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WO2003035742A1 - Composition de resine polyolefinique contenant une charge de type cellulose - Google Patents

Composition de resine polyolefinique contenant une charge de type cellulose Download PDF

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Publication number
WO2003035742A1
WO2003035742A1 PCT/JP2002/004310 JP0204310W WO03035742A1 WO 2003035742 A1 WO2003035742 A1 WO 2003035742A1 JP 0204310 W JP0204310 W JP 0204310W WO 03035742 A1 WO03035742 A1 WO 03035742A1
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WO
WIPO (PCT)
Prior art keywords
polyolefin
weight
filler
parts
cellulose
Prior art date
Application number
PCT/JP2002/004310
Other languages
English (en)
Japanese (ja)
Inventor
Keisuke Hashimoto
Kozo Makino
Original Assignee
Sekisui Chemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2001329368A external-priority patent/JP2002201319A/ja
Priority claimed from JP2001336588A external-priority patent/JP2002284938A/ja
Application filed by Sekisui Chemical Co., Ltd. filed Critical Sekisui Chemical Co., Ltd.
Publication of WO2003035742A1 publication Critical patent/WO2003035742A1/fr

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Classifications

    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials

Definitions

  • the present invention relates to a polyolefin-based resin composition containing a cellulose-based filler containing a polyolefin-based resin and a cellulose-based filler as main components, a method for producing a polyolefin-based resin composition containing a cellulose-based filler, and at least one surface.
  • the present invention relates to a wood-like molded article whose part is covered with a polyolefin resin composition containing a cell mouth filler.
  • Japanese Patent Publication No. 3-65453 discloses a composite resin composition in which a thermoplastic resin such as polyolefin is mixed with a cellulosic filler such as wood flour.
  • a thermoplastic resin such as polyolefin
  • a cellulosic filler such as wood flour.
  • the molded article of the composite resin yarn does not have sufficient weather resistance and is unsuitable for use in outdoor applications and the like. For this reason, it is necessary to take measures such as applying a coating on the surface of the molded body made of the composite resin composition or providing a coating film of a highly weather-resistant resin.
  • the above-mentioned coating film and the coating film having high weather resistance are not sufficiently formed when the molded body made of the composite resin composition has a complicated shape.
  • the body may be peeled off during processing such as cutting, transportation, construction, etc., and there is a problem that weather resistance deteriorates from the part where the body has been peeled off.
  • it is plastic-like due to the presence of a coating film on the surface despite the inclusion of cell-based filler.
  • Japanese Patent Application No. 2000-333042 describes a resin composition having a polyolefin-based resin and a cell-based filler as main components and having excellent weather resistance.
  • This resin thread composition is excellent in weather resistance and has a sufficient woody feel compared to a resin composition obtained by blending a cellulosic filler such as wood powder with a thermoplastic resin such as polyolefin which has been known for a long time. Although it has an additive, there is a problem that the cost is relatively high due to the need for the additive.
  • an object of the present invention is to provide a cellulose-filler-containing polyolefin-based resin having a high weather resistance suitable for outdoor use without requiring special construction such as painting on the surface of a molded product. It is an object of the present invention to provide a composition, a method for producing a polyolefin-based resin composition containing a cellulose-based filler, and a wood-like molded article having a relatively low cost, excellent weather resistance, and a woody feel.
  • the first aspect of the present invention provides a first polyolefin-based resin (100 parts by weight), a cellulose-based filler (25 to 250 parts by weight), and a cellulose-based filler more than the first polyolefin-based resin.
  • a polyolefin-based resin / cellulosic material containing 3 to 50 parts by weight of a second polyolefin-based resin having a high affinity for the polyolefin-based resin, wherein the second polyolefin-based resin is ethylene vinyl acetate.
  • a polyolefin-based resin composition containing a cellulose-based filler It is preferable that the cellulose-based filler is dispersed in the first polyolefin resin while being covered with the second polyolefin resin. Further, it is preferable that 0.5 to 25 parts by weight of a light absorbing agent and Z or a light shielding agent is added to 100 parts by weight of the polyolefin resin.
  • the second present invention provides 100 parts by weight of the first polyolefin-based resin, 25 to 250 parts by weight of the cellulose-based filler, and an affinity for the cellulose-based filler more than the first polyolefin-based resin.
  • a cellulose-filler-containing polyolefin-based resin composition containing 3 to 50 parts by weight of a second polyolefin-based resin having a high property and 0.5 to 25 parts by weight of a light absorbing agent and Z or a light shielding agent.
  • the cellulose-based filler is dispersed in the first polyolefin-based resin while being covered with the second polyolefin-based resin, and the light-absorbing agent in the second polyolefin-based resin is dispersed in the first polyolefin-based resin.
  • / or the concentration of the light shielding agent is higher than the concentration of the light absorbing agent and the light shielding agent in the first polyolefin-based resin. It is a polyolefin resin composition containing.
  • the second polyolefin-based resin includes ethylene-vinyl acetate copolymer, partially saponified ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and ethylene- (meth) acrylic acid (ester). It is preferably at least one selected from the group consisting of copolymers.
  • the light shielding agent used in the first or second polyolefin resin composition containing a cellulosic filler of the present invention is preferably titanium oxide particles.
