • antibacterial agent examples include octyl trimethyl ammonium chloride, didecyl dimethyl ammonium gluconic acid, chlorhexidine, chlorhexidine gluconate, allyl isothiocyanate, propylene glycol monomethyl ether, propylene glycol monopropyl ether and the like.
  • additive (B) a viscosity modifier, a plasticizer, a crystal nucleating agent, a crystallization rate regulator, a lubricant, a mold release agent, a strength improver, a crosslinking agent, a decomposition agent, a softener, a flame retardant, a flame retardant
  • These additives may be used alone or in combination of two or more. For example, as described in JP-A-11-80262, it is also possible to use a peroxide and a main chain cleavage inhibitor in combination.
  • ⁇ Solvent (C)> As described above, as the additive (B) in the present invention, one obtained by dissolving the additive in the solvent (C) can also be used as a liquid additive.
  • An arbitrary solvent can be used as a solvent (C), and an organic solvent and an aqueous solvent can be mentioned.
  • organic solvents such as aliphatic hydrocarbon solvents such as hexane and heptane; aromatic solvents such as benzene, toluene and xylene; halogen solvents such as chloroform and trichloromethane; alcohol solvents such as methanol and ethanol; Ketone solvents such as acetone; ether solvents such as diethyl ether, tetrahydrofuran (THF), dioxane and the like can be mentioned.
  • aliphatic hydrocarbon solvents such as hexane and heptane
  • aromatic solvents such as benzene, toluene and xylene
  • halogen solvents such as chloroform and trichloromethane
  • alcohol solvents such as methanol and ethanol
  • Ketone solvents such as acetone
  • ether solvents such as diethyl ether, tetrahydrofuran (THF), dioxane and the like
  • the content of the polypropylene-based resin (A) is 10% by mass or more, preferably 40% by mass or more, more preferably 70% by mass from the viewpoint of handling properties of the resin composition. % Or more and 99.6% by mass or less, preferably 98% by mass or less.
  • the content of the additive (B) is 0.4% by mass or more, preferably 2% by mass or more, and 90% by mass or less from the viewpoint of moldability, physical properties, functionality and the like of the resin composition. Preferably it is 60 mass% or less, More preferably, it is 30 mass% or less.
  • the total content of the polypropylene resin (A) and the additive (B) in the solid polypropylene resin composition of the present invention is preferably 70% by mass or more, more preferably 80% by mass with respect to 100% by mass of the resin composition. % By mass or more, more preferably 90% by mass or more.
  • the resin composition of the present invention may contain materials other than the above as long as the effects of the present invention are not impaired.
  • a thermoplastic resin for example, polystyrene resin, polyolefin resin, polyacrylic resin, polycarbonate resin, polysulfone resin, cellulose resin, polyester resin, (meth) acrylic ester / styrene copolymer resin, acetic acid Vinyl resin, ethylene / vinyl acetate copolymer resin, ABS resin, styrenic elastomer resin, ethylene propylene diene copolymer resin, polybutadiene, natural rubber, synthetic rubber, polyamide resin, polyvinyl butyrate resin, vinyl chloride resin, silicone resin, Phenolic resin, urea resin, melamine resin, rosin and derivatives thereof, terpene resin, terpene phenol resin, aromatic modified terpene resin, hydrogen
  • the resin composition of the present invention is solid from the viewpoint of the handling property of the resin composition. However, it is not limited to a perfect solid, and may be gel.
  • the form of the solid polypropylene resin composition of the present invention is preferably pellets or flakes, more preferably pellets, from the viewpoint of the handling property of the resin composition.
  • Pellets comprising the solid polypropylene resin composition of the present invention contain additives which are liquid at room temperature, are excellent in handling properties, and are useful as masterbatch pellets.
  • the method for producing the solid polypropylene resin composition of the present invention is not particularly limited, but pellets or flakes of the polypropylene resin (A) are immersed in the additive (B) to make the additive (B) polypropylene resin ( Preferred is a method comprising the step of impregnating in A) pellets or flakes.
  • the additive In the production of a common masterbatch, the additive is added after heating to a temperature above the melting point of the polyolefin, and the mixture is kneaded and pelletized.
  • additives that are liquid at room temperature are often unstable above the melting point of the polyolefin, and at a kneading temperature at the time of masterbatch production, the additives for plastic react to deteriorate or volatilize, and a predetermined amount is blended. It may not be.
  • the time for immersing the pellets or flakes of the polypropylene resin (A) in the additive (B) varies depending on the type of the additive (B), but is preferably 1 minute or more, and preferably 48 hours It is below.
  • the solid polypropylene resin composition of the present invention can also be produced by a method of degassing the solvent (C) at a temperature at which the additive (B) does not thermally decompose.
  • a commonly used mixing apparatus such as a container with a stirring function, a mixing stirrer, a mixer, a blender, a tumbler mixer or a Henschel mixer can be used.
  • the solid polypropylene-based resin composition of the present invention is excellent in handling properties, and is useful as a masterbatch pellet containing an additive liquid at room temperature. According to the present invention, it is possible to provide a masterbatch in which the liquid additive is unlikely to bleed out and the stickiness is suppressed. In addition, it is not necessary to mix an oil component alone with a resin component in a hot melt adhesive or an elastomer compound product. Therefore, the resin component can be easily mixed without separation of the liquid component and the solid component in the kneader. In addition, since the liquid substance is not handled, the mixing operation is simplified.
