WO1994010257A1 - Colle thermofusible autoadhesive contenant un polylactide - Google Patents

Colle thermofusible autoadhesive contenant un polylactide Download PDF

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Publication number
WO1994010257A1
WO1994010257A1 PCT/US1993/008913 US9308913W WO9410257A1 WO 1994010257 A1 WO1994010257 A1 WO 1994010257A1 US 9308913 W US9308913 W US 9308913W WO 9410257 A1 WO9410257 A1 WO 9410257A1
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WO
WIPO (PCT)
Prior art keywords
weight
adhesive
poly
ethylene
polylactide
Prior art date
Application number
PCT/US1993/008913
Other languages
English (en)
Inventor
Carmine P. Iovine
Thomas F. Kauffman
Jules E. Schoenberg
Paul P. Puletti
Original Assignee
National Starch And Chemical Investment Holding Corporation
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 US07/968,564 external-priority patent/US5252646A/en
Priority claimed from US08/000,153 external-priority patent/US5312850A/en
Application filed by National Starch And Chemical Investment Holding Corporation filed Critical National Starch And Chemical Investment Holding Corporation
Priority to EP93922271A priority Critical patent/EP0618948A1/fr
Priority to AU51332/93A priority patent/AU659353B2/en
Priority to JP6511050A priority patent/JPH07502069A/ja
Publication of WO1994010257A1 publication Critical patent/WO1994010257A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • Hot melt adhesives are used commercially for a wide variety of applications.
  • the major advantage of hot melt adhesive systems is the lack of a carrier fluid which eliminates the need for drying the adhesive film once it is applied to the substrate. This elimination of the drying step overcomes hazards associated with solvent usage and also allows for faster production line speeds and lower transportation costs.
  • the degree of tack of the hot melt adhesives may be varied over a wide range to produce adhesives varying from pressure sensitive to non-pressure sensitive in character. Non-pressure sensitive are used, for example, in bookbinding, bag ending, case and carton sealing.
  • Hot melt adhesives have historically been based on petroleum derived polymers such as polyethylene, ethylene-vinyl acetate, styrenic block copolymers, and polypropylene to name a few. These compositions are further tackified, plasticized, and reinforced with a variety of resins, oils and waxes which are derived from both petroleum and naturally occurring feedstocks such as wood, gum and tall oil rosin and terpenes. These classic compositions suffer from the cyclical price cycles common to all oil derived materials, and also are generally very resistant to degradation once the articles employing them are disposed of.
  • the present invention stems from the growing movement away from petroleum derived raw materials to those derived from renewable, natural resources and as part of an effort to utilize raw materials which have demonstrated some level of degradation.
  • the present invention utilizes a class of naturally occurring or synthetically produced thermoplastic, biodegradable .copolymers derived from a non-petroleum feedstock as the base polymer.
  • Such compositions advance the state of the art of hot melt adhesives by alleviating the dependence on petroleum based materials and by allowing for the development of hot melt adhesives which either degrade naturally after coming in contact with the soil or which can be composted.
  • hot melt adhesive compositions suitable for a variety of applications are obtained by use of polylactide (i.e., the bimolecular cyclic ester of lactic acid) or copolymers with other lactones such as glycolide and caprolactone, tackifiers, and optionally, waxes and/or plasticizers.
  • the adhesives may be formulated using conventional additives and may vary from pressure sensitive to non-pressure sensitive in character depending upon the desired application.
  • the present invention is directed to hot melt adhesive compositions comprising 20 to 98% by weight of a polylactide homo- or copolymer where the copolymer contains at least 20 molar percent of the lactide component (1 or d or d,l or meso or mixtures thereof) 2 to 80% by weight of a polar tackifier having a Ring and Ball softening point (as described by ASTM E- 26) greater than about 60°C; 0 to 50% by weight of a plasticizer; 0 to 30% by weight of a wax diluent and 0-3% by weight of a stabilizer.
  • a polar tackifier having a Ring and Ball softening point (as described by ASTM E- 26) greater than about 60°C; 0 to 50% by weight of a plasticizer; 0 to 30% by weight of a wax diluent and 0-3% by weight of a stabilizer.
  • pressure sensitive adhesives can be prepared using 20 to 70% by weight of the polylactide homo- or copolymer, 10 to 60% of a tackifying resin, 10 to 50% plasticizer and 0 to 3% of a stabilizer.
  • Preferred pressure sensitive adhesives are prepared using 30 to 60% of the polylactide homo- or copolymer; 20 to 50% of a tackifying resin, preferably a terpene phenolic resin; and 20 to 30% of a plasticizer, preferably Pycal 94, a phenyl ether of poly(ethylene glycol) from ICI; or Hercolyn D, a methyl ester of hydrogenated rosin from Hercules.
  • Lower levels of plasticizer may also be employed to produce adhesives useful for various end uses such as in construction adhesives for disposable products where some initial degree of tack is needed but no residual pressure sensitive properties are required.
