WO2019009389A1 - Solid polypropylene-based resin composition - Google Patents

Solid polypropylene-based resin composition 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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French (fr)
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/en

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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.

Abstract

A solid polypropylene-based resin composition which comprises 10-99.6 mass% polypropylene-based resin (A) having a melting endotherm (ΔH-D) of 0-80 J/g and 0.4-90 mass% additive (B) that is liquid at 23°C, the melting endotherm (ΔH-D) being obtained from a melting-endotherm curve obtained with a differential scanning calorimeter (DSC) by keeping a specimen in a nitrogen atmosphere at -10°C for 5 minutes and then heating the specimen at 10°C/min.

Description

固体状ポリプロピレン系樹脂組成物Solid polypropylene-based resin composition
　本発明は、固体状ポリプロピレン系樹脂組成物に関し、好ましくはポリプロピレン系マスターバッチペレットに関する。 The present invention relates to solid polypropylene-based resin compositions, preferably to polypropylene-based masterbatch pellets.
　熱可塑性樹脂には、種々のプラスチック用添加剤が配合されている。多くの場合、プラスチック用添加剤は、粉体や液体状であることが多く、ハンドリング性が悪い。また、ホットメルト接着剤やエラストマーコンパウンド製品において樹脂成分と可塑剤であるオイル成分とを配合する際に、オイル等の液体状の添加剤を配合する添加順序や添加量に不備があると、混練機内で、オイル成分がスクリューに纏わりつき、せん断力が樹脂に伝わらず、いわゆる「すべり現象」のため樹脂成分が混合されないという不具合が発生する場合がある。このように、常温で液体の添加剤を配合する際には特別な配慮を行う必要がある。そのため、添加剤のハンドリング性の問題や添加順序の問題を解消する観点から、熱可塑性樹脂に対して比較的高濃度にプラスチック用添加剤を含有するマスターバッチペレットを予め製造し、当該マスターバッチペレットを熱可塑性樹脂に添加する方法が知られている。
　特許文献１には、プラスチック用添加剤を１０～９５質量％、特定の条件を満たすオレフィン系重合体を１～５０質量％及び担体用ポリオレフィン樹脂を１～８９質量％の割合で含有するマスターバッチ組成物が開示されている。この特許文献１に開示されたマスターバッチ組成物によって、プラスチック用添加剤を添加する際のハンドリング性を向上することができる。
　特許文献２には、示差走査熱量計（ＤＳＣ）で測定した融解吸熱量ΔＨ－Ｄが０～８０Ｊ／ｇのオレフィン系重合体を含む油吸着用部材及び示差走査熱量計（ＤＳＣ）で測定した融解吸熱量ΔＨ－Ｄが０～８０Ｊ／ｇのオレフィン系重合体を含有する、可染性ポリオレフィン組成物が開示されている。この特許文献２に開示された組成物によって、吸油性能がより高い油吸着用部材、それを用いた繊維製品及び油吸着方法及び、ポリエステル等の異種高分子を混合することなく、染色性に優れた可染性ポリオレフィン組成物及び可染性成形体、並びにその染色方法が提供される。 The thermoplastic resin contains various additives for plastics. In many cases, additives for plastics are often in the form of powder or liquid, and their handling is poor. In addition, when 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. In the machine, 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". Thus, special considerations need to be taken when formulating additives that are liquid at ambient temperature. Therefore, from the viewpoint of solving the problem of the handling property and the order of addition of the additives, masterbatch pellets containing the additive for plastic at relatively high concentration to the thermoplastic resin are manufactured in advance, and the masterbatch pellets Methods are known for adding to thermoplastics.
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.
In Patent Document 2, an oil-adsorbing member containing an olefin polymer having a melting endotherm ΔH-D of 0 to 80 J / g measured by a differential scanning calorimeter (DSC) and a measurement by a differential scanning calorimeter (DSC) A dyeable polyolefin composition is disclosed that contains an olefin polymer having a melting endotherm ΔH-D of 0 to 80 J / g. By the composition disclosed in this patent document 2, the member for oil adsorption having higher oil absorption performance, the fiber product and the oil adsorption method using it, and the dyeability are excellent without mixing different polymers such as polyester. A dyeable polyolefin composition and a dyeable molded body, and a method for dyeing the same are provided.
特開２００６－１７６７５０号公報Japanese Patent Application Publication No. 2006-176750 特開２０１５－１４４９９１号公報JP, 2015-144991, A
　マスターバッチ組成物は一般に溶融混練により製造される。特許文献１では、その製造方法は特に限定はされないものの、二軸押出機などによる溶融混練が例示されている。この際、プラスチック用添加剤が常温で液体状の添加剤である場合、添加剤を含有するマスターバッチを製造する際にも、前述の「すべり現象」のため、そのままではオレフィン系重合体などと均一に混練しにくくマスターバッチを製造し難いという問題があることを見出した。
　また、マスターバッチを溶融混練により作成する際にはオレフィン系重合体の融点以上とする必要がある。特に特許文献１では担体用ポリオレフィン樹脂を配合することから混練温度を高くせざるを得ない。本発明者らは、常温で液体状の添加剤は高温下で反応や揮発が起こりやすいため、そのような液体状添加剤を含むマスターバッチを作成する際には、マスターバッチ製造時の混練温度でプラスチック用添加剤が反応して変質したり、揮発して所定量配合されなかったりする場合があることを見出した。
　また、特許文献２には、液体状の添加剤を含むハンドリング性に優れた固体状樹脂組成物やこれを用いたマスターバッチペレットについては開示が無い。 Masterbatch compositions are generally manufactured by melt-kneading. In patent document 1, although the manufacturing method in particular is not limited, the melt-kneading by a twin screw extruder etc. is illustrated. Under the present circumstances, when the additive for plastics is a liquid additive at normal temperature, also when manufacturing 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.
Moreover, when producing a masterbatch by melt-kneading, it is necessary to make it more than the melting point of an olefin polymer. In particular, in 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.
In addition, 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.
　したがって、本発明が解決しようとする課題は、室温で液体状の添加剤を含むハンドリング性に優れた固体状樹脂組成物（好ましくはマスターバッチペレット）を提供することである。 Therefore, 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.
　本願開示は、以下に関する。
＜１＞示差走査型熱量計（ＤＳＣ）を用い、試料を窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で昇温させることにより得られた融解吸熱カーブから得られる融解吸熱量（ΔＨ－Ｄ）が０Ｊ／ｇ以上８０Ｊ／ｇ以下であるポリプロピレン系樹脂（Ａ）１０質量％以上９９．６質量％以下、及び２３℃において液体状である添加剤（Ｂ）０．４質量％以上９０質量％以下を含む固体状ポリプロピレン系樹脂組成物。
＜２＞前記ポリプロピレン系樹脂（Ａ）が下記（１）を満たす、上記＜１＞に記載の固体状ポリプロピレン系樹脂組成物。
（１）示差走査型熱量計（ＤＳＣ）を用い、試料を窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で昇温させることにより得られた融解吸熱カーブの最も高温側に観測されるピークトップとして定義される融点（Ｔｍ－Ｄ）が、観測されないか又は０℃以上１２０℃以下である。
＜３＞前記ポリプロピレン系樹脂（Ａ）が、プロピレン単独重合体であるか、又はエチレン及び炭素数４～３０のα－オレフィンからなる群より選ばれる少なくとも１つの構成単位を０モル％を超え２０モル％以下含むプロピレン系共重合体である、上記＜１＞又は＜２＞に記載の固体状ポリプロピレン系樹脂組成物。
＜４＞前記添加剤（Ｂ）が、粘度調整剤、可塑剤、結晶核剤、結晶化速度調整剤、滑剤、離型剤、強度向上剤、架橋剤、分解剤、柔軟化剤、難燃剤、難燃助剤、スリップ剤、防曇剤、導電剤、帯電防止剤、熱伝導剤、発泡剤、着色剤、蛍光剤、香料、界面活性剤、防虫剤、酸化防止剤、老化防止剤、耐候剤、紫外線吸収剤、分解防止剤、防かび剤及び抗菌剤からなる群から選ばれる少なくとも１種である、上記＜１＞～＜３＞のいずれか１つに記載の固体状ポリプロピレン系樹脂組成物。
＜５＞上記＜１＞～＜４＞のいずれか１つに記載の固体状ポリプロピレン系樹脂組成物からなるペレット。
＜６＞前記ポリプロピレン系樹脂（Ａ）のペレット又はフレークを前記添加剤（Ｂ）に浸漬させて、前記添加剤（Ｂ）を前記ポリプロピレン系樹脂（Ａ）のペレット又はフレーク中に含浸させる工程を有する、上記＜１＞～＜４＞のいずれか１つに記載の固体状ポリプロピレン系樹脂組成物の製造方法。 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 (ΔH-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.
