WO2001070876A1 - Moulage fibreux d'élastomère de styrène thermoplastique - Google Patents

Moulage fibreux d'élastomère de styrène thermoplastique Download PDF

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Publication number
WO2001070876A1
WO2001070876A1 PCT/JP2001/002348 JP0102348W WO0170876A1 WO 2001070876 A1 WO2001070876 A1 WO 2001070876A1 JP 0102348 W JP0102348 W JP 0102348W WO 0170876 A1 WO0170876 A1 WO 0170876A1
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WO
WIPO (PCT)
Prior art keywords
cord
styrene
shaped molded
molded article
present
Prior art date
Application number
PCT/JP2001/002348
Other languages
English (en)
Japanese (ja)
Inventor
Mitsuru Sakashita
Yasuhito Suzuki
Akihiro Otaki
Original Assignee
Asahi Chemical Synthetic 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
Application filed by Asahi Chemical Synthetic Co., Ltd. filed Critical Asahi Chemical Synthetic Co., Ltd.
Publication of WO2001070876A1 publication Critical patent/WO2001070876A1/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
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes

Definitions

  • the present invention comprises a composition having a small compression set, excellent adhesion to an adherend, easy separation from the adherend, and low flowability at high temperatures.
  • An object of the present invention is to provide a molded product suitable for a sealing material having a small compression set, excellent adhesion to an adherend, good peelability, and excellent on-site workability. Is to do.
  • the present invention provides a cord-like molded article comprising a styrene-based thermoplastic elastomer and a composition containing 200 to 300 parts by weight of a liquid softener with respect to 100 parts by weight of the elastomer. I do.
  • Another object of the present invention is to provide a sheet comprising the string-shaped molded article or the composite string-shaped molded article. —To provide lumber.
  • FIG. 1 is a perspective view showing, as an example of the present invention, a state in which a cord-shaped molded body is wound around a core.
  • FIG. 2 is a diagram showing a cross section of a cord-like molded body as an example of an embodiment of the present invention.
  • FIG. 3 is a view showing a cross-section of a side-by-side type composite cord-shaped molded body according to one embodiment of the present invention.
  • FIG. 5 is a perspective view of a part of the roof material showing a state where the string-shaped molded body is placed on the bonded portion of the roof material in order to apply the cord-shaped molded body of the present invention to the joint of the roof material.
  • FIG. 6 is a cross-sectional view showing a state in which the cord-shaped molded article of the present invention is installed at the seam of the roof material and is fixed.
  • the present invention is a cord-shaped molded article having an arbitrary cross section and an arbitrary length, which is composed of a composition containing a styrene-based thermoplastic elastomer having a relatively high molecular weight and a relatively large amount of a liquid softener.
  • a preferred embodiment of the present invention is a string-shaped molded article having an arbitrary cross section and having an arbitrary cross section, which is composed of a composition containing a styrene-based thermoplastic elastomer having a relatively high molecular weight and a relatively large amount of a liquid softener.
  • the string-shaped molded article of the present invention refers to a continuous molded article having an arbitrary cross-sectional shape and an arbitrary length.
  • the present invention will be described in detail.
  • the styrene-based thermoplastic elastomer of the present invention preferably has an intrinsic viscosity [] of 1 or more.
  • the intrinsic viscosity [??] in the present invention refers to a value measured in decalin at 135 ° C.
  • the composition of the present invention contains 200 to 300 parts by weight of a liquid softener based on 100 parts by weight of the specific styrenic thermoplastic elastomer.
  • the more preferred amount of the liquid softener is 300 to 300 parts by weight, more preferably 500 to 2000 parts by weight, per 100 parts by weight of the styrene-based thermoplastic elastomer.
  • examples of the liquid softener used include at least one selected from the group consisting of process oils, liquid rubbers, and modified products thereof.
  • liquid tackifiers for example, rosin esters, modified rosin esters, terpene low polymers, modified terpene low polymers, C5-based liquid petroleum resins, and C5-C9-based liquid petroleum resins And the like can be used as the liquid softener of the present invention.
  • the composition to be selected has an even higher adhesiveness to the adherend, so that the composition can be used when the adhesiveness to the adherend is required.
  • composition of the present invention those having the following conditions can be used more preferably.
  • the softening point measured by the ring and ball method softening point measurement method is 120 to 230 ° C. And;
  • a tackifier can be added to the composition of the present invention to further improve the tackiness.
  • the tackifier include an aliphatic hydrogenated woodpecker, a resin, a modified rosin, or an ester thereof, an aliphatic petroleum resin, an alicyclic petroleum resin, an aromatic petroleum resin, an aliphatic component and an aromatic substance.
  • styrene-based tackifiers and rosin-based petroleum resin-based tackifiers are preferred, and styrene-based tackifiers are particularly preferred.
  • Specific examples of styrene-based pigment firers include those obtained by polymerizing styrene, styrene analogs or homologues such as mono-methyl styrene and mono-substituted styrene such as methylated styrene, alone or in combination, and Examples thereof include copolymers of styrene, analogs or homologs thereof, with aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, and the like.