  • the cellulosic filler is coated with the second polyolefin resin and dispersed in the first polyolefin resin.
  • a method for producing a resin composition wherein the second polyolefin resin is an ethylene monoacetate copolymer, a partially saponified ethylene monoacetate copolymer, an ethylene monobutyl alcohol copolymer, And a cellulose-based material which is at least one member selected from the group consisting of ethylene- (meth) acrylic acid (ester) copolymers
  • a method for producing a filler-containing polyolefin-based resin composition is also one aspect of the present invention.
  • Melt kneading to produce a kneaded material melt kneading the kneaded material, 100 parts by weight of the first polyolefin-based resin, and 25 to 250 parts by weight of the cellulose-based filler.
  • a method for producing a polyolefin-based resin composition containing a cellulosic filler having the following is also one aspect of the present invention.
  • a third aspect of the present invention is a woody molded article comprising a substrate and a coating layer comprising the cellulose-filler-containing polyolefin-based resin composition of the first aspect of the present invention formed on a surface of the substrate.
  • the base material is preferably a polyolefin-based resin composition comprising a polyolefin-based resin and a cellulose-based filler.
  • FIG. 1 is a diagram schematically showing the constitution of the first or second polyolefin resin composition containing a cellulosic filler of the present invention.
  • FIG. 2 is a schematic diagram of an extrusion molding apparatus used for producing the woody molded article of the third invention.
  • FIG. 3 is a backscattered electron image photograph of the polyolefin-based resin composition containing a cellulose-based filler of the first or second invention prepared in Example 5.
  • 1 represents the first polyolefin resin
  • 2 represents the cellulosic filler
  • 3 represents the second polyolefin resin
  • 4 represents the extruder
  • 5 represents the surface heating type
  • 6 represents a heating shaping mold
  • 7 represents a cooling mold
  • 8 represents a heating coating mold
  • 9 represents a resin composition flow path for a coating layer
  • 10 represents an extruder.
  • the first polyolefin-based resin composition containing a cellulose-based filler of the present invention contains a first polyolefin-based resin, a senorelose-based filler, and a second polyolefin-based resin.
  • the first polyolefin-based resin is not particularly limited, and examples thereof include polyethylene, polypropylene, polybutene, and poly-4-methyl-1-pentene. These may be used alone or in combination of two or more. Is also good.
  • polyethylene is preferable in terms of weather resistance.
  • Polypropylene is preferred in terms of mechanical strength and cost. Both are preferable in terms of recyclability.
  • the above-mentioned cellulose-based filler is not particularly limited as long as it is a particulate cellulose-based filler capable of imparting a woody appearance to a molded article.
  • Examples thereof include timber, pulp, cellulosic paper, paper, plywood, and particle board. , MDF, LVL, chippings, polishing chips, sawdust of plant materials such as bamboo; crushed material such as wood flour; grain or fruit husk such as rice husk or crushed material; plant fiber such as jute, kenaf or Pulverized products are mentioned, and among them, wood flour is preferably used because it can be easily and uniformly dispersed in the first polyolefin resin.
  • These cellulosic fillers may be used alone or 2 More than one type may be used in combination.
  • the lower limit is 25 parts by weight and the upper limit is 250 parts by weight based on 100 parts by weight of the first polyolefin-based resin. If it is less than 25 parts by weight, the wood texture such as touch will be close to that of plastic. If it exceeds 250 parts by weight, the weather resistance may decrease.
  • the second polyolefin-based resin includes ethylene-butyl acetate copolymer, partially saponified ethylene-butyl acetate copolymer, ethylene-bier alcohol copolymer, and ethylene- (meth) acrylic acid (ester). ) It is at least one selected from the group consisting of copolymers, and has a higher affinity for the cellulose-based filler than the first polyolefin-based resin. The surface of the particulate cellulose-based filler cannot be coated unless it has a higher affinity for the cellulose-based filler than the first polyolefin-based resin. Furthermore, these second polyolefin-based resins also have an affinity for the first polyolefin-based resin.
  • a resin having a higher affinity for a cellulose-based filler than the first polyolefin-based resin means the following.
  • the first polyolefin-based resin to be used After melting and kneading with the first polyolefin-based resin to be used, they are incompatible at room temperature. When such a resin is kneaded with the first polyolefin-based resin and the cellulosic filler, it has a structure covering the surface of the cellulose-based filler. It is difficult to quantify the compatibility between polymers. For example, one value of the solubility parameter (hereinafter, also referred to as SP value) is calculated based on the SP value similar to the SP value of the first polyolefin resin. Resins having these properties are not suitable, and resins having an SP value larger than the SP value of the first polyolefin-based resin are preferable.
  • SP value solubility parameter
  • the softening temperature is near or below the softening temperature of the first polyolefin-based resin. This is because a structure covering the surface of the cellulose-based filler cannot be obtained unless it is melted when kneading with the first polyolefin-based luster and the cellulose-based filler. More preferably, a resin having an affinity for the first polyolefin resin, such as one having an ethylene unit in the molecule, is more preferable than a resin having no degree of compatibility with the first polyolefin resin.