The solid-state polypropylene resin composition as described in said <1> in which <2> said polypropylene resin (A) satisfy | fills 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.
<3> The content of at least one structural unit selected from the group consisting of propylene homopolymers or ethylene and α-olefins having 4 to 30 carbon atoms in an amount of more than 0 mol% The solid polypropylene resin composition according to <1> or <2>, which is a propylene-based copolymer containing at most mol%.
<4> 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.
<5> 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.
　本発明によれば、室温で液体状の添加剤を含むハンドリング性に優れた固体状樹脂組成物（好ましくはマスターバッチペレット）を提供することができる。 According to the present invention, it is possible to provide a solid resin composition (preferably, a masterbatch pellet) excellent in handleability containing an additive which is liquid at room temperature.
　以下、本発明について詳細に説明する。なお、本明細書において、数値の記載に関する「Ａ～Ｂ」という用語は、「Ａ以上Ｂ以下」（Ａ＜Ｂの場合）又は「Ａ以下Ｂ以上」（Ａ＞Ｂの場合）を意味する。また、本発明において、好ましい態様の組み合わせは、より好ましい態様である。 Hereinafter, the present invention will be described in detail. In the present specification, 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.
　本発明の固体状ポリプロピレン系樹脂組成物は、特定のポリプロピレン系樹脂（Ａ）１０質量％以上９９．６質量％以下、及び２３℃において液体状である添加剤（Ｂ）０．４質量％以上９０質量％以下を含む。 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.
＜ポリプロピレン系樹脂（Ａ）＞
　本実施形態で用いるポリプロピレン系樹脂（Ａ）は、示差走査型熱量計（ＤＳＣ）を用い、試料を窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で昇温させることにより得られた融解吸熱カーブから得られる融解吸熱量（ΔＨ－Ｄ）が０Ｊ／ｇ以上８０Ｊ／ｇ以下である。融解吸熱量（ΔＨ－Ｄ）が８０Ｊ／ｇを超えると、液体状添加剤の含浸が不十分となる。このような観点から、融解吸熱量（ΔＨ－Ｄ）は、好ましくは７０Ｊ／ｇ以下、より好ましくは６０Ｊ／ｇ以下、更に好ましくは５０Ｊ／ｇ以下であり、そして、べたつきをより抑制する観点から、好ましくは１０Ｊ／ｇ以上、より好ましくは２０Ｊ／ｇ以上、更に好ましくは３０Ｊ／ｇ以上である。
　上記融解吸熱量（ΔＨ－Ｄ）は、熱量変化の無い低温側の点と熱量変化の無い高温側の点とを結んだ線をベースラインとして、ＤＳＣ測定により得られた融解吸熱カーブの最も高温側に観測されるピークを含むライン部分と当該ベースラインとで囲まれる面積を求めることで算出される。
　なお、融解吸熱量（ΔＨ－Ｄ）は、モノマー濃度や反応圧力を適宜調整することで制御することができる。 <Polypropylene resin (A)>
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 (ΔH-D) obtained from the melting endothermic curve is from 0 J / g to 80 J / g. When the melting endotherm (ΔH-D) exceeds 80 J / g, the impregnation of the liquid additive becomes insufficient. From such a viewpoint, the melting endotherm (ΔH-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 Preferably 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 (ΔH-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 (ΔH-D) can be controlled by appropriately adjusting the monomer concentration and the reaction pressure.
　ポリプロピレン系樹脂（Ａ）は、プロピレン単独重合体であってもよく、共重合体であってもよい。共重合体である場合、プロピレン単位の共重合比は、５０モル％を超え、好ましくは６０モル％以上、より好ましくは７０モル％以上、更に好ましくは９０モル％以上、更に好ましくは９５モル％以上である。共重合可能なモノマーとしては、エチレン及び炭素数４～３０のα－オレフィンからなる群より選ばれる少なくとも１つであり、具体例としては、エチレン、１－ブテン、１－ペンテン、１－ヘキセン、１－オクテン、１－デセン等が挙げられる。ポリプロピレン系樹脂（Ａ）が共重合体である場合、ポリプロピレン系樹脂（Ａ）は、エチレン及び炭素数４～３０のα－オレフィンからなる群より選ばれる少なくとも１つの構成単位を、０モル％を超え２０モル％以下含むことが好ましい。 The polypropylene resin (A) may be a propylene homopolymer or a copolymer. When it is 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 α-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. When 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 α-olefins having 4 to 30 carbon atoms. It is preferable to include more than 20 mol% or less.
　ポリプロピレン系樹脂（Ａ）は、下記（１）を満たすことが好ましい。
（１）示差走査型熱量計（ＤＳＣ）を用い、試料を窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で昇温させることにより得られた融解吸熱カーブの最も高温側に観測されるピークトップとして定義される融点（Ｔｍ－Ｄ）が、観測されないか又は０℃以上１２０℃以下である。 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.
　ポリプロピレン系樹脂（Ａ）の融点（Ｔｍ－Ｄ）は、液体状添加剤の含浸の観点から、観測されないか又は０℃以上１２０℃以下であることが好ましい。融点が観測される場合には、同様の観点から、より好ましくは３０℃以上、更に好ましくは３５℃以上、より更に好ましくは４０℃以上であり、そして、より好ましくは９０℃以下、更に好ましくは８５℃以下である。
　なお、融点は、モノマー濃度や反応圧力を適宜調整することで制御可能である。 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. When 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.
　また、ポリプロピレン系樹脂（Ａ）の極限粘度［η］は、液体状添加剤の含浸の観点から、好ましくは０．０１ｄＬ／ｇ以上、より好ましくは０．１０ｄＬ／ｇ以上、更に好ましくは０．３０ｄＬ／ｇ以上、より更に好ましくは０．４０ｄＬ／ｇ以上であり、そして、好ましくは１．８０ｄＬ／ｇ以下、より好ましくは１．５０ｄＬ／ｇ以下、更に好ましくは１．３０ｄＬ／ｇ以下、より更に好ましくは１．２０ｄＬ／ｇ以下、より更に好ましくは１．００ｄＬ／ｇ以下である。 The intrinsic viscosity [η] 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.
　なお、上記極限粘度［η］は、１３５℃のテトラリン中、ウベローデ型粘度計で還元粘度（ηSP／ｃ）を測定し、下記式（ハギンスの式）を用いて算出される。
　　ηSP／ｃ＝［η］＋Ｋ［η］2ｃ
　　ηSP／ｃ（ｄＬ／ｇ）：還元粘度
　　［η］（ｄＬ／ｇ）：極限粘度
　　ｃ（ｇ／ｄＬ）：ポリマー粘度
　　Ｋ＝０．３５（ハギンス定数） The intrinsic viscosity [極限] is calculated by using a Ubbelohde viscometer to measure the reduced viscosity (η SP / c) in tetralin at 135 ° C., and using the following equation (Hagins' equation).