  • composition of the present invention may contain a modifier such as a polyolefin wax, an inorganic and / or organic filler, or an additive such as a pigment or a stabilizer, as long as the object of the present invention is not impaired. it can.
  • a modifier such as a polyolefin wax, an inorganic and / or organic filler, or an additive such as a pigment or a stabilizer
  • wax examples include paraffin wax, microcrystalline phosphorus wax, polyethylene wax, polypropylene wax, Fischer-Tropx, polyethylene oxide wax, maleated polyethylene wax, and modified products thereof.
  • thermoplastic elastomers and thermoplastic resins include styrene-butadiene rubber, ethylene propylene rubber, butyl rubber, acrylic rubber, ethylene vinyl acetate copolymer, polyethylene, polypropylene, polystyrene, polybutene, and borbutadiene.
  • Inorganic fillers include inorganic fibers and inorganic foams such as calcium carbonate, zinc oxide, glass beads, titanium oxide, alumina, carbon black, clay, ferrite, talc, mica powder, aerosil, silica, and glass fiber.
  • the body is illustrated.
  • organic filler examples include powder of a thermosetting resin such as an epoxy resin, carbon fiber, synthetic fiber, and synthetic pulp.
  • the stabilizer examples include a phenol-based antioxidant, a phosphorus-based antioxidant, a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and a hindered amine-based radical scavenger.
  • composition of the present invention is obtained by mixing the above components.
  • a conventionally known method can be used without any particular limitation.
  • kneading and mixing with one another is one of the preferable production methods.
  • the string-shaped molded article having an arbitrary cross-section and having an arbitrary cross-section made of the composition of the present invention has a circular shape such as a perfect circle, an oblong shape, and an elliptical shape, a polygonal shape such as a triangle, a quadrangle, a hexagon, and an octagon, and the like. Any shape such as a star or other irregular shape can be taken. Among them, a circular shape is preferable.
  • the length is not particularly limited, but it is usually preferably a so-called string shape having at least 10 times, preferably 50 times or more the maximum diameter in the cross-sectional direction.
  • the length is appropriately selected depending on the mode used, but is usually 1 ⁇ ! To 100 m, preferably about 1 m to 10 m.
  • FIG. 1 shows an example of the cord-like molded article of the present invention.
  • FIG. 1 is a perspective view showing a state in which a cord-shaped molded body of the present invention is wound around a core as an example of the present invention. Note that Since the cord-shaped molded article of the present invention is sticky, when handling such as transportation in the state of FIG. 1, it is preferable to sandwich paper, a resin film, or the like between the cord-shaped molded articles. .
  • Fig. 2 shows a cross-section of an example of the same cord-shaped molded body having a different cross-sectional shape. Indicates an oval cross section, a star-shaped mouth, and an octagonal cross section.
  • the string-shaped molded article of the present invention when used as a sealing material, when the sealing material needs to be replaced due to breakage or the like, the composition of the present invention has an easy peeling property. It can be easily removed by making use of it, and the sealing material can be replaced on the spot with the cord-shaped molded article of the present invention, so that the workability is remarkably improved.
  • the properties of the substance (B) different from the composition (A) of the present invention include peelability, tackiness, weather resistance, surface hardness, oil resistance, water resistance, heat resistance and the like.
  • the above properties can be selected and the substance (B) suitable for the properties can be arbitrarily selected according to the purpose of use of the composite cord-like molded article of the present invention.
  • the above-mentioned composite cord-like molded article is preferably one in which the composition of the present invention is formed by continuously forming at least a part of the surface of the cord-like molded article in the length direction.
  • the substance may be of various shapes, such as a substance formed alternately along the circumferential direction in a fan shape in the cross section of the cord-like molded body, or a substance formed alternately in the shape of a strip.
  • the substance constituting the composite cord-like molded product may be added with a coloring agent, a heat stabilizer, a lubricant, a nucleating agent, other polymers, etc. within a range not to impair the object of the present invention. Can be blended.
  • coloring agent examples include inorganic coloring agents such as titanium oxide and calcium carbonate, and organic coloring agents such as phthalocyanine.
  • heat stabilizer examples include phenol-based stabilizers such as BHT (2,6-di-t-butyl-4-methylphenol).
  • lubricant examples include oleic acid amide, erlic acid amide, stearic acid amide and the like.
  • a lubricant it is particularly preferable to add 0.1 to 0.5% by weight of a lubricant to the ⁇ -shaped olefin-based polymer (A), since the resulting composite cord-like molded article has improved friction fastness.
  • the core-sheath type composite cord-like molded article according to the present invention is a core-sheath type composite cord-like molded article composed of a sheath part composed of the composition (A) of the present invention and a core part composed of the substance (B). Even if Alternatively, it may be a core-sheath type composite cord-like molded article comprising a sheath made of the substance (B) and a core made of the composition (A) of the present invention.
  • a composite cord-like molded article which is an example of a core-sheath type comprising a resin part (a) composed of the composition (A) of the present invention and a resin part (b) composed of the resin (B)
  • the cross section is shown.
  • (1) is an example of a concentric core-sheath composite string-shaped molded article
  • (2) is an example of an eccentric core-sheath composite cord-shaped molded article.