  • the lower limit of the blending amount of the second polyolefin-based resin is 3 parts by weight and the upper limit is 50 parts by weight based on 100 parts by weight of the first polyolefin-based resin. If the amount is less than 3 parts by weight, the cellulose-based filler cannot be sufficiently coated. If it exceeds 50 parts by weight, there are problems such as high cost.
  • the above-mentioned cellulose-based filler is dispersed in the first polyolefin-based resin in a state of being covered with the second polyolefin-based resin.
  • the method for coating the above-mentioned cellulose-based filler with the second polyolefin-based resin is not particularly limited, and a step of coating the second polyolefin-based resin on the surface of the cellulose-based filler may be separately provided.
  • a step of coating the second polyolefin-based resin on the surface of the cellulose-based filler may be separately provided.
  • the cellulose-based filler of the first polyolefin-based resin and the second polyolefin-based resin is kneaded. According to the difference in affinity for the filler, a coating layer of the second polyolefin resin is formed on the surface of the cellulosic filler.
  • the polyolefin-based resin composition containing a cellulosic filler of the first aspect of the present invention preferably contains a light absorbing agent and / or a light shielding agent. Thereby, further improvement of weather resistance and appearance quality of the obtained molded body is exhibited.
  • the light absorber is not particularly limited. Examples thereof include benzoate-based, benzotriazole-based, benzophenone-based, salicylate-based, and cyanoacrylate-based ultraviolet absorbers; piperidine-based, sepage-based HA LS, and the like. And a quencher such as a nickel complex.
  • the light-shielding agent is not particularly limited, and examples thereof include titanium oxide, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron ferrous brown, titanium-cobalt-based concept, cobanoleto green, cobanoleto bunore, copper-chromium-based.
  • examples include inorganic particles such as black, copper-iron ferrous black, graphite, molybdate orange, navy blue, carbon black, and cerium oxide.
  • titanium oxide particles are preferable, and particularly, titanium oxide particles having a low photoactivity and a rutile structure are preferable.
  • the second polyolefin resin composition containing a cellulose-based filler of the present invention comprises: 100 parts by weight of a first polyolefin-based resin, 25 to 250 parts by weight of a cellulose-based filler, and 25 parts by weight of the first polyolefin-based resin.
  • Cellulose-based filler containing 3 to 50 parts by weight of a second polyolefin-based resin having a higher affinity for the above-mentioned cellulosic filler, and 0.5 to 25 parts by weight of a light absorber and / or a light shielding agent Material containing polyolefin resin yarn, wherein the cellulosic filler is dispersed in the first polyolefin resin while being covered with the second polyolefin resin.
  • the concentration of the light absorbing agent and / or light shielding agent in the polyolefin-based resin 2 is higher than the concentration of the light absorbing agent and Z or the light shielding agent in the first polyolefin resin. There is something.
  • the second polyolefin resin may be, for example, an ethylene monoacetate copolymer, or a partially modified vinyl ester of an ethylene monoacetate copolymer.
  • ethylene-vinyl alcohol copolymers acryl-based resins such as poly (meth) atalilic acid and poly (meth) acrylate
  • vinyl-based resins such as polyvinyl chloride, polyacetate biel, polyarylonitrile, and polybutyl alcohol
  • a polyvinylidene-based resin such as polyvinylidene chloride; polyester-based resin, polyamide-based resin, polyether-based resin, polyurethane-based resin, polyurea-based resin, etc., among which cellulose-based filler and polyolefin are preferable.
  • Etch with affinity for both resin It is selected from the group consisting of a copolymer of ethylene monoacetate, a partially saponified ethylene monoacetate copolymer, an ethylene monovinyl alcohol copolymer, and an ethylene mono (meth) atalinoleic acid (ester) copolymer. Preferably, at least one kind is used.
  • These second polyolefin-based resins may be used alone, 4310
  • Two or more kinds may be used in combination.
  • the concentration of the light absorber and / or Z or the light shielding agent in the second polyolefin-based resin is the same as the light absorber and the light absorber in the first polyolefin-based resin.
  • the concentration is higher than the concentration of Z or the light shielding agent.
  • the cellulosic filler-containing polyolefin-based resin composition of the first or second aspect of the present invention may, if necessary, prevent discoloration of an organic pigment, an antioxidant, and a cellulose-based filler within a range that does not impair the effects of the present invention.
  • organic pigment commonly used organic pigments can be used, and examples thereof include azo pigments, phthalocyanines, and condensed polycyclic pigments.
  • antioxidants can be used, and examples thereof include phenol-based antioxidants, amine-based antioxidants, zeo-based antioxidants, and phosphorus-based antioxidants. .
  • discoloration preventing agent for the above-mentioned cellulose-based filler generally used compounds can be used, and examples thereof include semicarbazide compounds.
  • the lubricant is not particularly restricted but includes, for example, hydrocarbon lubricants such as liquid paraffin, natural paraffin, microwax and polyethylene wax; fatty acid lubricants such as stearic acid; stearic acid amide, palmitic acid amide, methylene bistea Fatty acid amide lubricants such as mouth amides; ester lubricants such as butyl acrylate, hardened castor oil, and ethylene glycol monostearate; alcohol lubricants such as cetyl alcohol and stearyl alcohol; zinc stearate, calcium stearate, and stearic acid Metal stones such as lead may be used. These lubricants may be used alone or in combination of two or more.