η SP / c = [η] + K [η] 2 c
SP SP / c (dL / g): Reduced viscosity [η] (dL / g): Intrinsic viscosity c (g / dL): Polymer viscosity K = 0.35 (Huggins constant)
　ポリプロピレン系樹脂（Ａ）の重量平均分子量（Ｍｗ）は、液体状添加剤の含浸の観点から、好ましくは３０，０００以上、より好ましくは５０，０００以上、更に好ましくは７０，０００以上であり、そして、好ましくは２００，０００以下、より好ましくは１８０，０００以下、更に好ましくは１５０，０００以下である。 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.
　ポリプロピレン系樹脂（Ａ）の分子量分布（Ｍｗ／Ｍｎ）は、液体状添加剤の含浸の観点から、好ましくは３．０以下、より好ましくは２．８以下、更に好ましくは２．６以下、より更に好ましくは２．５以下であり、そして、好ましくは１．５以上、より好ましくは１．６以上、更に好ましくは１．７以上、より更に好ましくは１．８以上である。 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.
　上記の重量平均分子量（Ｍｗ）及び分子量分布（Ｍｗ／Ｍｎ）は、ゲルパーミエイションクロマトグラフィ（ＧＰＣ）測定により求められる。重量平均分子量は、下記の装置及び条件で測定したポリスチレン換算の重量平均分子量であり、分子量分布は、同様にして測定した数平均分子量（Ｍｎ）及び上記重量平均分子量より算出した値である。
＜ＧＰＣ測定装置＞
カラム　　　　　：東ソー（株）製「ＴＯＳＯ　ＧＭＨＨＲ－Ｈ（Ｓ）ＨＴ」
検出器　　　　　：液体クロマトグラム用ＲＩ検出　ウォーターズ・コーポレーション製「ＷＡＴＥＲＳ　１５０Ｃ」
＜測定条件＞
　溶媒　　　　　：１，２，４－トリクロロベンゼン
　測定温度　　　：１４５℃
　流速　　　　　：１．０ｍＬ／分
　試料濃度　　　：２．２ｍｇ／ｍＬ
　注入量　　　　：１６０μＬ
　検量線　　　　：Ｕｎｉｖｅｒｓａｌ　Ｃａｌｉｂｒａｔｉｏｎ
　解析プログラム：ＨＴ－ＧＰＣ（Ｖｅｒ．１．０） 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 μL
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver. 1.0)
　ポリプロピレン系樹脂（Ａ）のメルトフローレート（ＭＦＲ）は、液体状添加剤の含浸の観点から、好ましくは１ｇ／１０分以上、より好ましくは７ｇ／１０分以上、更に好ましくは１０ｇ／１０分以上であり、そして、好ましくは５０００ｇ／１０分以下、より好ましくは４０００ｇ／１０分以下、更に好ましくは３０００ｇ／１０分以下である。ポリプロピレン系樹脂（Ａ）のＭＦＲの測定方法は、ＩＳＯ　１１３３：１９９７に準拠し、温度２３０℃、荷重２１．１８Ｎの条件で測定される。 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.
　ポリプロピレン系樹脂（Ａ）としては市販品を用いることができる。具体例としては、「Ｌ－ＭＯＤＵ」（登録商標）（出光興産（株）製）の「Ｓ４００」、「Ｓ６００」、「Ｓ９０１」が挙げられる。非晶質ポリα－オレフィンの市販品として、ＲＥＸｔａｃ，ＬＬＣ社製の「ＡＰＡＯ」、エボニック社製の「Ｖｅｓｔｏｐｌａｓｔ」等も挙げられる（いずれも商品名）。プロピレン系エラストマーの市販品として、三井化学（株）製の「タフマーＸＭ」、「タフマーＰＮ」、「タフマーＳＮ」；住友化学（株）製の「タフセレン」；（株）プライムポリマー製の「プライムＴＰＯ」；ダウ・ケミカル（株）製の「Ｖｅｒｓｉｆｙ」；エクソンモービル社製の「Ｖｉｓｔａｍａｘｘ」、「Ｌｉｎｘａｒ」、クラリアント社製の「Ｌｉｃｏｃｅｎｅ」；バセル社製の「Ａｄｆｌｅｘ」等も挙げられる（いずれも商品名）。 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-α-olefin include “APAO” manufactured by REXtac, LLC, “Vestoplast” manufactured by Evonik, etc. (all are trade names). 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).
＜添加剤（Ｂ）＞
　本実施形態で用いる添加剤（Ｂ）は、２３℃において液体状である。
　添加剤（Ｂ）は、熱可塑性樹脂の成形性改良、物性改良、改質、機能性付与、安定化等の目的で用いられるものであり、２３℃において液体状であれば特に限定されない。なお、本発明における添加剤（Ｂ）としては、それ自体が２３℃において液体状である添加剤であってもよく、添加剤を後述の溶剤（Ｃ）に溶解したものを液体状添加剤として使用することもできる。本発明の樹脂組成物において、添加剤（Ｂ）は、ポリプロピレン系樹脂（Ａ）に含浸していることが好ましい。 <Additive (B)>
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. In the resin composition of the present invention, the additive (B) is preferably impregnated in the polypropylene resin (A).
　添加剤（Ｂ）としては、例えば、成形性改良剤、物性改良剤、機能性付与剤及び安定化剤からなる群から選ばれる少なくとも１種であることが好ましい。 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.
　成形性改良剤としては、粘度調整剤（増粘剤、減粘剤）、可塑剤、結晶核剤、結晶化速度調整剤、滑剤、離型剤等が挙げられる。
　増粘剤としては、糖重合体、タンパク質、その誘導体を好ましく例示できる。例えば、アミロース、セルロース、コラーゲン、その誘導体として、グルコースを側鎖に有するアミロペクチン、キシロースやガラクトースを側鎖に有するキシログルカンを好ましく例示できる。デンプンやゼラチンとして添加されてもよい。デンプンは、片栗粉として市販されているものを用いることができる。また、ポリグリセリン又はその誘導体、アミン価を有する水溶性樹脂、例えば、アミン価を有するポリアクリル酸誘導体、ポリアクリルアミド誘導体、アミン価を有するポリビニルアルコール誘導体等を好ましく挙げることができる。
　減粘剤としては、ミツロウ、カルナバロウ、鯨ロウ、ラノリン、液体状ラノリン、還元ラノリン、硬質ラノリン、カンデリラロウ、シェラックロウ、ライスワックス、スクワレン、スクワラン、プリスタン、米糠ロウ、サトウキビロウ、パームロウ、イボタロウ、羊毛ロウ、モンタンロウ等のロウ類又はこれらロウ類の水素添加物又はその誘導体；パラフィン（パラフィンワックス）、流動パラフィン、ワセリン、ワックス、オゾケライト、セレシン、マイクロクリスタリンワックス、ミネラルオイル等の鉱物油類又は水素添加物又はその誘導体、パラフィン系鉱油、ナフテン系鉱油、芳香族系鉱油等が挙げられる。
　可塑剤としては、フタル酸系、脂肪族系、リン酸系、アジピン酸系、セバシン酸系、アゼライン酸系、クエン酸系等のエステル系化合物；ポリエステル系、エポキシ系等の主にポリ塩化ビニル用可塑剤として知られている可塑剤；パラフィン系、芳香族系、ナフテン系の鉱物系油；植物系脂肪油；シリコーンオイル、エステル系等の合成油等が挙げられる。
　結晶核剤としては、溶解型でも塩型でもよく、ノニトールやジベンジリデンソルビトール系等のソルビトール系造核剤、リン系造核剤、カルボン酸金属塩系造核剤、ポリマー系造核剤、無機化合物等が挙げられる。
　結晶化速度調整剤としては、亜鉛、コバルト、カルシウム塩、ニグロシン等が挙げられる。
　滑剤としては、流動パラフィン、パラフィンワックス、マイクロクリスタリンワックス、ワセリン、フィッシャートロプシュ系ワックス等のワックス系滑剤；ミネラルオイル、ポリエチレンワックスやポリプロピレンワックス等のポリオレフィン系ワックス、モンタンワックス、ビートワックス、セレシンワックス、植物ロウ、動物ロウ；ステアリン酸やヒドロキシステアリン酸等の脂肪酸系滑剤；オレイン酸アミド、ステアリン酸アミド、エルカ酸アミド、ラウリン酸アミド、パルミチン酸アミド、ベヘン酸アミド、エチレンビスステアロアミド等の脂肪酸アミド；脂肪酸メチル、ブチルステアレート、ブチルオレエート、イソプロピルミリステート、ラウリルラウレート、ネオペンチルポリオール脂肪酸等の脂肪酸エステル；ステアリルアルコール、セチルアルコール等のアルコール系滑剤；金属石鹸等が挙げられる。
　離型剤としては、ステアリン酸ブチル等の高級脂肪酸の低級アルコールエステル、ひまし油等の脂肪酸の多価アルコールエステル、流動パラフィン、シリコーン系離型剤等が挙げられる。 Examples of moldability improvers include viscosity modifiers (thickeners, viscosity reducing agents), plasticizers, crystal nucleating agents, crystallization rate modifiers, lubricants, and mold release agents.