  • non-pressure sensitive adhesives can be prepared using 20-98% by weight of the polylactide homo- or copolymer, 2-80% tackifying resin, 0-30% of a wax-like diluent, 0-30% plasticizer and 0 to 3% of a stabilizer.
  • Preferred non-pressure sensitive adhesives are prepared using 30-80% of the polylactide homo- or copolymer; 10- 40% tackifying resin, preferably terpene-phenolic resins or rosin derivatives; 0-25% of a plasticizer, preferably the phenyl ether of poly(ethylene glycol) or the methyl ester of hydrogenated wood rosin; and 0-20% of a wax-like diluent, preferably hydrogenated castor oil (also known as castor wax) or 12-hydroxystearamide.
  • polymers other than the polylactide may be incorporated into the hot melt adhesives at levels less than about 20% by weight. Representative formulations and applications are discussed hereinbelow and illustrated by the examples, however, these should not be construed as limiting the invention.
  • the major component of the adhesive of the invention present in an amount of 20 to 98% by weight of the adhesive, comprises a homo- or copolymer of polylactide containing at least 20 molar percent of the lactide comonomer.
  • the general structure of the polylactide is shown below:
  • Suitable polymers for use herein have a number average molecular weight (M n ) within the range of 10,000 to 200,000.
  • poly(d,1-lactide) and the meso- are essentially amorphous
  • poly(1-lactide) and poly(d- lactide) is crystalline in nature and has a crystalline melting point of 186°C depending on its molecular weight and stereopurity.
  • the polymers may be prepared by ring- opening polymerization of the bimolecular cyclic ester of lactic acid with acid or base catalysts such as PbO, SnCl 2 , SnCl 4 , ZnCl 2 , SbF 5 , Sb 2 0 3 , or triethylamine using solution, precipitation or melt processes. Alternatively, they may be obtained commercially from Henley Chemicals, Inc. under the Resomer® tradename; from Poly Sciences Inc. or from Ecological Chemical Products Company (EcoChem) .
  • poly(d-lactide) , poly(d,1-lactide) , and poly(meso-lactide) suitable polymers for use herein may also be prepared by copolymerization with other lactones such as glycolide or caprolactone.
  • lactones such as glycolide or caprolactone.
  • poly(d,1-lactide-co-glycolide) polymers containing equimolar amounts of the lactide and glycolide components are available from Henley Chemicals as Resomer RG502, 503, 504, 505 and 506 and are suitable for use herein.
  • poly(d,1-lactide-co- glycolide) polymers known as Resomer RG752, 755 and 756 containing 75% of the lactide component as well as the Resomer 858 polymer which contains 85% lactide are also suitable.
  • the tackifying resins useful in the adhesive compositions are generally polar in nature and have a Ring and Ball softening point greater than 60°C and include rosin and rosin derivatives, terpene phenolics, pure phenolic resins, and the like.
  • the useful tackifying resins include any compatible resins or mixtures thereof such as (1) natural and modified rosins such, for example, as gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin; (2) glycerol and pentaerythritol esters of natural and modified rosins, such, for example as the glycerol ester of pale, wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerized rosin, the pentaerythritol ester of hydrogenated rosin, and the phenolic-modified pentaerythritol ester of rosin; (3) phenolic modified terpene resins and hydrogenated derivatives thereof such, for example, as the resin product resulting from the condensation, in an acidic medium, of a bicyclic terpene and a phenol;
  • Patent Nos. 4,073,776 and 4,023,826 Mixtures of two or more of the above described tackifying resins, as well as blends of the above resins with small amounts of (e.g., less than about 10% of the adhesive) less compatible resins may be utilized for some formulations. While the tackifier may comprise up to about 80% of the adhesive, it is generally used in amounts of 10 to 60% by weight.
  • compatible plasticizing or extending oils may also be present in the composition.
  • Preferred compatible plasticizers include phthalate plasticizers such as dioctyl phthalate; liquid polyesters such as Dynacol 720 from Huls; benzoate plasticizers such as 1,4- cyclohexane dimethanol dibenzoate (e.g., Benzoflex 352 available commercially from Velsicol) ; phosphate plasticizer such as t-butylphenyl diphenyl phosphate (e.g., Santicizer 154 available commercially from Monsanto) ; poly(ethylene glycols) and derivatives thereof such as the phenyl ether of poly(ethylene glycol) (e.g., Pycal 94 available commercially from ICI) as well as liquid rosin derivatives having Ring and Ball melting points below about 60°C such as the methyl ester of hydrogenated rosin (e.g., Hercolyn D from phthalate plasticizers such as dioctyl phthalate
  • Suitable waxes include 12-hydroxystearamide wax, hydrogenated castor oil, oxidized synthetic waxes, poly(ethylene oxide) having a weight average molecular weight above about 1000 and functionalized synthetic waxes such as carbonyl containing Escomer HlOl from Exxon.
  • adhesive formulations described herein may contain both wax and plasticizer components so that the presence of one or the other is not mutually exclusive.
  • hindered phenols include: 1,3,5- trimethyl-2,4,6-tris(3, 5-di-tert-butyl-4-hydroxy- benzyl)benzene; pentaerythritol tetrakis-3-(3,5-di-tert- butyl-4-hydroxyphenyl)propionate; n-octadecyl 3,5-di- tert-buty1-4-hydroxypheny1) propionate; 4,4'-methylene- bis (2,6-di-tert-butylphenol) ; 4,4'-thiobis (6-tert- butyl-o-cresol) ; 2,6-di-tert-butylphenol; 6-(4-hydroxy- phenoxy)-2,4-bis(n-octylthio)