  • the melting endotherms ( ⁇ H-D) and the melting points (Tm-D) of the polypropylenes (1) and (2) were measured by the following methods.
  • [DSC measurement] A sample of 10 mg was held at -10 ° C. for 5 minutes in a nitrogen atmosphere using a differential scanning calorimeter (Perkin Elmer, “DSC-7”), and then obtained by raising the temperature at 10 ° C./min. It was determined as the melting endotherm ( ⁇ H-D) from the melting endothermic curve. Further, the melting point (Tm-D) was determined from the peak top of the peak observed on the highest temperature side of the obtained melting endothermic curve.
  • the melting endotherm ( ⁇ H-D) is a differential scanning calorimeter (manufactured by Perkin-Elmer Co., Ltd.) with a line connecting the point on the low temperature side with no change in calorific value and the point on the high temperature side with no change in calorific value as a baseline.
  • DSC-7 differential scanning calorimeter
  • Example 1 100 g of pellets of polypropylene (1) were immersed in 100 mL of liquid paraffin and held at 23 ° C. for 1 day, and then filtered. The filtered pellet is left on paper waste ("Kimwipe" manufactured by Nippon Paper Cress Co., Ltd.) for 10 minutes, then one paper waste is folded in two and the pellet is wiped by hand to obtain a resin composition pellet The It was 102.15g when the mass of the resin composition pellet was measured. That is, the resin composition pellet of Example 1 contains 100 g (97.9% by mass) of polypropylene (1) and 2.15 g (2.1% by mass) of liquid paraffin, and polypropylene (1) contains liquid paraffin Was impregnated. The resin composition pellets did not stick to each other, and the handling properties were good.
  • Comparative Example 1 Resin composition pellets were obtained in the same manner as in Example 1 except that polypropylene (1) was changed to polypropylene (2) in Example 1. It was 100.32g when the mass of the resin composition pellet was measured. That is, the pellet of Comparative Example 1 contained 100 g (99.7% by mass) of polypropylene (2) and 0.32 g (0.3% by mass) of liquid paraffin and contained substantially no liquid paraffin.
  • Example 2 100 g of a pellet of polypropylene (1) was immersed in 200 mL (137 g) of heptane as a foaming agent and maintained at 23 ° C. for 5 minutes, and then filtered with a 120 mesh wire mesh for 10 minutes. The filtered pellet was swollen. The obtained pellet surface was wiped with filter paper, and left for 45 minutes to obtain a resin composition pellet. It was 130.4 g when the mass of the resin composition pellet was measured. That is, the resin composition pellet of Example 2 contains 100 g (76.7% by mass) of polypropylene (1) and 30.4 g (23.3% by mass) of heptane, and the polypropylene (1) is impregnated with heptane. It had been.
  • Comparative example 2 Resin composition pellets were obtained in the same manner as in Example 2 except that polypropylene (1) was changed to polypropylene (2) in Example 2. It was 100 g when the mass of the resin composition pellet was measured. That is, the pellets of Comparative Example 2 did not contain heptane at all.
  • Example 3 First, a rose-based flavor (6 parts of phenethyl alcohol, 1 part of nerol, 1 part of ⁇ -citronellol, 1 part of geraniol) was prepared. 1.0 mL of the perfume was diluted 5-fold with heptane to prepare a perfume dilution. 100 g of pellets of polypropylene (1) were placed in a 300 mL eggplant type flask, and 5.0 mL of perfume dilution liquid was added. Then, using a rotary evaporator, the flask was rotated at a rotational speed of 120 times / minute under normal temperature (23 ° C.) for 1 hour.
  • the obtained resin composition pellet was washed with 100 mL of ethanol and then dried under reduced pressure at 60 ° C. for 10 hours. It was 100.58g when the mass of the resin composition pellet was measured. That is, the resin composition pellet of Example 3 contains 100 g (99.4 mass%) of polypropylene (1) and 0.58 g (0.6 mass%) of a perfume, and the polypropylene (1) is impregnated with the perfume. It had been. The resin composition pellets did not stick.
  • Comparative example 3 Resin composition pellets were obtained in the same manner as in Example 3 except that polypropylene (1) was changed to polypropylene (2) in Example 3. The resin composition pellet was washed with 100 mL of ethanol and then dried under reduced pressure at 60 ° C. for 10 hours. It was 100.12g when the mass of the resin composition pellet was measured. That is, the resin composition pellet of Comparative Example 3 contained 100 g (99.9 mass%) of polypropylene (2) and 0.12 g (0.1 mass%) of a fragrance.
  • Example 4 20 g of pellets of polypropylene (1) were placed in a 300 mL eggplant type flask, and 6.0 mL of a 20 mass% heptane solution of hinokitiol was added. Then, using a rotary evaporator, the flask was rotated at a rotational speed of 120 times / minute under normal temperature (23 ° C.) for 1 hour. The obtained resin composition pellet was washed with 50 mL of ethanol and then dried under reduced pressure at 60 ° C. for 10 hours. It was 20.10 g when the mass of the resin composition pellet was measured.
  • the resin composition pellet of Example 4 contains 20 g (99.5% by mass) of polypropylene (1) and 0.10 g (0.5% by mass) of hinokitiol, and polypropylene (1) is impregnated with hinokitiol. It had been.
  • the resin composition pellet had a smell of hinokitiol.
  • Comparative example 4 Resin composition pellets were obtained in the same manner as in Example 4 except that polypropylene (1) was changed to polypropylene (2) in Example 4. It was 20 g when the mass of the resin composition pellet was measured. That is, the resin composition pellet of Comparative Example 4 did not contain hinokitiol at all. The resin composition pellets showed almost no smell.