As a thickener, a sugar polymer, protein, and its derivative can be illustrated preferably. For example, amylose, cellulose, collagen, derivatives thereof such as amylopectin having glucose in the side chain, xyloglucan having xylose and galactose in the side chain can be preferably exemplified. It may be added as starch or gelatin. As starch, commercially available starch as starch can be used. Further, 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.
As a viscosity reducing agent, beeswax, carnauba wax, beeswax, lanolin, liquid lanolin, reduced lanolin, hard lanolin, candelilla wax, shellac wax, rice wax, squalene, squalane, pristane, rice bran wax, sugar cane wax, palm wax, ivota wax, wool Waxes, waxes such as montan wax or hydrogenated products of these waxes or derivatives thereof; paraffins (paraffin wax), liquid paraffin, petrolatum, wax, ozokerite, ceresin, microcrystalline waxes, mineral oils such as mineral oil or hydrogenation Or derivatives thereof, paraffinic mineral oil, naphthenic mineral oil, aromatic mineral oil and the like.
As a plasticizer, 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.
Examples of the crystallization rate modifier include zinc, cobalt, calcium salt, nigrosine and the like.
Examples of lubricants 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. 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.
　物性改良剤としては、強度向上剤、架橋剤、分解剤、柔軟化剤、難燃剤、難燃助剤、カップリング剤、感光剤、光重合開始剤、硬化剤等が挙げられる。
　強度向上剤としては、無機充填剤や有機充填剤が挙げられ、でんぷんやセルロース及びその誘導体、グリセリン系、グルコール系、高分子繊維等が挙げられる。
　架橋剤としては、例えば一分子中に複数のビニル基を有する有機化合物が用いられ、ジビニルベンゼン、トリメチロールプロパントリメタクリレート、メチルメタクリレート、１，９－ノナンジオールジメタクリレート、１，１０－デカンジオールジメタクリレート、トリメリット酸トリアリルエステル、トリアリルイソシアヌレート、エチルビニルベンゼン、ネオペンチルグリコールジメタクリレート、１，２，４－ベンゼントリカルボン酸トリアリルエステル、１，６－ヘキサンジオールジメタクリレート、ラウリルメタクリレート、ステアリルメタクリレート、フタル酸ジアリル、テレフタル酸ジアリル、イソフタル酸ジアリル等が挙げられる。また、イオウやオキシム類、アニリン類、ニトロソベンゼン、ジフェニルグアジン、トリメチロールプロパン、イミド類等も挙げられる。
　分解剤としては、過酸化物が挙げられ、従来からポリプロピレン系樹脂を低分子量化する目的、高密度ポリエチレン（ＨＤＰＥ）や低密度ポリエチレン（ＬＤＰＥ）を軽度に架橋する目的、これらのポリオレフィン樹脂に不飽和酸をグラフトする目的等で使用されている過酸化物であればいずれも使用可能であり、ジアシルパーオキサイド類、パーオキシジカーボネート類、パーオキシエステル類、パーオキシケタール類、ジアルキルパーオキサイド類、ハイドロパーオキサイド類等が挙げられる。
　柔軟化剤としては、エチレンやプロピレン等とα－オレフィンの共重合体等からなるオレフィン系エラストマーやプラストマー、プロセスオイル、潤滑油、パラフィン、流動パラフィン、ポリエチレンワックス、ポリプロピレンワックス、ポリブテン、アスファルト、ワセリン、コールタール、ひまし油等の脂肪油系軟化剤、蜜蝋、カルナバロウ、ラノリン等のロウ類、パルミチン酸等の脂肪酸及びその脂肪酸塩、エステル系軟化剤、マイクロクリスタリンワックス、フィッシャートロプシュワックス、液状ポリブタジエンや液状ポリイソプレンとその水素化物や誘導体等が挙げられる。
　難燃剤としてはリン系、ハロゲン系、塩素系、臭素系等の有機系難燃剤や、水酸化アルミニウムやアンチモン系、水酸化マグネシウム系等の無機系難燃剤が挙げられる。
　カップリング剤としては、シラン系、チタネート系、アルミニウム系、ジルコニウム系等のカップリング剤が挙げられる。
　感光剤としては、重クロム酸塩系、ビスアジド化合物系、ナフトキノンジアド系、ジアゾレジン系等の感光剤が挙げられる。
　光重合開始剤としては、アセトフェノン系、ベンゾイン系、ベンゾフェノン系、チオキサントン系、アミン系、リン系、ジカルボニル化合物系等のラジカル重合開始剤や、カチオン系重合開始剤が挙げられる。
　硬化剤としては、トリエチレンテトラミンを代表とする鎖状脂肪族アミン；イソフォロンジアミンを代表とする環状脂肪族アミン；ｍ－キシリレンジアミン、ポリアミドアミン、ジアミノジフェニルメタンに代表される芳香族アミン等のアミン系硬化剤；メチルテトラヒドロ無水フタル酸等の酸無水物系硬化剤；ノボラック型フェノール等のフェノール樹脂系硬化剤；メルカプタン系硬化剤等が挙げられる。
　このほか、重合性のモノマーが挙げられる。特に限定はされないが、ラジカル重合性のモノマーが好ましく、一置換エチレン、１，１－二置換エチレン、１，２－二置換エチレン、ジエン化合物が挙げられる。具体的には、ビニル化合物として、スチレン誘導体、アクリル酸エステル、アクリロニトリル、アクリルアミド誘導体などの共役モノマー、塩化ビニル等のハロゲン化ビニルやビニルエステル、Ｎ－ビニルピロリドン等のビニルアミド類、α－オレフィン、ビニルエーテル、アリル化合物等の非共役モノマーが挙げられる。また、ビニリデン化合物として、メタクリル酸エステル、メタクリルアミド誘導体、塩化ビニリデン、フッ化ビニリデン、α－メチルスチレン、イソブチレン等が挙げられる。そのほか、Ｎ－アルキル置換マレイミド等のマレイミド誘導体、アセナフチレン、ビニレンカーボネート、無水マレイン酸、無水フタル酸、１，３－ブタジエン、イソプレン、クロロプレン、ジメタクリレート、ジビニルベンゼン、ジメタクリルアミド、ジアリルアンモニウム塩等も挙げられる。 Examples of the physical property improver 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.
As the 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.
As the 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. Further, sulfur, oximes, anilines, nitrosobenzenes, diphenyl guadine, trimethylolpropane, imides and the like can also be mentioned.
As a decomposing agent, 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.
As a softener, olefin elastomers and plastomers comprising ethylene or propylene and a copolymer of α-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.
Examples of the flame retardant include organic flame retardants such as phosphorus, halogen, chlorine and bromine, and inorganic flame retardants such as aluminum hydroxide, antimony and magnesium hydroxide.
As a coupling agent, coupling agents, such as a silane type, a titanate type, an aluminum type, a zirconium type, are mentioned.
Examples of the photosensitizer include photosensitizers such as a dichromate type, a bisazide compound type, a naphthoquinone diad type, and a diazoresin type.