  • the flame retardant is not particularly limited, and examples thereof include a phosphate, a halogen-containing phosphate, a condensed phosphate, a polyphosphate, a polyphosphate, and a red phosphorus.
  • Phosphorus-based flame retardants such as antimony trioxide and guanidine salt; and reactive flame retardants such as tetrapromobisphenol A and tripromophanol. These flame retardants may be used alone or in combination of two or more.
  • the above-mentioned reinforcing agent is not particularly limited, and examples thereof include glass fiber and carbon fiber. These reinforcing agents may be used alone or in combination of two or more.
  • the non-cellulosic filler is not particularly limited, and includes, for example, inorganic fillers such as marble powder, calcium carbonate, talc, and clay; and metal fillers such as metal powder. These non-cellulosic fillers may be used alone or in combination of two or more.
  • the foaming agent is not particularly limited, and examples thereof include inorganic foaming agents such as ammonium carbonate and sodium bicarbonate; jetrosopentamethylenetetramine, N, N'-dimethyl-1-N, N'-dinitrosoterephthalamide , Benzenesulfonylhydrazide, p-toluenesulferhydrazide, P, P'-oxybis (benzenesnorefoni-norethhydrazide), 3,3,1-dishonolephonhydrazide phe-norresnorefone, azobisisobutyronitrile, azodicarbonamide
  • Organic foaming agents such as barium and ethyl azodicarboxylate are exemplified.
  • FIG. 1 schematically shows the constitution of the polyolefin resin composition containing a cellulosic filler according to the first or second invention.
  • the first or second cellulosic filler-containing polyolefin-based resin composition of the present invention comprises a particulate polycellular filler 2 coated with a second polyolefin resin 3 and a first polyolefin-based resin 1. It has a configuration that is dispersed inside.
  • Cellulose-based filler-containing polyolefin-based resin composition of the first or second invention According to the above, since the above-mentioned cellulose-based filler is covered with the second polyolefin resin, and deterioration of the cellulose-based filler can be effectively prevented, a highly durable molded article can be obtained using this composition as a material. Can be.
  • the resin-coated material of the cellulose-based filler particles is dispersed in the first polyolefin-based resin, the advantages of the first polyolefin-based resin such as easy moldability and durability, and the warmth are obtained.
  • a molded article having the advantages of cellulose-based filler such as heat retention, heat retention, and woody appearance can be obtained.
  • the cell opening is coated with the second polyolefin-based resin, and the cellulose is dispersed in the first polyolefin-based resin.
  • Cellulose that is at least one selected from the group consisting of alcohol copolymers and ethylene- (meth) acrylic acid (ester) copolymers
  • Method for producing a filler-containing polyolefin resin composition which is one of the also present invention.
  • the second polyolefin-based resin more reliably coats the periphery of the cellulose-based filler, which is susceptible to deterioration and discoloration due to the presence of these additives. Configuration can be obtained.
  • At least 0.5 to 25 parts by weight of a light absorber and / or a light shielding agent is added to 3 to 50 parts by weight of the second polyolefin resin having a higher affinity for the cellulose-based filler than the first polyolefin resin. Kneading and melting and kneading to produce a kneaded material; the kneaded material; 100 parts by weight of the first polyolefin-based resin; and the cell opening
  • a method for producing a polyolefin-based resin composition containing a cellulose-based filler, which comprises a step of melt-kneading 25 to 250 parts by weight of a cellulose-based filler is also one aspect of the present invention.
  • Examples of the apparatus used in the method for producing the polyolefin-based resin composition containing a cellulose-based filler of the present invention include a general heating and mixing apparatus such as a mixer, a Uder, a roll, and an extruder equipped with a heating apparatus.
  • a general heating and mixing apparatus such as a mixer, a Uder, a roll, and an extruder equipped with a heating apparatus.
  • Examples of the production method for obtaining a molded product using the cellulosic filler-containing polyolefin-based resin composition of the first or second invention as a raw material include, for example, an extrusion molding method, an injection molding method, a compression molding method, and a calendar molding method. , Stamping molding, transfer molding and the like.
  • the cellulose-filler-containing polyolefin-based resin composition of the first or second aspect of the present invention may be formed into a molded product such as a sheet, a film, a pipe, a deformed product, or a molded product by the above-described molding method. Can be.
  • the wood-like molded article of the third aspect of the present invention comprises a polyolefin resin composition containing a cellulosic filler according to the first or second aspect of the present invention (hereinafter also referred to as a resin composition for coating) on the surface of a substrate. Is formed.
  • the substrate is not particularly limited, and includes, for example, an organic material such as wood and plastics; an inorganic material such as metals, ceramics and concrete; and other various composite materials.
  • a polyolefin-based resin composition comprising a polyolefin-based resin and a cellulose-based filler is preferably used as in the case of the coating layer.
  • Such a polyolefin-based resin composition has an advantage of being excellent in adhesion to the resin composition for coating and also excellent in recyclability and the like.