  • the stabilizer is present in levels of about 0.1 to 3% by weight.
  • Optional additives may be incorporated into the hot melt compositions in order to modify certain properties thereof. Among these additives may be included colorants such as titanium dioxide; and fillers such as talc and clay, etc.
  • colorants such as titanium dioxide
  • fillers such as talc and clay, etc.
  • There may also be present in the adhesive small amounts (e.g. , less than about 20% by weight, and preferably 5 to 20% by weight) of certain thermoplastic polymers such as ethylene vinyl acetate, ethylene acrylic acid, ethylene methyl aerylate and ethylene n-butyl acrylate copolymers containing about 12 to 50% vinyl acetate as well as caprolactone polymers. These polymers are employed in order to impart flexibility, toughness and strength.
  • hot melt adhesive it may be desirable to incorporate into the hot melt adhesive up to 20% by weight of certain hydrophilic polymers such as poly(vinyl alcohol) , hydroxyethyl cellulose, starch, modified starch, poly(vinyl methyl ether) , poly(ethylene oxide) , or poly(hydroxy butyrate/hydroxy valerate) which will function to increase the water sensitivity of the adhesives which may be desired for some applications.
  • hydrophilic polymers such as poly(vinyl alcohol) , hydroxyethyl cellulose, starch, modified starch, poly(vinyl methyl ether) , poly(ethylene oxide) , or poly(hydroxy butyrate/hydroxy valerate) which will function to increase the water sensitivity of the adhesives which may be desired for some applications.
  • hydrophilic polymers such as poly(vinyl alcohol) , hydroxyethyl cellulose, starch, modified starch, poly(vinyl methyl ether) , poly(ethylene oxide) , or poly(hydroxy butyrate/
  • An exemplary procedure involves placing approximately 40% of the total tackifying resin concentration with all the polymer, wax, plasticizers and stabilizers in a jacketed mixing kettle, preferably in a jacketed heavy duty mixer, which is equipped with rotors and thereupon raising the temperature to a range of from up to about 190°C. After the resin has melted, the temperature is lowered to 150° to 165°C. Mixing and heating are continued until a smooth, homogeneous mass is obtained whereupon the remainder of the tackifying resin is thoroughly and uniformly admixed therewith.
  • the adhesives disclosed herein may be employed in a wide variety of uses as are known in the art. The adhesives described herein may be effectively utilized in a variety of packaging and carton sealing applications.
  • the non-pressure sensitive adhesives may also be used to bind a plurality of sheets in a wide range of bookbinding operations. They may also be used for laminating tissue and/or screen-reinforced tissue layers such as are used in individual or roll use applications as in wipers, paper towels, toilet tissue and other consumer or industrial end uses.
  • the resultant adhesives may be used in the assembly or construction of various disposable applications including, but not limited to, sanitary napkins, disposable diapers, hospital gowns, bed pads and the like.
  • adhesives are useful for the assembly of disposable articles using multi-line construction techniques wherein at least one flexible film substrate is bonded to at least one tissue, non- woven, polyolefin or other flexible polymeric film substrate.
  • the adhesives may be useful in the bonding of elastic to polyethylene, polypropylene or non-woven substrate so as, for example, to impart elongation resistant gathers thereto.
  • the adhesive may also be utilized in less demanding disposable construction applications such as for end or perimeter sealing.
  • Peel Temperature Test A bead of test adhesive approximately 1/8 inch in diameter is applied at 325°F to 350°F with a glass rod onto 60 pound/ream kraft paper. A second sheet of the same paper is superimposed on the first sheet within 2 seconds and pressed thereto to form a kraft-to-kraft bond. The bonded sheets are then cut perpendicular to the adhesive line into 1 inch wide strips. Duplicate bonded specimens are placed in an oven with one free end of the specimen attached to a fixed support and a 100 gram load suspended from the other sheet at the same end of the bond. The oven temperature is then increased in 10°F increments at 15 minute intervals.
  • Shear Temperature Test Samples are prepared as in peel temperature test but separate sheets of Kraft at opposite ends of the bonded specimen are suspended and weighted to stress the bond in a shear mode. The temperature of the oven is increased as in peel test until failure occurs.
  • Adhesion Test A molten bead of hot melt at 325°F to 350°F was drawn across the middle (widthwise) of a 1" x 3" strip of Kraft paper. A second strip of Kraft paper was then immediately superimposed upon the first and a 50 gram weight placed on top of the construction. The Kraft to Kraft bonds were then aged 24 hours at either room temperature (RT or 70°F) or at 40°F. After aging, the samples were stressed by hand at the temperature of storage in a 90° peel mode. The presence or absence of fiber tear was then noted.
  • test results presented above show the adhesives to be particularly suitable for packaging applications such as case and carton sealing due to its low viscosity, good fiber tear and acceptable peel and shear values.
  • compositions and test results are shown in Table II.
  • NC 350°F
  • Foral NC is a calcium salt of rosin from Hercules Irganox 1010 is a hindered phenol antioxidant from Ciba Geigy