Examples of the photopolymerization initiator 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.
Examples of 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; 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.
Besides, 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. Specifically, as 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, α-olefins and vinyl ethers And non-conjugated monomers such as allyl compounds. Further, examples of the vinylidene compound include methacrylic acid esters, methacrylamide derivatives, vinylidene chloride, vinylidene fluoride, α-methylstyrene, isobutylene and the like. In addition, 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.
　機能性付与剤としては、摺動剤（スリップ剤）、防曇剤、導電剤、帯電防止剤、熱伝導剤、発泡剤、着色剤（染料、顔料）、蛍光剤、香料、消臭剤、界面活性剤、防虫剤、殺虫剤、防菌・防かび剤等が挙げられる。
　防曇剤としては、カチオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤、ノニオン系界面活性剤等が挙げられる。
　帯電防止剤又は界面活性剤としては、アニオン系、カチオン系等のイオン系界面活性剤や、非イオン系界面活性剤、両性界面活性剤等が挙げられる。
　発泡剤としては、アゾ化合物系、スルホヒドラジド系、ニトロソ系等の有機系発泡剤；重炭酸ナトリウムや絨毯酸アンモニウム等の無機系発泡剤；プロパン、ｎ－ブタン、ｉｓｏ－ブタン、ｎ－ペンタン、ｉｓｏ－ペンタン、シクロペンタン、ヘキサン、ヘプタン、ベンゼン等の脂肪族炭化水素；１，２－ジクロロテトラフルオロエタン、１－クロロテトラフルオロエタン、１，１－ジフルオロエタン、１，１，１，２－テトラフルオロエタン等のハロゲン化炭化水素系ガス；ＨＦＣ１５２ａ、ＨＣＦＣ１４２ｂ、ＨＦＣ１３４ａ等の代替フロンガスを主とするハロゲン化炭化水素化合物類等が挙げられる。
　染料としては、アゾ系やキノフタロン系、アントラキノン系等の分散染料や、直接染料、酸性染料、カチオン染料等が挙げられる。
　顔料としては、フタロシアニンブルー及びグリーン顔料、ジアリリドイエロー及びオレンジ顔料、トルイジンレッド、リソ（ｌｉｔｈｏ）赤、ナフトールレッド等のアゾ型赤色及び黄色顔料、並びに茶色顔料等の有機顔料；酸化鉄（黄色、赤色、茶色又は黒色）、フェロシアン化第二鉄アンモニウム（青色）、マンガンバイオレット、ウルトラマリンブルー、酸化クロム（緑色）、タルク、レシチン変性タルク、ゼオライト、カオリン、レシチン変性カオリン、二酸化チタン（白色）、酸化亜鉛、及びそれらの混合物等の無機顔料；一次粒子の平均粒径が１μｍ以下もしくは０．１μｍ以下の硫酸バリウムや炭酸カルシウム等の透明顔料に類するものが挙げられる。
　香料としては、アセチルセドレン、アミルシンナムアルデヒド、アリルアミルグリコレート、β－イオノン、イソイースーパー、イソブチルキノリン、イリス油、イロン、インドール、イランイラン油、ウンデカナール、ウンデセナール、γ－ウンデカラクトン、エストラゴール、オイゲノール、オークモス、オポパナックスレジノイド、オレンジ油、オイゲノール、オーランチオール、ヒノキチオール、ガラクソリッド、カルバクロール、Ｌ－カルボン、カンファー、キャノン、キャロットシード油、クローブ油、ケイヒ酸メチル、ゲラニオール、ゲラニルニトリル、酢酸イソボルニル、酢酸ゲラニル、酢酸ジメチルベンジルカルビニル、酢酸スチラリル、酢酸セドリル、酢酸テレピネル、酢酸ｐ－ｔ－ブチルシクロヘキシル、酢酸ベチベリル、酢酸ベンジル、酢酸リナリル、サリチル酸イソペンチル、サリチル酸ベンジル、サンダルウッド油、サンタロール、シクラメンアルデヒド、シクロペンタデカノリド、ジヒドロジャスモン酸メチル、ジヒドロミルセノール、ジャスミンアブソリュート、ジャスミンラクトン、ｃｉｓ－ジャスモン、シトラール、シトロネロール、シトロネラール、シナモンバーク油、１，８－シネオール、シンナムアルデヒド、スチラックスレジノイド、セダーウッド油、セドレン、セドロール、セロリシード油、タイム油、ダマスコン、ダマセノン、チモール、チュベローズアブソリュート、デカナール、デカラクトン、テルピネオール、γ－テルピネン、トリプラール、ネロール、ノナナール、２，６－ノナジエノール、ノナラクトン、パチョリアルコール、バニラアブソリュート、バニリン、バジル油、パチョリ油、ヒドロキシシトロネラール、α－ピネン、ピペリトン、フェネチルアルコール、フェニルアセトアルデヒド、プチグレン油、ヘキシルシンナムアルデヒド、ｃｉｓ－３－ヘキセノール、ペルーバルサム、ベチバー油、ベチベロール、ペパーミント油、ペパー油、ヘリオトロピン、ベルガモット油、ベンジルベンゾエート、ボルネオール、ミルレジノイド、ムスクケトン、メチルノニルアセトアルデヒド、γ－メチルヨノン、メントール、Ｌ－メントール、Ｌ－メントン、ユーカリ油、β－ヨノン、ライム油、ラベンダー油、Ｄ－リモネン、リナロール、リラール、リリアール、レモン油、ローズアブソリュート、ローズオキシド、ローズ油、ローズマリー油、各種精油等の合成香料及び天然香料並びに各種調合香料等が挙げられる。
　消臭剤としては、例えば、ジクロロイソシアヌル酸塩；イネ、松、ヒノキ、笹、柿、茶等の植物の抽出物；脱塩型ベタイン化合物；変性有機酸化合物；アルカノールアミン；安定化二酸化塩素；アルデヒド化合物；グリコールエーテル化合物；フィトンチッド系香料；低級脂肪族アルデヒド系香料等が挙げられる。
　防虫剤としては、ピレスロイド系化合物、ナフタレン系化合物、パラジクロロベンゼン系化合物、樟脳等が挙げられる。殺虫剤としては、ヒノキチオール、ヒバ油、アリルイソチオシアネート、プロピレングリコールモノメチルエーテル、エタノール、プロパノール、１．８―シネオール等が挙げられる。
　防菌・防かび剤としては、２－（４－チアゾリル）－ベンズイミダゾール、１０，１０’‐オキシビスフェノキサアルシン、Ｎ－（フルオロジクロロメチルチオ）－フタルイミド、２－ｎ－オクチル－４－イソチアゾリン－３‐オン、ビス（２－ピロジルチオ－１－オキシド）亜鉛、２，３，５，６－テトラクロロ－４－（メチルスルフォニル）ピリジン等が挙げられる。 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.
Examples of the antifogging agent include cationic surfactants, anionic surfactants, amphoteric surfactants, nonionic surfactants and the like.
Examples of the antistatic agent or surfactant include ionic surfactants such as anionic and cationic surfactants, nonionic surfactants and amphoteric surfactants.
As the foaming agent, 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.
Examples of the dye include disperse dyes such as azo dyes, quinophthalone dyes and anthraquinone dyes, direct dyes, acid dyes and cationic dyes.
As pigments, 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 μm or less or 0.1 μm or less.
