WO2003020518A1 - Feuille composite conductrice biodegradable ; moulage et bande support renfermant tout deux ladite feuille - Google Patents

Feuille composite conductrice biodegradable ; moulage et bande support renfermant tout deux ladite feuille Download PDF

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Publication number
WO2003020518A1
WO2003020518A1 PCT/JP2001/007506 JP0107506W WO03020518A1 WO 2003020518 A1 WO2003020518 A1 WO 2003020518A1 JP 0107506 W JP0107506 W JP 0107506W WO 03020518 A1 WO03020518 A1 WO 03020518A1
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WO
WIPO (PCT)
Prior art keywords
biodegradable
acid
composite sheet
conductive
conductive composite
Prior art date
Application number
PCT/JP2001/007506
Other languages
English (en)
Japanese (ja)
Inventor
Yoshihiro Yamazaki
Original Assignee
Mitsubishi Plastics, Inc.
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 Mitsubishi Plastics, Inc. filed Critical Mitsubishi Plastics, Inc.
Priority to PCT/JP2001/007506 priority Critical patent/WO2003020518A1/fr
Publication of WO2003020518A1 publication Critical patent/WO2003020518A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents

Definitions

  • the present invention relates to a conductive composite sheet made of a biodegradable resin, a molded article using the same, and a carrier tape.
  • chip-type electronic components such as Ic, transistors, diodes, and the like
  • chip-type electronic components are usually housed in a carrier tape or tray obtained by secondary molding of a plastic sheet by vacuum molding, air pressure molding or press molding, and are transported and stored.
  • top tape which is a lid material, and supplied as a package.
  • this carrier tape is a conductive sheet obtained by integrally laminating a styrene-based resin composition obtained by kneading a large amount of a conductive filler on the front and back of a base material layer made of a styrene-based resin by co-extrusion, and a vinyl chloride-based resin.
  • the carrier tape made of the conductive sheet described above has environmental problems, and therefore has properties suitable for the carrier tape during use and biodegrades in a short time under natural environment after use. Rear tape is required.
  • biodegradable resin examples include a polylactic acid-based resin and a polyalkylalkanoate-based resin disclosed in JP-A-11-93945.
  • a biodegradable conductive carrier tape formed from a biodegradable conductive sheet to which the like is added.
  • an object of the present invention is to obtain a conductive composite sheet having a sufficient surface resistance even if the amount of the conductive filler used is small. Disclosure of the invention
  • the present invention relates to a biodegradable conductive composite sheet comprising a plurality of layers, wherein the outer layer contains a polylactic acid-based polymer, a biodegradable aliphatic polyester and a conductive agent, and the inner layer is a polylactic acid-based polymer and a biodegradable conductive sheet.
  • the above problem was solved by containing a degradable aliphatic polyester.
  • the amount of the conductive material used can be reduced.
  • the density of the conductive agent near the surface can be increased, and sufficient surface resistance can be obtained.
  • the biodegradable conductive composite sheet according to the present invention includes a plurality of layers.
  • Outer layers of the multilayer structure include a polylactic acid-based polymer, a biodegradable aliphatic polyester, and a conductive agent.
  • the inner layer contains a polylactic acid-based polymer and a biodegradable aliphatic polyester.
  • the number of layers of the laminate may be at least three, and may be four or more. When there are four or more layers, at least one of the layers other than the outer layer may constitute the above-mentioned inner layer.
  • the above polylactic acid-based polymer includes poly (L-lactic acid) whose structural unit is L-lactic acid, poly (D-lactic acid) whose structural unit is D-lactic acid, and L-lactic acid and D-lactic acid whose structural units are L-lactic acid Poly (DL-lactic acid) or a mixture thereof, and may also be a copolymer with a hydroxycarboxylic acid unit described below.
  • any known method such as a condensation polymerization method and an open polymerization method can be employed.
  • L-lactic acid or D-lactic acid or a mixture thereof can be directly subjected to dehydration polycondensation to obtain a polylactic acid-based polymer having an arbitrary composition.
  • a polylactic acid-based polymer can be obtained from lactide, which is a cyclic dimer of lactic acid, by using a selected catalyst while using a polymerization regulator and the like as necessary.
  • Lactide includes L-lactic acid dimer, L-lactide and D-lactic acid dimer
  • D-lactide and L-lactate and also DL-lactide consisting of D-lactic acid can be mixed and polymerized as necessary to obtain polylactic acid having any composition and crystallinity. it can.
  • a non-aliphatic dicarboxylic acid such as terephthalic acid and a non-aliphatic diol such as an ethylene oxide adduct of Z or bisphenol A may be used as a small copolymerization component.
  • a small amount of a chain extender for example, a diisocyanate compound, an epoxy compound, or an acid anhydride can be used for the purpose of increasing the molecular weight.
  • the preferred range of the weight average molecular weight of the polymer is from 60,000 to 100,000. If it is below this range, practical physical properties are hardly exhibited, and if it exceeds this range, the melt viscosity is too high and the moldability is too high. Inferior.
  • hydroxycarboxylic acid units copolymerized with polylactic acid include the optical isomers of lactic acid (D-lactic acid for L-lactic acid, L-lactic acid for D-lactic acid), glycol Acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyn-butyric acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-1--3-butyric acid, 2-methylbutyric acid, 2 — Bifunctional aliphatic hydroxycarboxylic acids such as hydroxycabronic acid and lactones such as caprolactone, ptloractone, and valerolactone.
  • biodegradable aliphatic polyester examples include polyhydroxycarboxylic acids other than polylactic acid, aliphatic polyesters obtained by condensing aliphatic diols and aliphatic dicarboxylic acids, and aliphatic polyesters obtained by ring-opening polymerization of cyclic lactones. And synthetic aliphatic polyesters and aliphatic polyesters biosynthesized in cells.
  • polyhydroxycarboxylic acids other than the above-mentioned polylactic acid examples include 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyn-butyric acid, 2-hydroxy-3,3-dimethylbutyric acid, and 2-hydroxybutyric acid.
  • examples include homopolymers and copolymers of hydroxycarboxylic acids such as 3-methylbutyric acid, 2-methyllactic acid, and 2-hydroxycabroic acid.
  • aliphatic diol examples include ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol and the like.
  • Typical examples of the aliphatic dicarboxylic acids include succinic acid, adipic acid, suberic acid, sebacic acid, and dodecane diacid. These aliphatic diols and aliphatic dicarboxylic acids As the aliphatic polyester obtained by condensing an acid, one or more of each of the above compounds may be selected for condensation polymerization or, if necessary, jump-up with an isocyanate compound or the like to obtain a desired polymer. Obtainable.