  • a is a resin portion composed of the composition (A) of the composite cord-shaped molded article of the present invention
  • b is the resin (B) of the composite cord-shaped molded article of the present invention.
  • the composition (A) of the present invention and the resin (B) are supplied to different applicators one by one to form a core-sheath structure.
  • a method for producing a core-sheath type composite cord-like molded product by performing a composite spinning by discharging a nozzle for producing a composite molded product which is configured to be discharged.
  • the core-sheath type composite cord-shaped molded product has a composition (A) / resin (B) weight ratio [(A) / (B)] of the present invention of 5/95 to 50/50. Preferably, it is 10/90 to 30/70.
  • a coloring agent, a heat stabilizer, a lubricant, a nucleating agent, other polymers, and the like can be blended into the composite cord-shaped molded article within a range not to impair the object of the present invention. Specifically, those exemplified for the side-by-side type composite cord-like molded product can be exemplified.
  • the core-sheath type composite cord-shaped molded article of the present invention may be of a concentric type in which a circular core is wrapped in a doughnut-shaped sheath having the same center in a section of the cord-shaped molded article.
  • An eccentric type in which the center of the sheath and the center of the sheath are shifted and the core is wrapped in the sheath may be used.
  • the core may be an eccentric core-sheath type conjugate fiber partially exposed on the fiber surface.
  • the cross section of the composite cord-shaped molded article of the present invention can take any shape including a circle, an ellipse, and a polygon.
  • the cord-shaped molded article of the present invention By making the cord-shaped molded article of the present invention a composite cord-shaped molded article, it is possible to give a property different from the property derived from the composition of the present invention to the surface or the side face of the cord-shaped molded article.
  • the composition of the present invention can be expected to be used in a wider range of applications than plain string-shaped molded articles.
  • a sheath of a composite cord-shaped molded article having a core-in-sheath structure is formed by using a substance having higher adhesiveness than the composition of the present invention
  • the adhesiveness of the surface of the cord-shaped molded article of the present invention is maintained while maintaining the properties of the cord-shaped molded article. Performance can be improved.
  • a side-by-side structure is formed using the same highly adhesive substance, a composite string-shaped molded article having a surface having excellent releasability and a surface having excellent adhesiveness can be obtained.
  • a substance having excellent tackiness for example, butyl rubber can be mentioned.
  • the substance (B) is preferably a thermoplastic resin that can be applied to an extruder or a hot melt discharger.
  • specific examples include synthetic rubbers such as butyl rubber, styrene-butanediene rubber (SBR) and acrylonitrile-butadiene rubber (NBR); other thermoplastic elastomers such as styrene-based propylene copolymers and thermoplastic polyurethanes; polyethylene and polypropylene.
  • Polyolefins such as: Polyamides, polyesters, vinyl chloride polymers, ethylene-vinyl acetate copolymers, and ethylene-ethyl acrylate copolymers.
  • substances (B) may be used alone or as a mixture with other substances.
  • a different pigment can be blended with the composition (A) of the present invention and the substance (B) to obtain a composite cord-like molded article.
  • the color is made different by blending a pigment with only one of the constituent components.
  • the substance (B) may be the same as the composition (A) of the present invention, and a different string may be blended with each of the compositions to form a composite cord-like molded article composed of components having different colors. .
  • Such a cord-like molded body is also an embodiment of the present invention.
  • the composite string-shaped molded articles having different colors not only enhance the visual sensation, but also provide an effect of distinguishing the constituent components, and the change of the light transmittance due to the blending of the pigment causes the composite string-shaped molded article to have a different color. New features can be added to the appearance.
  • the cord-shaped molded article of the present invention By making the cord-shaped molded article of the present invention a composite cord-shaped molded article, it is possible to give a property different from the property derived from the composition of the present invention to the surface or the side face of the cord-shaped molded article. However, the composition of the present invention can be expected to be used in a wider range of applications than the plain string-shaped molded product.
  • each physical property of the hot melt composition was measured by the following methods. Preparation of test piece: A cylinder having a height of 2 O mm and a diameter of 27 mm was formed from the hot melt composition to obtain a test piece.
  • ⁇ The change ratio from the projected area was less than 10%.
  • FIG. 5 is a perspective view of a part of the roofing material showing a state in which the string-shaped molding 1 is placed at the bonding portion of the roofing material in order to apply the string-shaped molding 1 of the present invention to the joint of the roofing material 3.
  • FIG. 6 shows a state in which the string-shaped molded body 1 of the present invention is installed at the seam of the roofing material 3 and is fixed by the fixture 4.
  • a composite cord-like molded body having a small compression set and excellent adhesiveness to an adherend, having good peelability, and being suitable for a sealing material having excellent on-site workability is provided.
  • a cord-like molded article is provided.