As a flavoring agent, acetyl cedrene, amyl cinnamaldehyde, allyl amyl glycolate, β-ionone, isoe super, isobutyl quinoline, iris oil, ylone, indole, yylan oil, undecanal, undecenal, γ-undecanal, Estragole, Eugenol, Okemos, Opopax Resinoid, Orange Oil, Eugenol, Orlanthiol, Hinokitiol, Galac Solid, Carvacrol, L-Carvone, Camphor, Cannon, Carrot Seed Oil, Clove Oil, Methyl Cyanate, Geraniol, Geranylnitrile, isobornyl acetate, geranyl acetate, dimethylbenzylcarbinyl acetate, styrylyl acetate, sedryl acetate, heptyl acetate, p-t-butylcyclohexyl acetate, vetiver acetate Le, benzyl acetate, linalyl acetate, isopentyl salicylate, benzyl salicylate, sandalwood oil, santarol, cyclamenaldehyde, cyclopentadecanolide, methyl dihydrojasmonate, dihydromyrusenol, jasmine absolute, jasmine lactone, cis-jasmon, Citral, Citronellol, Citronellal, Cinnamon Burk Oil, 1,8-Cineole, Cinnamaldehyde, Stilax Resinoid, Sederwood Oil, Cedrene, Cedrol, Celery Seed Oil, Thyme Oil, Damascon, Damasenone, Thymol, Chubels Absolute, Decanoles, Decalactone, Terpineol, γ-Terpinene, Triplar, Nerol, Nonanal, 2,6-Nonadienol, Nonalactone, Patorial , Vanilla absolute, vanillin, basil oil, patchouli oil, hydroxycitronellal, α-pinene, piperitone, phenethyl alcohol, phenylacetaldehyde, petit glen oil, hexyl cinnamaldehyde, cis-3-hexenol, peru balsam, vetiver oil, Vetiberol, peppermint oil, pepper oil, heliotropin, bergamot oil, benzyl benzoate, borneol, myrresinoid, musk ketone, methylnonylacetaldehyde, γ-methylionone, menthol, L-menthol, L-menthol, eucalyptus oil, β-ionone, lime Synthesis of oil, lavender oil, D-limonene, linalool, rillal, liliar, lemon oil, rose absolute, rose oxide, rose oil, rosemary oil, various essential oils, etc. 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. Examples of insecticides 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.
　安定化剤としては、酸化防止剤、老化防止剤、耐候剤、光安定剤、熱や加水分解による主鎖切断等の分解防止剤、抗菌剤等が挙げられる。
　酸化防止剤又は老化防止剤としては、ホスファイト系、ラクトン系、フェノール系、イオウ系、アミン系、チオエーテル系等の酸化防止剤又は老化防止剤が挙げられる。
　光安定剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、シアノアクリレート系、ニッケルキレート系等の紫外線吸収剤、ヒンダードアミン系光安定剤（ＨＡＬＳ）等が挙げられる。
　抗菌剤としては、オクチルトリメチルアンモニウムクロライド、ジデシルジメチルアンモニウムグルコン酸、クロルヘキシジン、グルコン酸クロルヘキシジン、アリルイソチオシアネート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル等が挙げられる。 Examples of the stabilizer 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.
Examples of 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).
Examples of the antibacterial agent 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.
　添加剤（Ｂ）としては、粘度調整剤、可塑剤、結晶核剤、結晶化速度調整剤、滑剤、離型剤、強度向上剤、架橋剤、分解剤、柔軟化剤、難燃剤、難燃助剤、スリップ剤、防曇剤、導電剤、帯電防止剤、熱伝導剤、発泡剤、着色剤、蛍光剤、香料、界面活性剤、防虫剤、酸化防止剤、老化防止剤、耐候剤、紫外線吸収剤、分解防止剤、防かび剤及び抗菌剤からなる群から選ばれる少なくとも１種であることが好ましい。
　これらの添加剤は１種単独でも２種以上の組合せであってよい。例えば特開平１１－８０２６２号公報に記載されているように、過酸化物及び主鎖切断防止剤を併用することも可能である。 As an 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 Auxiliary agents, slip agents, anti-fog agents, conductive agents, antistatic agents, heat conductive agents, foaming agents, colorants, fluorescent agents, fragrances, surfactants, insect repellents, antioxidants, anti-aging agents, weathering agents, It is preferable that it is at least one selected from the group consisting of a UV absorber, an antidegradant, a fungicide and an antibacterial agent.
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.
＜溶剤（Ｃ）＞
　上述のとおり、本発明における添加剤（Ｂ）としては、添加剤を溶剤（Ｃ）に溶解したものを液体状添加剤として使用することもできる。
　溶剤（Ｃ）としては任意の溶剤を使用することができ、有機溶剤や水系溶剤を挙げることができる。また、有機溶剤としては、ヘキサン、ヘプタン等の脂肪族炭化水素系溶剤；ベンゼン、トルエン、キシレン等の芳香族系溶剤；クロロホルム、トリクロロメタン等のハロゲン系溶剤；メタノール、エタノール等のアルコール系溶剤；アセトン等のケトン系溶剤；ジエチルエーテル、テトラヒドロフラン（ＴＨＦ）、ジオキサン等のエーテル系溶剤等を挙げることができる。 <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. In addition, as organic solvents, 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.
　本発明の固体状ポリプロピレン系樹脂組成物において、ポリプロピレン系樹脂（Ａ）の含有量は、樹脂組成物のハンドリング性の観点から、１０質量％以上、好ましくは４０質量％以上、より好ましくは７０質量％以上であり、そして、９９．６質量％以下、好ましくは９８質量％以下である。また、添加剤（Ｂ）の含有量は、樹脂組成物の成形性、物性、機能性等の観点から、０．４質量％以上、好ましくは２質量％以上であり、そして、９０質量％以下、好ましくは６０質量％以下、より好ましくは３０質量％以下である。 In the solid polypropylene-based resin composition of the present invention, 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.
　本発明の固体状ポリプロピレン系樹脂組成物におけるポリプロピレン系樹脂（Ａ）及び添加剤（Ｂ）の合計含有量は、樹脂組成物１００質量％に対して、好ましくは７０質量％以上、より好ましくは８０質量％以上、更に好ましくは９０質量％以上である。 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.
　本発明の樹脂組成物は、本発明の効果を阻害しない範囲内で上記以外の材料を含んでもよい。例えば、熱可塑性樹脂や、固体添加剤であるフィラー等を含んでもよい。熱可塑性樹脂としては、例えば、ポリスチレン系樹脂、ポリオレフィン系樹脂、ポリアクリル系樹脂、ポリカーボネート系樹脂、ポリスルホン系樹脂、セルロース系樹脂、ポリエステル系樹脂、（メタ）アクリル酸エステル・スチレン共重合樹脂、酢酸ビニル樹脂、エチレン・酢酸ビニル共重合樹脂、ＡＢＳ樹脂、スチレン系エラストマー樹脂、エチレンプロピレンジエン共重合体樹脂、ポリブタジエン、天然ゴム、合成ゴム、ポリアミド樹脂、ポリビニルブチレート樹脂、塩化ビニル樹脂、シリコーン樹脂、フェノール樹脂、尿素樹脂、メラミン樹脂、ロジン及びその誘導体、テルペン樹脂、テルペンフェノール樹脂、芳香族変性テルペン樹脂、水素化テルペン樹脂、脂肪族系石油樹脂、芳香族系石油樹脂、共重合系石油樹脂、脂環式系石油樹脂、水素化石油樹脂、アルキルフェノール樹脂等が挙げられる。 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. For example, a thermoplastic resin, a filler that is a solid additive, and the like may be included. As 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, hydrogenated terpene resin, aliphatic petroleum resin, aromatic petroleum resin, copolymer petroleum resin, Alicyclic stone Resins, hydrogenated petroleum resins, alkylphenol resins.
　本発明の樹脂組成物は、樹脂組成物のハンドリング性の観点から、固体状である。ただし、完全な固体に限定されず、ゲル状であってもよい。 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.
　本発明の固体状ポリプロピレン系樹脂組成物の形態は、樹脂組成物のハンドリング性の観点から、好ましくはペレット又はフレークであり、より好ましくはペレットである。本発明の固体状ポリプロピレン系樹脂組成物からなるペレットは、室温で液体状の添加剤を含み、ハンドリング性に優れ、マスターバッチペレットとして有用である。 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.