Abstract

Des compositions de colle thermofusible autoadhésive sont préparées à partir de 20 à 98 % en poids d'un homo- ou copolymère polylactide contenant au moins 20 pour cent en mole du composant lactide; de 2 à 80 % en poids d'une colle polaire présentant un point de ramollissement (tel que décrit par l'ASTM-E 26) supérieur à environ 60 °C; de 0 à 50 % en poids d'un plastifiant; de 0 à 30 % en poids d'un diluant à la cire; de 0 à 3 % par poids d'un stabilisant; et de 0 à 20 % d'un polymère. En utilisant un copolymère biodégradable, thermoplastique, d'origine naturelle comme polymère de base, ces colles constituent un progrès par rapport à la technique antérieure des colles thermofusibles autoadhésives en réduisant la dépendance vis à vis des produits du pétrole et en perfectionnant les colles thermofusibles auto-adhésives qui, soit se dégradent naturellement après avoir été en contact du sol, soit peuvent être compostées.
PCT/US1993/008913 1992-10-29 1993-09-20 Colle thermofusible autoadhesive contenant un polylactide WO1994010257A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP93922271A EP0618948A1 (fr) 1992-10-29 1993-09-20 Colle thermofusible autoadhesive contenant un polylactide
AU51332/93A AU659353B2 (en) 1992-10-29 1993-09-20 Polylactide containing hot melt adhesive
JP6511050A JPH07502069A (ja) 1992-10-29 1993-09-20 ポリラクチド含有ホットメルト接着剤