  • the polyolefin-based resin used for the base material is not particularly limited, and examples thereof include the same ones as used for the coating resin composition. Among them, polyethylene and polypropylene are particularly preferably used.
  • the cellulose-based filler used in the base material is not particularly limited, and examples thereof include those similar to those used in the coating resin composition.
  • the base material can be appropriately selected according to the intended use. For example, when high mechanical properties are required, metals and the like are preferably used.
  • the thickness of the coating layer is not particularly limited. However, since the resin composition for coating contains a cellulosic filler, it is necessary to coat the coating composition to a thickness larger than the particle size of the cellulose-based filler.
  • a third method for producing a woody molded article of the present invention for example, after forming a resin composition for coating into a sheet shape, it is integrated with a base material by fusion, or an adhesive layer made of an adhesive or the like is formed. And a method of extruding the resin composition for coating along the substrate in a molten state with an extruder or the like to integrate the resin composition with the substrate.
  • a coating layer can be formed by a multilayer extrusion device simultaneously with the extrusion of the substrate by a multilayer extrusion technique.
  • a coated molded article having a complicated shape such as a modified multilayer extrusion can be favorably produced at a low cost.
  • a polyolefin-based resin composition serving as a base material is heated and kneaded by an extruder, and then extruded into a heat shaping die connected to the extruder.
  • Cooling type which has a resin flow path with the same cross-sectional shape as the heating shaping type, which is directly connected, and surface heating type, and has a resin flow path cross-sectional shape wider by the coating layer than the surface-heating type resin flow path cross-section, and is reheated.
  • Extrusion molding is performed through a heating coating mold in which a coating layer can be disposed at the gap between the mold and the resin flow path cross-sectional shape, and a base material is produced.
  • the resin composition is extruded by another extruder connected to a coating die, and is manufactured using a multilayer extrusion molding line for coating the surface of a base material with a polyolefin resin composition containing a cellulose-based filler.
  • FIG. 2 schematically shows one embodiment of an extrusion molding apparatus used for producing the third wood-like molded product of the present invention.
  • the extrusion molding apparatus has an extruder 4, a heating shaping die 6, a cooling die 7, a surface heating die 5, and a heating coating die 8, and the heating shaping die 6 and the cooling die 7 are directly connected. Having a configuration.
  • the polyolefin-based resin composition was charged into an extruder 4 and connected to a heating shaping die 6 connected to the extruder 4, a cooling die 7 directly connected to the heating shaping die 6, and a cooling die 7.
  • the base material was prepared by sequentially supplying to the surface heating mold 5, and the polyolefin-based resin composition containing the cellulose-based filler was extruded from the extruder 10.
  • a coating layer is formed on the surface of the base material by supplying to the heating coating die 8 connected to the surface heating die 5.
  • solidification extrusion molding can be performed by directly connecting the heating shaping mold 6 and the cooling mold 7, and cooling solidification can be performed while applying a back pressure to the material during extrusion molding.
  • the density of the product increases and the physical properties become better.
  • the woody molded article of the third aspect of the present invention can further enhance the woody feel by subjecting the surface of the coating layer to a grinding treatment such as sanding, thereby exposing the cellulosic filler.
  • the woody molded article of the third aspect of the present invention is covered with a coating resin composition having excellent weather resistance and a woody feel, it can be suitably used as a woody material for outdoor use.
  • the mechanism for improving the weather resistance of the woody molded article of the third present invention by using the cellulosic filler-containing polyolefin-based resin composition of the first or second present invention is considered as follows.
  • the cellulose-based filler In a general cellulose-based filler-containing polyolefin-based resin composition, the cellulose-based filler generates a brown decomposition product due to heat during the production process. It is eluted by rain or the like and changes color. If cracks or the like are present at the interface between the matrix resin and the cellulosic filler, the discoloration proceeds more quickly.
  • the wood-like molded article of the third invention has a base material surface coated with the cellulose-based filler-containing polyolefin resin composition of the first or second invention,
  • the polyolefin-based resin composition containing a cellulose-based filler of the present invention by covering the surface of the cellulose-based filler with a resin having a high affinity for the cellulose-based filler, the brown component is more than the polyolefin.
  • the resin stays in the resin with high affinity and is hardly eluted, and the crack resistance does not occur at the interface between the matrix resin and the cellulose-based filler, thereby improving the weather resistance.
  • cellulosic fillers are easily discolored by light, and generally contain light shielding materials such as pigments, light stabilizers such as ultraviolet absorbers and HALS, and other additives that prevent discoloration of cellulosic fillers.
  • light shielding materials such as pigments, light stabilizers such as ultraviolet absorbers and HALS, and other additives that prevent discoloration of cellulosic fillers.
  • the additive is uniformly distributed throughout the molded body, so that the cellulosic filler near the surface that causes discoloration has a low concentration in the additive and is not protected by force. Becomes When a large amount of additive is added, the improvement of weather resistance can be expected, but the additive existing inside the molded body is Since it does not contribute to improving the weather resistance at all, a large amount of useless additives are generated.
  • the cellulosic filler is covered with a resin having a high affinity for the cell-based filler, and the coating layer is further coated with a pigment or the like.
  • Light-blocking materials, UV absorbers, light stabilizers such as HALS, and other additives that prevent discoloration of the cellulosic filler can be added.