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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)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne une composition solide de résine à base de polypropylène qui comprend de 10 à 99,6 % en masse de résine à base de polypropylène (A) ayant un endotherme de fusion (ΔH-D) de 0 à 80 J/g et de 0,4 à 90 % en masse d'additif (B) qui est liquide à 23 °C, l'endotherme de fusion (ΔH-D) étant obtenu à partir d'une courbe d'endotherme de fusion obtenue avec un calorimètre à balayage différentiel (ACD) en maintenant un échantillon sous une atmosphère d'azote à -10 °C durant 5 minutes puis en chauffant l'échantillon à 10 °C/min.
PCT/JP2018/025621 2017-07-06 2018-07-06 Composition solide de résine à base de polypropylène WO2019009389A1 (fr)

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CN115052933A (zh) * 2020-04-03 2022-09-13 株式会社Tbm 用于制造延伸片材的树脂组合物、延伸片材以及延伸片材的制造方法

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KR102129411B1 (ko) * 2019-07-26 2020-07-03 (주)몰리테크 합성수지와 오일을 포함하는 펠렛

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JPS4824016B1 (fr) * 1969-06-23 1973-07-18
JPH08506612A (ja) * 1993-02-11 1996-07-16 ミネソタ マイニング アンド マニュファクチャリング カンパニー ポリマーの含浸法
JP2011021137A (ja) * 2009-07-17 2011-02-03 Sumitomo Chemical Co Ltd ポリプロピレン無延伸フィルムの製造方法
JP2011052123A (ja) * 2009-09-02 2011-03-17 Sumitomo Chemical Co Ltd ポリプロピレン系樹脂組成物および延伸フィルム
JP2017071680A (ja) * 2015-10-06 2017-04-13 信越ポリマー株式会社 摺動材料、摺動部材、複合部材及び複合部材の製造方法

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JPS4824016B1 (fr) * 1969-06-23 1973-07-18
JPH08506612A (ja) * 1993-02-11 1996-07-16 ミネソタ マイニング アンド マニュファクチャリング カンパニー ポリマーの含浸法
JP2011021137A (ja) * 2009-07-17 2011-02-03 Sumitomo Chemical Co Ltd ポリプロピレン無延伸フィルムの製造方法
JP2011052123A (ja) * 2009-09-02 2011-03-17 Sumitomo Chemical Co Ltd ポリプロピレン系樹脂組成物および延伸フィルム
JP2017071680A (ja) * 2015-10-06 2017-04-13 信越ポリマー株式会社 摺動材料、摺動部材、複合部材及び複合部材の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115052933A (zh) * 2020-04-03 2022-09-13 株式会社Tbm 用于制造延伸片材的树脂组合物、延伸片材以及延伸片材的制造方法
CN115052933B (zh) * 2020-04-03 2023-07-04 株式会社Tbm 用于制造延伸片材的树脂组合物、延伸片材以及延伸片材的制造方法

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