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US07/968,564 US5252646A (en) 1992-10-29 1992-10-29 Polylactide containing hot melt adhesive
US968,564 1992-10-29
US000,153 1993-01-04
US08/000,153 US5312850A (en) 1993-01-04 1993-01-04 Polylactide and starch containing hot melt adhesive

Publications (1)

Publication Number Publication Date
WO1994010257A1 true WO1994010257A1 (fr) 1994-05-11

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PCT/US1993/008913 WO1994010257A1 (fr) 1992-10-29 1993-09-20 Colle thermofusible autoadhesive contenant un polylactide

Country Status (5)

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EP (1) EP0618948A1 (fr)
JP (1) JPH07502069A (fr)
AU (1) AU659353B2 (fr)
CA (1) CA2126849C (fr)
WO (1) WO1994010257A1 (fr)

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WO1998029506A1 (fr) * 1996-12-31 1998-07-09 Kimberly-Clark Worldwide, Inc. Compositions polymeres sensibles a l'eau et leur procede de preparation
US6010972A (en) * 1996-04-15 2000-01-04 Kimberly-Clark Worldwide, Inc. Oil-resistant disposable absorbent product
US6500897B2 (en) 2000-12-29 2002-12-31 Kimberly-Clark Worldwide, Inc. Modified biodegradable compositions and a reactive-extrusion process to make the same
US6552124B2 (en) 2000-12-29 2003-04-22 Kimberly-Clark Worldwide, Inc. Method of making a polymer blend composition by reactive extrusion
US6552162B1 (en) 1997-07-31 2003-04-22 Kimberly-Clark Worldwide, Inc. Water-responsive, biodegradable compositions and films and articles comprising a blend of polylactide and polyvinyl alcohol and methods for making the same
US6579934B1 (en) 2000-12-29 2003-06-17 Kimberly-Clark Worldwide, Inc. Reactive extrusion process for making modifiied biodegradable compositions
US6767961B1 (en) 2000-06-19 2004-07-27 Kimberly-Clark Worldwide, Inc. Blends of poly (vinyl alcohol) and poly (ethylene oxide) and articles made therewith
WO2004076583A1 (fr) * 2003-02-21 2004-09-10 Metabolix Inc. Compositions adhesives de pha
US6890989B2 (en) 2001-03-12 2005-05-10 Kimberly-Clark Worldwide, Inc. Water-responsive biodegradable polymer compositions and method of making same
WO2005056680A1 (fr) * 2003-12-12 2005-06-23 Biomet Deutschland Gmbh Adhesif fusible biodegradable
US6958371B1 (en) 2000-06-19 2005-10-25 Kimberly-Clark Worldwide, Inc. Method of making blends of poly(vinyl alcohol) and poly(ethylene oxide)
US7053151B2 (en) 2000-12-29 2006-05-30 Kimberly-Clark Worldwide, Inc. Grafted biodegradable polymer blend compositions
US7465770B2 (en) 2001-03-02 2008-12-16 Tate & Lyle Public Limited Company Environmentally degradable polymeric compounds their preparation and use as hot melt adhesive
FR2937975A1 (fr) * 2008-11-06 2010-05-07 Cvlc Adhesif thermofusible a faible temperature d'application a base de polymere d'acide lactique et procede de preparation
US7781539B2 (en) 2003-02-21 2010-08-24 Metabolix Inc. PHA blends
US8003719B2 (en) 2003-12-30 2011-08-23 Metabolix, Inc. Nucleating agents
KR101145374B1 (ko) * 2010-11-02 2012-05-15 대상 주식회사 전분계 핫멜트 접착제용 조성물
EP2647682A1 (fr) * 2012-02-24 2013-10-09 tesa SE Adhésif biodégradable
WO2013162059A1 (fr) * 2012-04-26 2013-10-31 Henkel Japan Ltd. Adhésif thermofusible
CN103937438A (zh) * 2007-02-16 2014-07-23 阿肯马法国公司 共聚酰胺，含有这样的共聚酰胺的组合物及其用途
EP2781573A1 (fr) 2013-03-22 2014-09-24 Jowat AG Nouvelles compositions d'adhésif à base de matières premières renouvelables et leur utilisation
EP2781532A1 (fr) * 2013-03-22 2014-09-24 Novamelt GmbH Klebstofftechnologie Composition, procédé de fabrication et utilisation d'un adhésif à base de polylactide modifié
WO2015153226A1 (fr) * 2014-03-31 2015-10-08 3M Innovative Properties Company Colles thermofusibles biosourcées
WO2015150580A1 (fr) * 2014-06-03 2015-10-08 Purac Biochem Bv Adhésif thermofusible non réactif, sa fabrication et son utilisation dans le scellement d'emballages
EP2841517A4 (fr) * 2012-04-26 2015-12-23 Henkel Ag & Co Kgaa Adhésif thermofusible
US9790409B2 (en) 2013-05-30 2017-10-17 Henkel Ag & Co. Kgaa Hot melt adhesive
US9828535B2 (en) 2012-09-27 2017-11-28 Henkel Ag & Co. Kgaa Hot melt pressure-sensitive adhesive for labeling
US10030135B2 (en) 2012-08-17 2018-07-24 Cj Cheiljedang Corporation Biobased rubber modifiers for polymer blends
US10611903B2 (en) 2014-03-27 2020-04-07 Cj Cheiljedang Corporation Highly filled polymer systems
US10669417B2 (en) 2013-05-30 2020-06-02 Cj Cheiljedang Corporation Recyclate blends
CN112708257A (zh) * 2020-12-31 2021-04-27 宁波能之光新材料科技股份有限公司 一种高弹耐磨的户外木塑表层材料及其制备方法
ES2942331A1 (es) * 2022-12-29 2023-05-31 Asociacion Investig De Industria Textil Aitex Procedimiento para la fabricacion de un adhesivo termofusible y adhesivo termofusible obtenido por dicho procedimiento