  • the cellulosic filler can be protected more effectively and economically.
  • the cellulose-filler-containing polyolefin-based resin composition had a problem that the discoloration was severe when exposed outdoors. This is due to the phenomenon that the cellulose-based filler undergoes discoloration due to light, and furthermore, water and the like. This is a result of the phenomenon in which the color components enter the material and the colored components flow out.
  • the cellulose / filler is a cellulose-based filler rather than a polyolefin-based resin.
  • the weather resistance of a polyolefin resin composition containing a cellulosic filler has been improved by a method in which an additive that provides photostability is dispersed in a matrix.
  • an additive that provides photostability is dispersed in a matrix.
  • Ethylene-Butyl acetate copolymer 79 parts by weight, titanium oxide 20 parts by weight, and deterioration 1 part by weight of an inhibitor (manufactured by Kyodo Yakuhin, "AL-103") was kneaded with a roll mill to form a pellet. 30 parts by weight of this pellet, 60 parts by weight of polypropylene (manufactured by S-Polychem, "Novatec PP"), 150 parts by weight of wood powder as a cellulose-based filler, 150 parts by weight of 100 mesh path, and brown pigment master 10 parts by weight of the batch were kneaded and molded into a pellet by an extrusion molding apparatus. This was used as the coating resin composition for the next multilayer extrusion molding.
  • a resin composition composed of 100 parts by weight of polypropylene (“Novatech PP”, manufactured by Nippon Polychem Co., Ltd.) and 150 parts by weight of a wood powder of 45 mesh pass was used.
  • a test piece was molded using the resin composition for coating and the resin composition for base material.
  • the molding apparatus has a heating shaping die at the outlet of the extruder for heating, kneading and extruding the resin composition for a base material, and further has a resin flow path having the same cross-sectional shape as the heating shaping die which is directly connected in order. Cooling type, surface heating type, and coating layer shall be provided at the gap between the reheating type resin flow path cross-sectional shape and the resin flow path cross-sectional shape wider than the resin flow path cross-sectional shape of the surface heating type by the coating layer.
  • Extrusion equipment was used.
  • Partially saponified compound of the butyl ester of ethylene monoacetate copolymer (Mersen H, manufactured by Tosoichi Co., Ltd.) 79 parts by weight, 20 parts by weight of titanium oxide, and a deterioration inhibitor (manufactured by Kyodo Yakuhin, "AL-103") 1 part by weight was kneaded with a roll mill to form a pellet. 30 parts by weight of these pellets, 60 parts by weight of polypropylene (Novatec PP, manufactured by Nippon Polychem), 150 parts by weight of wood flour (100 mesh pass), and 10 parts by weight of brown pigment masterbatch was kneaded and molded by an extruder to form a pellet. This was used as the following coating resin composition for multilayer extrusion molding.
  • a resin composition composed of 100 parts by weight of polypropylene (“Novatech PP” manufactured by Nippon Polychem Co., Ltd.) and 150 parts by weight of wood flour (45 mesh pass) is used as the base material.
  • Example 3 Specimens were molded using the above coating resin composition and the base resin composition.
  • the molding device the multilayer extrusion device described in Example 1 was used. (Example 3)
  • a resin composition comprising 100 parts by weight of polypropylene (“Novatech PP” manufactured by Nippon Polychem Co., Ltd.) and 150 parts by weight of wood flour (45 mesh pass) was used.
  • Specimens were molded using the resin composition for coating and the resin composition for base material.
  • the molding device the multilayer extrusion device described in Example 1 was used.
  • a resin composition comprising 100 parts by weight of polypropylene (“Novatech PP” manufactured by Nippon Polychem Co., Ltd.) and 150 parts by weight of wood flour (45 mesh pass) is used. Using.
  • Example 5 Specimens were molded using the above coating resin composition and the base resin composition.
  • the molding device the multilayer extrusion device described in Example 1 was used. (Example 5)
  • 79 parts by weight of ethylene monoacetate biel copolymer, 20 parts by weight of titanium oxide, and 1 part by weight of a degradation inhibitor (manufactured by Kyodo Yakuhin Co., Ltd., “AL-103”) are kneaded with a roll mill, Pellets were used. 30 parts by weight of this pellet, 60 parts by weight of polyethylene (manufactured by Nippon Polychem, Novatec HD J), 150 parts by weight of wood flour (100 mesh pass), and 10 parts by weight of brown pigment masterbatch This was kneaded and formed with an extruder to obtain a pellet, which was used as a coating resin composition for the following multilayer extrusion molding.
  • a degradation inhibitor manufactured by Kyodo Yakuhin Co., Ltd., “AL-103”
  • a resin composition composed of 100 parts by weight of polyethylene (“Novatech HD” manufactured by Nippon Polychem Co., Ltd.) and 150 parts by weight of wood flour (45 mesh pass) was used.
  • a test piece was molded using the resin composition for coating and the resin composition for base material.
  • the molding device the multilayer extrusion device described in Example 1 was used.