　本発明の固体状ポリプロピレン系樹脂組成物の製造方法は特に限定されないが、ポリプロピレン系樹脂（Ａ）のペレット又はフレークを添加剤（Ｂ）に浸漬させて、添加剤（Ｂ）をポリプロピレン系樹脂（Ａ）のペレット又はフレーク中に含浸させる工程を有する方法が好ましい。 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.
　一般的なマスターバッチの製造では、ポリオレフィンの融点以上に加熱してから添加剤を配合し、混練し、ペレット化する。しかしながら、室温で液体状の添加剤は、ポリオレフィンの融点以上で不安定な場合が多く、マスターバッチ製造時の混練温度でプラスチック用添加剤が反応して変質したり、揮発して所定量配合されなかったりする場合がある。これに対して、上記方法によれば、熱をかけて溶融混練する必要が無く、高温で揮発や反応しやすい添加剤（Ｂ）の変質や反応を抑制することができ、そのような添加剤（Ｂ）を含有するマスターバッチを製造することができる。
　ここで、一般的なポリオレフィンを添加剤（Ｂ）に浸漬させても、添加剤（Ｂ）はポリオレフィン中にはほとんど含浸されない。本発明に用いられるポリプロピレン系樹脂（Ａ）中に添加剤（Ｂ）が含浸する理由については解明されていないが、ポリプロピレン系樹脂（Ａ）は、一般的なポリオレフィンに比べて非晶質成分が多いことが関与していると推定される。 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. However, 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. On the other hand, according to the above-mentioned method, it is not necessary to melt and knead by applying heat, and it is possible to suppress the deterioration or reaction of the additive (B) which is easily volatilized or reacted at high temperature, such an additive A masterbatch containing (B) can be produced.
Here, even if a general polyolefin is dipped in the additive (B), the additive (B) is hardly impregnated in the polyolefin. Although the reason why the additive (B) is impregnated into the polypropylene resin (A) used in the present invention has not been clarified, the polypropylene resin (A) has an amorphous component compared to a general polyolefin. It is estimated that many things are involved.
　ポリプロピレン系樹脂（Ａ）のペレット又はフレークを添加剤（Ｂ）に浸漬させる時間としては、添加剤（Ｂ）の種類に応じて異なるが、好ましくは１分以上であり、そして、好ましくは４８時間以下である。 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.
　本発明における添加剤（Ｂ）として、添加剤を溶剤（Ｃ）に溶解したものを液体状添加剤として使用する場合、ポリプロピレン系樹脂（Ａ）、添加剤（Ｂ）及び溶剤（Ｃ）を配合した後、添加剤（Ｂ）が加熱分解しない温度において溶剤（Ｃ）を脱揮させる方法によって本発明の固体状ポリプロピレン系樹脂組成物を製造することもできる。配合には、撹拌機能付きの容器、混合攪拌機、ミキサー、ブレンダー、タンブラーミキサー又はヘンシェルミキサー等の一般的に用いられる混合装置を用いることができる。 When using what melt | dissolved the additive in the solvent (C) as a liquid additive as an additive (B) in this invention, a polypropylene resin (A), an additive (B), and a solvent (C) are mix | blended After that, 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. For mixing, 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.
　本発明の固体状ポリプロピレン系樹脂組成物は、ハンドリング性に優れ、室温で液体状の添加剤を含むマスターバッチペレットとして有用である。本発明によれば、液体状添加剤がブリードアウトしにくく、ベタツキが抑制されたマスターバッチを提供することができる。
　また、ホットメルト接着剤やエラストマーコンパウンド製品において、オイル成分を単独で樹脂成分と配合させる必要が無い。そのため、混練機内で液体成分と固体成分とが分離することが無く、容易に樹脂成分を混合できる。また、液状物質を取り扱わないため、混合作業が簡便になる。 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.
　次に、本発明を実施例により更に詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。 EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto.
ポリプロピレン（１）：
　商品名「エルモーデュ　Ｓ４００」、出光興産（株）製、融解吸熱量（ΔＨ－Ｄ）＝３６Ｊ／ｇ、融点（Ｔｍ－Ｄ）＝８０℃ Polypropylene (1):
Trade name “El Modue S400”, manufactured by Idemitsu Kosan Co., Ltd., melting heat absorption (ΔH-D) = 36 J / g, melting point (Tm-D) = 80 ° C.
ポリプロピレン（２）：
　商品名「プライムポリプロ　Ｓ１１９」、（株）プライムポリマー製、融解吸熱量（ΔＨ－Ｄ）＝９２Ｊ／ｇ、融点（Ｔｍ－Ｄ）＝１６６℃ Polypropylene (2):
Trade name "Prime Polypro S119", manufactured by Prime Polymer Co., Ltd., Melting endotherm (ΔH-D) = 92 J / g, melting point (Tm-D) = 166 ° C.
　ポリプロピレン（１）及び（２）の融解吸熱量（ΔＨ－Ｄ）及び融点（Ｔｍ－Ｄ）は下記方法で測定した。
〔ＤＳＣ測定〕
　示差走査型熱量計（パーキン・エルマー社製、「ＤＳＣ－７」）を用い、試料１０ｍｇを窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で昇温させることにより得られた融解吸熱カーブから融解吸熱量（ΔＨ－Ｄ）として求めた。また、得られた融解吸熱カーブの最も高温側に観測されるピークのピークトップから融点（Ｔｍ－Ｄ）を求めた。
　なお、融解吸熱量（ΔＨ－Ｄ）は、熱量変化の無い低温側の点と熱量変化の無い高温側の点とを結んだ線をベースラインとして、示差走査型熱量計（パーキン・エルマー社製、「ＤＳＣ－７」）を用いた、ＤＳＣ測定により得られた融解吸熱カーブのピークを含むライン部分と当該ベースラインとで囲まれる面積を求めることで算出される。 The melting endotherms (ΔH-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 (ΔH-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.
In addition, the melting endotherm (ΔH-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”), which is calculated by obtaining an area surrounded by a line portion including a peak of a melting endothermic curve obtained by DSC measurement and the baseline.
実施例１
　ポリプロピレン（１）のペレット１００ｇを、流動パラフィン１００ｍＬに浸漬させて２３℃で１日間保持した後、ろ過した。ろ過したペレットを紙製ウエス（日本製紙クレシア（株）製、「キムワイプ」）上で１０分間放置した後、紙製ウエス１枚を二つ折りにしてペレットを手押しで拭い、樹脂組成物ペレットを得た。樹脂組成物ペレットの質量を測定したところ、１０２．１５ｇであった。すなわち、実施例１の樹脂組成物ペレットは、ポリプロピレン（１）１００ｇ（９７．９質量％）及び流動パラフィン２．１５ｇ（２．１質量％）を含有しており、ポリプロピレン（１）に流動パラフィンが含浸されていた。樹脂組成物ペレット同士はくっつかず、ハンドリング性は良好であった。 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.
比較例１
　実施例１において、ポリプロピレン（１）をポリプロピレン（２）に変更したこと以外は実施例１と同様にして樹脂組成物ペレットを得た。樹脂組成物ペレットの質量を測定したところ、１００．３２ｇであった。すなわち、比較例１のペレットは、ポリプロピレン（２）１００ｇ（９９．７質量％）及び流動パラフィン０．３２ｇ（０．３質量％）を含有し、流動パラフィンをほとんど含まないものであった。 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.
実施例２
　ポリプロピレン（１）のペレット１００ｇを、発泡剤であるヘプタン２００ｍＬ（１３７ｇ）に浸漬させて２３℃で５分間保持した後、１２０メッシュの金網で１０分間ろ過した。ろ過したペレットは膨潤していた。得られたペレット表面を濾紙で拭った後、４５分放置して樹脂組成物ペレットを得た。樹脂組成物ペレットの質量を測定したところ、１３０．４ｇであった。すなわち、実施例２の樹脂組成物ペレットは、ポリプロピレン（１）１００ｇ（７６．７質量％）及びヘプタン３０．４ｇ（２３．３質量％）を含有しており、ポリプロピレン（１）にヘプタンが含浸されていた。 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.