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JPWO2008044651A1 (ja) * 2006-10-06 2010-02-12 国立大学法人大阪大学 ポリ乳酸系接着剤
US8870871B2 (en) * 2007-01-17 2014-10-28 University Of Massachusetts Lowell Biodegradable bone plates and bonding systems
JP6154725B2 (ja) * 2013-10-24 2017-06-28 ヘンケルジャパン株式会社 ホットメルト接着剤
CN108026426A (zh) * 2015-10-01 2018-05-11 普拉克生化公司 具有固化时间改进剂的非反应性热熔粘合剂
JP6531658B2 (ja) * 2016-01-28 2019-06-19 東洋インキＳｃホールディングス株式会社 ホットメルト接着剤組成物および塗工物
CN106947403A (zh) * 2017-02-27 2017-07-14 东莞市蓝恩科技有限公司 一种可生物降解的保护膜
JP6419376B1 (ja) * 2018-05-18 2018-11-07 株式会社Ｂｐコンサルティング ポリ乳酸系ホットメルト接着剤の製造方法

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Cited By (42)

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Publication number Priority date Publication date Assignee Title
US6010972A (en) * 1996-04-15 2000-01-04 Kimberly-Clark Worldwide, Inc. Oil-resistant disposable absorbent product
US6664333B2 (en) 1996-12-31 2003-12-16 Kimberly-Clark Worldwide, Inc. Cold-water flushable compositions comprising polylactic acid dispersed in polyvinyl alcohol
WO1998029506A1 (fr) * 1996-12-31 1998-07-09 Kimberly-Clark Worldwide, Inc. Compositions polymeres sensibles a l'eau et leur procede de preparation
US6552162B1 (en) 1997-07-31 2003-04-22 Kimberly-Clark Worldwide, Inc. Water-responsive, biodegradable compositions and films and articles comprising a blend of polylactide and polyvinyl alcohol and methods for making the same
US6958371B1 (en) 2000-06-19 2005-10-25 Kimberly-Clark Worldwide, Inc. Method of making blends of poly(vinyl alcohol) and poly(ethylene oxide)
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JPH07502069A (ja) 1995-03-02
CA2126849C (fr) 1999-01-12
AU659353B2 (en) 1995-05-11
AU5133293A (en) 1994-05-24
CA2126849A1 (fr) 1994-05-11
EP0618948A1 (fr) 1994-10-12

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