  • ethylene monoacetate biel copolymer 20 parts by weight of titanium oxide, and 1 part by weight of a degradation inhibitor (manufactured by Kyodo Yakuhin Co., Ltd., “AL-103”) are kneaded with a roll mill, Pellets were used. 6 parts by weight of these pellets, 60 parts by weight of polyethylene (“Novatech HD” manufactured by Nippon Polychem Co., Ltd.), 30 parts by weight of wood flour (100 mesh pass), and 4 parts by weight of brown pigment master patch The mixture was kneaded and molded into pellets. This was used as the following coating resin composition for multilayer extrusion molding.
  • a degradation inhibitor manufactured by Kyodo Yakuhin Co., Ltd., “AL-103”
  • a resin composition composed of 100 parts by weight of polyethylene (Novectech HD, manufactured by Nippon Polychem Co., Ltd.) and 150 parts by weight of wood flour (45 mesh pass) was used.
  • test piece was molded using the resin composition for coating and the resin composition for base material.
  • the molding device the multilayer extrusion device described in Example 1 was used. (Example 7)
  • “Novatec HD”) 72 parts by weight, 20 parts by weight of wood flour (100 mesh pass), and 4 parts by weight of a brown pigment master batch were kneaded and formed by an extruder into pellets. This was used as the following coating resin composition for multilayer extrusion molding.
  • a resin composition comprising 100 parts by weight of polyethylene (“Novatech HD” manufactured by Nippon Polychem Co., Ltd.) and 150 parts by weight of wood flour (45 mesh pass) was used.
  • Specimens were molded using the above-described resin composition for coating and the resin composition for base materials.
  • the molding device the multilayer extrusion device described in Example 1 was used.
  • a resin composition composed of 100 parts by weight of polyethylene (“Novatec HD” manufactured by Nippon Polychem Co., Ltd.) and 150 parts by weight of wood flour (45 mesh pass) was used.
  • Example 1 Specimens were molded using the coating resin, the composition, and the resin composition for a base material.
  • the multilayer extrusion device described in Example 1 was used as a molding device. (Comparative Example 1)
  • Polypropylene (Novatec PP, manufactured by Nippon Polychem Co., Ltd.) 83.7 parts by weight, 100-mesh pass wood flour as a cellulosic filler 150 parts by weight, brown pigment master batch 10 parts by weight, titanium oxide 6 parts by weight, and 0.3 parts by weight of a deterioration inhibitor (“AL-103” manufactured by Kyodo Yakuhin) was kneaded and molded by an extruder.
  • A-103 deterioration inhibitor manufactured by Kyodo Yakuhin
  • Polypropylene resin (Nippon Polychem, Novatec PP) 72 parts by weight, brown pigment masterbatch 4 parts by weight, titanium oxide 0.8 parts by weight, and deterioration inhibitor (Kyodo Yakuhin, AL_103 ”) 0.04 parts by weight was kneaded and molded by an extruder.
  • Tables 1 and 2 show the composition of the coating resin composition and the base resin composition in Examples 1 to 8 and Comparative Examples 1 and 2, respectively.
  • Example 1 Ingredients (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Polypropylene 60 60 60
  • Group Deterioration inhibitor 0.3 0.3 0.3 0.3 0.3 0.06 0.04 0.3 0.3 0.04 titanium oxide 6 6 6 6 6 1.2 0.8 3.6 6 0.8
  • Examples 1 to 8 exhibited lower color differences than the Comparative Examples. Decreasing the color difference means that the life of the product will be prolonged in actual use, which is not only economical, but also effective in terms of environmental impact when discarded. .
  • Example 8 although the amount of titanium oxide was smaller than that of Comparative Example 1, it is considered that the color difference was small because the titanium oxide concentration in polyethylene was high and the affinity resin covered the wood powder.
  • Examples 1 and 5 have exactly the same composition except that polyethylene is used instead of polypropylene as the olefin resin.
  • the results of the accelerated weather resistance tests of Examples 1 and 5 show that polyethylene is more excellent in weather resistance than polypropylene as the olefin resin.
  • the compounding ratio of the wood flour used as the cellulosic filler is 60% by weight, 30% by weight, and 20% by weight, respectively.
  • each sample was cut with an 8 mesh mesh sandpaper, and each arbitrarily selected 10 persons touched each sample for evaluation.
  • Tables 4 and 5 show their composition and sensory evaluation results. In addition, the same test was performed on the sample of Comparative Example 2 containing no wood flour as a control sample. Table 4
  • Plastic feeling 0 0 8 10 As can be seen from Table 5, in Comparative Example 2 containing no wood flour, no wood texture was obtained, but when the wood flour ratio was 20% by weight or more, more than half of the people felt wood texture. It was found that when the wood flour ratio was 30% by weight or more, everyone could feel the wood texture, and the wood texture was further improved.
  • the coating resin composition was dyed with ruthenium tetroxide, and then a thin film was prepared and observed with a transmission electron microscope. By staining, only the ethylene monoacetate butyl copolymer appeared to be colored. As a result, it was confirmed that the dyed ethylene monoacetate copolymer covered the wood flour surface.
  • FIG. 3 shows a backscattered electron image photograph of the resin composition for coating obtained in Example 5.
  • the composition of the observation surface can be observed.
  • the titanium atoms contained in the titanium oxide appeared to shine.