  • the aliphatic polyester obtained by opening and polymerizing the above cyclic lactones is obtained by polymerizing one or more kinds of cyclic monomers as a cyclic monomer such as £ -force prolacton, cJ-valerolactone, and 3-methyl- (5-valerolactone). It is manufactured by doing.
  • Examples of the synthetic aliphatic polyester include a cyclic acid anhydride and an oxysilane, for example, a copolymer of succinic anhydride and ethylene oxide, propion oxide, or the like.
  • aliphatic polyester biosynthesized in the above-mentioned cells aliphatic polyester biosynthesized by acetylcoenzyme A (acetyl CoA) in the cells such as A. ligenes-trofus is known.
  • This aliphatic polyester is mainly poly-hydroxybutyric acid (poly 3 HB), but in order to improve the practical properties as a plastic, valeric acid unit (HV) is copolymerized. It is industrially advantageous to use a copolymer of (3HB-co-3HV).
  • the HV copolymerization ratio is generally between 0 and 40%. Further, a long-chain hydroxy alcohol may be copolymerized.
  • Examples of the conductive agent include conductive carbon, tin oxide, antimony oxide, and indium oxide. These may be used alone or in combination of two or more. Among these, conductive rubber is preferred from the viewpoints of moldability, resistance after molding, and the like.
  • Examples of the conductive carbon include Ketjen Black EC, furnace black, channel black, acetylene black, and the like.Ketjen Black EC is, for example, used in the point that high conductivity can be obtained with a small amount of addition. More preferred. When using Kagen Black E C, the addition amount is small and the mechanical properties of the biodegradable conductive composite sheet are less likely to decrease.
  • the average particle size of the conductive agent is preferably from 0.01 to 10 m, particularly preferably from 0.05 to 5 m. If it is less than 0.01 / m, the dispersion in the aliphatic polyester is poor, and if it exceeds 10 zm, the rigidity of the biodegradable conductive composite sheet obtained becomes high, and the properties desired as a carrier tape are lost. Because it is
  • the outer layer of the laminate is composed of the polylactic acid-based polymer, the biodegradable aliphatic polyester and the conductor, and the inner layer is composed of the polylactic acid-based polymer and the biodegradable fat. Composed of tri-polyester.
  • the mixing ratio of the above-mentioned polylactic acid-based polymer and biodegradable aliphatic polyester in the outer layer and the inner layer is expressed by weight ratio, polylactic acid-based polymer / biodegradable aliphatic polyester.
  • the mixing ratio is greater than 9/1, the resulting biodegradable conductive composite sheet tends to be brittle, and may break when notched or crack when winding the conductive composite sheet. is there. If the ratio is smaller than 1/9, the resulting biodegradable conductive composite sheet becomes less rigid and difficult to handle.
  • the amount of the conductive agent in the outer layer is determined by the surface resistance of the biodegradable conductive composite sheet described later.
  • the ratio is preferably within a predetermined range. Specifically, the weight ratio is preferably 3 to 15%, more preferably 3 to 12%, based on the entire outer layer. If it is less than 3%, the resulting biodegradable conductive composite sheet will not have sufficient conductivity, and if it is more than 15%, the cost of the obtained biodegradable conductive composite sheet will increase, and It is easy to become brittle.
  • the above outer layer and inner layer may contain behenic acid, stearic acid, pendant erythritol monoester, pendant erythritol diester, pendant erythritol, in addition to the above components, as long as the effects of the present invention are not impaired.
  • Lubricants such as tall tetrastearate, pentayl erythritol monoadipate-stearate complex ester, dipentyl erythritol monoadipate-stearic acid complex ester, dipentyl erythritol hexastearate, and plasticizers such as octyl phthalate
  • plasticizers such as octyl phthalate
  • Various surfactants such as acetylene glycol, acetylene alcohol, glycerin fatty acid ester and polyglycerin aliphatic ester, dyes, pigments, and other additives can be added.
  • a commonly used laminating method such as a co-extrusion method and a thermocompression bonding method can be used.
  • the coextrusion method is a method in which a plurality of extruders are connected to a single die in a feed block type or a multi-manifold type. Examples of the die include a T die, an I die, and a round die.
  • thermocompression bonding method is a method in which another type of film is formed on the surface of the unwound mixed film using a roll or a press plate to form a laminate.
  • the surface resistivity of the biodegradable conductive composite sheet obtained in this way 1 0 3 - It is preferably in the range of 1 0 8 ⁇ .
  • the biodegradable conductive composite sheet can be molded into various molded articles.
  • the mixture was supplied to a twin-screw extruder, melt-kneaded and discharged in a strand shape, and then pulverized into a pellet with a pelletizer to obtain an inner layer pellet.
  • the surface resistivity and tear strength of the obtained laminated film were measured. As a result, the surface resistivity was 5 ⁇ 10 s, and the tear strength was 160 N / mm 2 .
  • the surface resistivity of the obtained laminated film was measured using a surface resistivity meter with a surface resistivity comparator (MCP-TESTR (Mitsubishi Chemical Corporation, trade name)).
  • a single-layer film having a thickness of 300 ⁇ m and the same composition as the outer layer used in Example 1 was produced.
  • the surface resistivity and tear strength of this single-layer film were measured. As a result, the surface resistivity was 5 ⁇ 10 s, and the tear strength was 110 N / mm 2 .
  • Example 1 After the sheet prepared in Example 1 was slit, it was vacuum-formed, and a storage portion capable of storing an IC chip was continuously formed to obtain a carrier tape.
  • the sheet After slitting the sheet prepared in Comparative Example 1, the sheet was vacuum-formed, and a storage portion capable of storing an IC chip was continuously formed to obtain a carrier tape.
  • the tear strength was 1300 N / mm ! Or more in Examples 1 and 2, and sufficient tear strength was obtained. In Comparative Example 1, however, the tear strength was less than that, and the tear strength was sufficient. Was not obtained.
  • the carrier tape of Example 3 obtained from the sheet of Example 1 has sufficient formability and handleability, and has a tear strength of 130 N / mm 2 or more. Is easy to protect from shock. Industrial applicability
  • the outer layer of the laminated structure contains the conductive agent, the amount of the conductive agent used can be reduced.
  • the outer layer of the laminated structure contains a conductive agent, even if the amount of the conductive agent is reduced, the density of the conductive agent near the surface can be increased, and sufficient surface resistance can be obtained. .