比較例２
　実施例２において、ポリプロピレン（１）をポリプロピレン（２）に変更したこと以外は実施例２と同様にして樹脂組成物ペレットを得た。樹脂組成物ペレットの質量を測定したところ、１００ｇであった。すなわち、比較例２のペレットは、ヘプタンを全く含まないものであった。 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.
実施例３
　まず、バラ系香料（フェネチルアルコール６部、ネロール１部、β－シトロネロール１部、ゲラニオール１部）を調製した。当該香料１．０ｍＬをヘプタンで５倍に希釈し、香料希釈液を調製した。
　３００ｍＬナス型フラスコにポリプロピレン（１）のペレット１００ｇを入れ、香料希釈液５．０ｍＬを添加した。次いで、ロータリーエバポレーターを用いて、常温下（２３℃）１時間、回転数１２０回／分で前記フラスコを回転させた。得られた樹脂組成物ペレットをエタノール１００ｍＬで洗浄後、６０℃で１０時間減圧乾燥した。樹脂組成物ペレットの質量を測定したところ、１００．５８ｇであった。すなわち、実施例３の樹脂組成物ペレットは、ポリプロピレン（１）１００ｇ（９９．４質量％）及び香料０．５８ｇ（０．６質量％）を含有しており、ポリプロピレン（１）に香料が含浸されていた。樹脂組成物ペレットはベタツキが無かった。 Example 3
First, a rose-based flavor (6 parts of phenethyl alcohol, 1 part of nerol, 1 part of β-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.
比較例３
　実施例３において、ポリプロピレン（１）をポリプロピレン（２）に変更したこと以外は実施例３と同様にして樹脂組成物ペレットを得た。樹脂組成物ペレットをエタノール１００ｍＬで洗浄後、６０℃１０時間減圧乾燥した。樹脂組成物ペレットの質量を測定したところ、１００．１２ｇであった。すなわち、比較例３の樹脂組成物ペレットは、ポリプロピレン（２）１００ｇ（９９．９質量％）及び香料０．１２ｇ（０．１質量％）を含有していた。 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.
実施例４
　３００ｍＬナス型フラスコにポリプロピレン（１）のペレット２０ｇを入れ、ヒノキチオールのヘプタン２０質量％溶液６．０ｍＬを添加した。次いで、ロータリーエバポレーターを用いて、常温下（２３℃）１時間、回転数１２０回／分で前記フラスコを回転させた。得られた樹脂組成物ペレットをエタノール５０ｍＬで洗浄後、６０℃、１０時間減圧乾燥した。樹脂組成物ペレットの質量を測定したところ、２０．１０ｇであった。すなわち、実施例４の樹脂組成物ペレットは、ポリプロピレン（１）２０ｇ（９９．５質量％）及びヒノキチオール０．１０ｇ（０．５質量％）を含有しており、ポリプロピレン（１）にヒノキチオールが含浸されていた。樹脂組成物ペレットはヒノキチオールの香りが感じられた。 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. That is, 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.
比較例４
　実施例４において、ポリプロピレン（１）をポリプロピレン（２）に変更したこと以外は実施例４と同様にして樹脂組成物ペレットを得た。樹脂組成物ペレットの質量を測定したところ、２０ｇであった。すなわち、比較例４の樹脂組成物ペレットは、ヒノキチオールを全く含まないものであった。樹脂組成物ペレットは殆ど香りが感じられなかった。 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.

Claims (6)

  1. 　示差走査型熱量計（ＤＳＣ）を用い、試料を窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で昇温させることにより得られた融解吸熱カーブから得られる融解吸熱量（ΔＨ－Ｄ）が０Ｊ／ｇ以上８０Ｊ／ｇ以下であるポリプロピレン系樹脂（Ａ）１０質量％以上９９．６質量％以下、及び
    　２３℃において液体状である添加剤（Ｂ）０．４質量％以上９０質量％以下
    を含む固体状ポリプロピレン系樹脂組成物。     After holding the sample at -10 ° C for 5 minutes in a nitrogen atmosphere using a differential scanning calorimeter (DSC), the melting endotherm obtained from the melting endothermic curve obtained by raising the temperature at 10 ° C / min (ΔH 10% by mass to 99.6% by mass of a polypropylene resin (A) in which D is -0J / g or more and 80J / g or less, and 0.4% by mass or more of an additive (B) which is liquid at 23 ° C Solid polypropylene resin composition containing 90 mass% or less.
  2. 　前記ポリプロピレン系樹脂（Ａ）が下記（１）を満たす、請求項１に記載の固体状ポリプロピレン系樹脂組成物。
    （１）示差走査型熱量計（ＤＳＣ）を用い、試料を窒素雰囲気下－１０℃で５分間保持した後、１０℃／分で昇温させることにより得られた融解吸熱カーブの最も高温側に観測されるピークトップとして定義される融点（Ｔｍ－Ｄ）が、観測されないか又は０℃以上１２０℃以下である。     The solid polypropylene resin composition according to claim 1, wherein the polypropylene resin (A) 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.
  3. 　前記ポリプロピレン系樹脂（Ａ）が、プロピレン単独重合体であるか、又はエチレン及び炭素数４～３０のα－オレフィンからなる群より選ばれる少なくとも１つの構成単位を０モル％を超え２０モル％以下含むプロピレン系共重合体である、請求項１又は２に記載の固体状ポリプロピレン系樹脂組成物。 The content of at least one structural unit selected from the group consisting of propylene homopolymers or ethylene and an α-olefin having 4 to 30 carbon atoms is more than 0% by mole and not more than 20% by mole of the polypropylene-based resin (A) The solid polypropylene resin composition according to claim 1 or 2, which is a propylene-based copolymer.
  4. 　前記添加剤（Ｂ）が、粘度調整剤、可塑剤、結晶核剤、結晶化速度調整剤、滑剤、離型剤、強度向上剤、架橋剤、分解剤、柔軟化剤、難燃剤、難燃助剤、スリップ剤、防曇剤、導電剤、帯電防止剤、熱伝導剤、発泡剤、着色剤、蛍光剤、香料、界面活性剤、防虫剤、酸化防止剤、老化防止剤、耐候剤、紫外線吸収剤、分解防止剤、防かび剤及び抗菌剤からなる群から選ばれる少なくとも１種である、請求項１～３のいずれか１つに記載の固体状ポリプロピレン系樹脂組成物。 The additive (B) is a viscosity modifier, a plasticizer, a crystal nucleating agent, a crystallization rate modifier, a lubricant, a mold release agent, a strength improver, a crosslinking agent, a decomposition agent, a softener, a flame retardant, a flame retardant Auxiliary agents, slip agents, anti-fog agents, conductive agents, antistatic agents, heat conductive agents, foaming agents, colorants, fluorescent agents, fragrances, surfactants, insect repellents, antioxidants, anti-aging agents, weathering agents, The solid polypropylene resin composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of a UV absorber, a decomposition inhibitor, a fungicide and an antibacterial agent.
  5. 　請求項１～４のいずれか１つに記載の固体状ポリプロピレン系樹脂組成物からなるペレット。 A pellet comprising the solid polypropylene resin composition according to any one of claims 1 to 4.
  6. 　前記ポリプロピレン系樹脂（Ａ）のペレット又はフレークを前記添加剤（Ｂ）に浸漬させて、前記添加剤（Ｂ）を前記ポリプロピレン系樹脂（Ａ）のペレット又はフレーク中に含浸させる工程を有する、請求項１～４のいずれか１つに記載の固体状ポリプロピレン系樹脂組成物の製造方法。 The pellet or flakes of the polypropylene resin (A) are immersed in the additive (B) to impregnate the additive (B) into the pellets or flakes of the polypropylene resin (A). The method for producing a solid polypropylene resin composition according to any one of Items 1 to 4.
PCT/JP2018/025621 2017-07-06 2018-07-06 Solid polypropylene-based resin composition WO2019009389A1 (en)

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