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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)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Building Environments (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Cette invention a trait à un moulage fibreux fait d'une composition comportant 100 parties en poids d'un élastomère de styrène thermoplastique et de 200 à 3000 parties en poids d'un émollient liquide. L'invention concerne également un matériau d'étanchéité renfermant ce moulage fibreux.
PCT/JP2001/002348 2000-03-24 2001-03-23 Moulage fibreux d'élastomère de styrène thermoplastique WO2001070876A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000085165A JP2001270991A (ja) 2000-03-24 2000-03-24 スチレン系熱可塑性エラストマーの紐状連続成形体
JP2000-85165 2000-03-24

Publications (1)

Publication Number Publication Date
WO2001070876A1 true WO2001070876A1 (fr) 2001-09-27

Family

ID=18601543

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2001/002348 WO2001070876A1 (fr) 2000-03-24 2001-03-23 Moulage fibreux d'élastomère de styrène thermoplastique

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JP (1) JP2001270991A (fr)
WO (1) WO2001070876A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5628002B2 (ja) * 2010-11-18 2014-11-19 株式会社ブリヂストン タイヤ、及びタイヤの製造方法
JP7196404B2 (ja) 2017-03-17 2022-12-27 Ｍｃｐｐイノベーション合同会社 炭素繊維強化プラスチック接着積層用熱可塑性エラストマー
CN110685365A (zh) * 2019-09-20 2020-01-14 中国五冶集团有限公司 基于丙烯酸聚合物水泥防水涂料的穿墙管道防水构造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04110381A (ja) * 1990-08-30 1992-04-10 Sekisui Chem Co Ltd ホットメルトガスケット組成物
EP0653464A2 (fr) * 1993-11-17 1995-05-17 Bridgestone Corporation Composition polymérique de faible module et procédé pour sa fabrication
JPH08158494A (ja) * 1994-12-12 1996-06-18 Bridgestone Corp シーリング材
JPH09208928A (ja) * 1996-01-30 1997-08-12 Toagosei Co Ltd シーリング剤組成物

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08283443A (ja) * 1995-04-12 1996-10-29 Mitsui Toatsu Chem Inc 熱可塑性エラストマーの発泡成形物
JPH101574A (ja) * 1996-06-14 1998-01-06 Japan Synthetic Rubber Co Ltd ポリプロピレン系樹脂組成物
DE69841494D1 (de) * 1998-03-17 2010-03-25 Asahi Chemical Synthetic Schmelzklebstoffzusammensetzung und deren Verwendung
JPH11349744A (ja) * 1998-04-07 1999-12-21 Sumitomo Chem Co Ltd 架橋熱可塑性エラストマ―組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04110381A (ja) * 1990-08-30 1992-04-10 Sekisui Chem Co Ltd ホットメルトガスケット組成物
EP0653464A2 (fr) * 1993-11-17 1995-05-17 Bridgestone Corporation Composition polymérique de faible module et procédé pour sa fabrication
JPH08158494A (ja) * 1994-12-12 1996-06-18 Bridgestone Corp シーリング材
JPH09208928A (ja) * 1996-01-30 1997-08-12 Toagosei Co Ltd シーリング剤組成物

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