  • the surface of the cellulose filler is covered with a resin coating layer, and the weather resistance of the cell mouth filler is effectively reduced.
  • the molded product obtained from this composition can maintain excellent weather resistance.
  • the molded article of this resin composition can be used as an outdoor member which could not be applied with the molded article of the conventional cellulosic filler-containing composition.
  • a molded article having high weather resistance can be obtained according to the first or second cellulosic filler-containing polyolefin-based luster composition of the present invention. No post-processing is required, and the wood texture of the molded product surface is not impaired by painting or the like. It can be provided at a lower cost.
  • the surface of the cellulosic filler can be reliably coated with a resin film containing various additives.
  • the polyolefin resin composition containing a cellulose-based filler of the first or second aspect of the present invention can be held in a stable state.
  • a separate step of treating the cellulosic filler before the molding step is required.
  • the number of processes is increased, and not only a pretreatment device is required, but also a heat treatment is required for the cell-base filler, which has an adverse effect such as discoloration due to burning.
  • a pretreatment device is required, but also a heat treatment is required for the cell-base filler, which has an adverse effect such as discoloration due to burning.
  • the cellulosic filler is not pre-treated, it is possible to produce the cellulosic filler with less adverse effect such as discoloration.
  • the third wood-like molded product of the present invention it is possible to provide a wood-like molded product that is relatively inexpensive, has excellent weather resistance, and has a woody feel.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine polyoléfinique contenant une charge de type cellulose qui comprend 100 parties en poids d'une première résine polyoléfinique, de 25 à 250 parties en poids d'une charge de type cellulose, et de 3 à 50 parties en poids d'une seconde résine polyoléfinique, dans laquelle la seconde résine polyoléfinique présente une affinité supérieure pour la charge de type cellulose par rapport à la première résine polyoléfinique, et est au moins une résine sélectionnée dans le groupe constitué par un copolymère éthylène-acétate de vinyle, un produit en partie saponifié constitué d'un copolymère éthylène-acétate de vinyle, un copolymère éthylène alcool de vinyle et un copolymère éthylène-[(méth)acrylate] d'acide (méth)acrylique. La composition de résine polyoléfinique peut être utilisée pour produire, à faible coût, un article formé de type bois présentant une résistance aux intempéries excellente.
PCT/JP2002/004310 2001-10-26 2002-04-30 Composition de resine polyolefinique contenant une charge de type cellulose WO2003035742A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001329368A JP2002201319A (ja) 2000-10-31 2001-10-26 植物系充填材含有ポリオレフィン系樹脂組成物、及びその製造方法
JP2001-329368 2001-10-26
JP2001336588A JP2002284938A (ja) 2001-01-17 2001-11-01 木質様成形体及びその製造方法
JP2001-336588 2001-11-01

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WO2006103992A1 (fr) * 2005-03-25 2006-10-05 Sekisui Jushi Kabushiki Kaisha Composition pour former des couches de revetement fibreux et des pieces fibreuses
CN117106237A (zh) * 2023-07-05 2023-11-24 湖南联塑科技实业有限公司 一种复合改性剂及其聚丙烯组合物

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JPH1071636A (ja) * 1996-08-30 1998-03-17 Ain Eng Kk 合成木材用組成物
JPH10130438A (ja) * 1996-10-30 1998-05-19 Sekisui Chem Co Ltd 木質感を有する樹脂成形体
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JP2001113583A (ja) * 1999-10-19 2001-04-24 Okura Ind Co Ltd 二層構造を有するポリオレフィン系樹脂製丸棒、及びその製造方法
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JP2002038019A (ja) * 2000-07-19 2002-02-06 Sumitomo Chem Co Ltd 木粉充填熱可塑性樹脂組成物およびその製造方法

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JPH0336349A (ja) * 1989-06-30 1991-02-18 Moriya Sangyo Kk 板材用組成物
JPH1071636A (ja) * 1996-08-30 1998-03-17 Ain Eng Kk 合成木材用組成物
JPH10130438A (ja) * 1996-10-30 1998-05-19 Sekisui Chem Co Ltd 木質感を有する樹脂成形体
JPH10273538A (ja) * 1997-03-31 1998-10-13 Mitsui Chem Inc 木質材料含有ポリオレフィン組成物の製造法
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JP2001113583A (ja) * 1999-10-19 2001-04-24 Okura Ind Co Ltd 二層構造を有するポリオレフィン系樹脂製丸棒、及びその製造方法
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JP2002038019A (ja) * 2000-07-19 2002-02-06 Sumitomo Chem Co Ltd 木粉充填熱可塑性樹脂組成物およびその製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006103992A1 (fr) * 2005-03-25 2006-10-05 Sekisui Jushi Kabushiki Kaisha Composition pour former des couches de revetement fibreux et des pieces fibreuses
KR101182622B1 (ko) 2005-03-25 2012-09-17 세키수이주시 가부시키가이샤 목질계 성형품
CN117106237A (zh) * 2023-07-05 2023-11-24 湖南联塑科技实业有限公司 一种复合改性剂及其聚丙烯组合物
CN117106237B (zh) * 2023-07-05 2024-03-26 湖南联塑科技实业有限公司 一种复合改性剂及其聚丙烯组合物

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