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  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention concerne une feuille composite conductrice présentant une résistance superficielle suffisante, même quand elle renferme une petite quantité de matériau de charge conducteur. Constituée d'au moins deux couches, cette feuille composite conductrice biodégradable se caractérise en ce que la couche extérieure comprend un polymère acide polylactique, un polyester aliphatique biodégradable et un matériau conducteur, et que la couche intérieure comprend un polymère acide polylactique et un polyester aliphatique biodégradable.
PCT/JP2001/007506 2001-08-30 2001-08-30 Feuille composite conductrice biodegradable ; moulage et bande support renfermant tout deux ladite feuille WO2003020518A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2001/007506 WO2003020518A1 (fr) 2001-08-30 2001-08-30 Feuille composite conductrice biodegradable ; moulage et bande support renfermant tout deux ladite feuille

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2001/007506 WO2003020518A1 (fr) 2001-08-30 2001-08-30 Feuille composite conductrice biodegradable ; moulage et bande support renfermant tout deux ladite feuille

Publications (1)

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WO2003020518A1 true WO2003020518A1 (fr) 2003-03-13

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1139945A (ja) * 1997-07-18 1999-02-12 Shin Etsu Polymer Co Ltd 生分解導電性シート及びそれを用いた生分解導電性キャリアテープ
JP2000355089A (ja) * 1999-06-15 2000-12-26 Dainippon Ink & Chem Inc 導電性を付与した生分解性ポリマー積層体又は容器
JP2001239634A (ja) * 2000-03-01 2001-09-04 Mitsubishi Plastics Ind Ltd 生分解性導電性複合シート、それを用いてなる成形体及びキャリアテープ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1139945A (ja) * 1997-07-18 1999-02-12 Shin Etsu Polymer Co Ltd 生分解導電性シート及びそれを用いた生分解導電性キャリアテープ
JP2000355089A (ja) * 1999-06-15 2000-12-26 Dainippon Ink & Chem Inc 導電性を付与した生分解性ポリマー積層体又は容器
JP2001239634A (ja) * 2000-03-01 2001-09-04 Mitsubishi Plastics Ind Ltd 生分解性導電性複合シート、それを用いてなる成形体及びキャリアテープ

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