WO2008044651A1 - Adhésif à base d'acide polylactique - Google Patents

Adhésif à base d'acide polylactique Download PDF

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Publication number
WO2008044651A1
WO2008044651A1 PCT/JP2007/069603 JP2007069603W WO2008044651A1 WO 2008044651 A1 WO2008044651 A1 WO 2008044651A1 JP 2007069603 W JP2007069603 W JP 2007069603W WO 2008044651 A1 WO2008044651 A1 WO 2008044651A1
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WIPO (PCT)
Prior art keywords
polylactic acid
plasticizer
acid
solvent
crystalline
Prior art date
Application number
PCT/JP2007/069603
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English (en)
Japanese (ja)
Inventor
Mitsuru Akashi
Amornrat Lertworasirikul
Kazuyuki Sashida
Soichiro Kamiya
Original Assignee
Osaka University
Riken Vitamin 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 Osaka University, Riken Vitamin Co., Ltd. filed Critical Osaka University
Priority to JP2008538712A priority Critical patent/JPWO2008044651A1/ja
Publication of WO2008044651A1 publication Critical patent/WO2008044651A1/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
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/18—Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a biodegradable polylactic acid-based adhesive.
  • Polylactic acid is obtained by producing lactic acid through lactic acid fermentation by microorganisms using plant resources such as corn and sweet potato as raw materials, and polymerizing the lactic acid or lactide.
  • Polylactic acid is an environmentally-circulating biodegradable polymer that returns to lactic acid by hydrolysis and enzymatic degradation in an ecological environment, and further decomposes to carbon dioxide and water.
  • Polylactic acid has been attracting attention as an alternative material to replace petroleum resources, and research is being actively conducted from the viewpoint of protecting the global environment and effectively using global resources.
  • Polylactic acid is a polymer having very excellent biocompatibility and biodegradability. Its production cost is high, and its application range is very limited. In recent decades, production technology has advanced significantly and industrial mass production has become possible, so recently polylactic acid can be obtained at low cost.
  • Polylactic acid has been developed and put into the market, utilizing its properties such as adhesiveness and strength, and various practical products including daily necessities such as adhesives.
  • a plasticizer may be blended with polylactic acid irradiated with light by a light source that emits ultraviolet rays having a wavelength of 400 nm or less and an intensity value of 120 mW / cm 2 or more.
  • a plasticized polylactic acid composition has been proposed, and the use of plasticized polylactic acid as an adhesive raw material is described.
  • the molar ratio of L-lactic acid to D-lactic acid is 0.1 to 9
  • the intrinsic viscosity is 0.5 to 2.2
  • the softening point is 70 °.
  • a polyester resin for adhesives characterized by containing 60% by mass or more of polylactic acid having a weight average molecular weight to number average molecular weight ratio (Mw / Mn) of less than 3.0.
  • Patent Document 1 Japanese Patent Laid-Open No. 2000-86877
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-82319
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a polylactic acid adhesive that retains excellent adhesiveness and transparency over a long period of time.
  • the present invention consists essentially of crystalline polylactic acid, amorphous polylactic acid and a plasticizer, and the amorphous polylactic acid is 5 to 5 times the total amount of crystalline polylactic acid and amorphous polylactic acid. 33% by mass
  • the present invention also relates to a polylactic acid-based adhesive comprising a polylactic acid resin composition containing a plasticizer in a proportion of 5 to 30% by mass of the total amount of the composition.
  • the polylactic acid-based adhesive of the present invention is flexible and transparent after adhesive curing, has practical adhesive strength and environmental resistance, and can retain these properties for a long period of time. As a result, excellent adhesion and transparency can be exhibited over a relatively long period of time.
  • the polylactic acid-based adhesive of the present invention contains a specific polylactic acid resin composition and usually further contains a solvent, and the constituent components of the composition are dissolved in the solvent.
  • the polylactic acid resin composition constituting the polylactic acid-based adhesive of the present invention consists essentially of crystalline polylactic acid, amorphous polylactic acid and a plasticizer.
  • Crystalstalline polylactic acid and! /
  • the term “crystallinity” is used to mean that the crystal domain is observed with a polarizing microscope after crystallization under moderate conditions. is doing.
  • the crystalline polylactic acid is used to include a polymer of D lactic acid (hereinafter referred to as “poly D lactic acid”) or a polymer of L lactic acid (hereinafter referred to as “poly L lactic acid”).
  • Poly D lactic acid or poly-L-lactic acid is a known compound, and as such, has inherently hard and brittle properties.
  • L-lactic acid monomer units or lactic acid monomers such as aliphatic hydroxycarboxylic acid, aliphatic diol, and aliphatic dicarboxylic acid are used. It may contain other monomer units that can be copolymerized with.
  • poly L-lactic acid such as a copolymer is also included in the crystalline polylactic acid.
  • poly L-lactic acid is preferable because it is easy to obtain due to its high crystallinity.
  • the crystalline polylactic acid that can be used in the present invention is not particularly limited as long as it has a molecular weight that can be dissolved in an appropriate solvent and removed from the solution to form a polylactic acid film.
  • Such crystalline polylactic acid can be produced or obtained in a weight average molecular weight (Mw) of 50,000-1, 000,000, preferably in the range of 100,000-500,000. ⁇ ⁇ Lacy H-100 (manufactured by Mitsui Chemicals), Toyota Eco Plastic U's (manufactured by Toyota Motor Corporation), etc. are available as commercial products.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) used in the present invention are standard polystyrene equivalent values measured by size exclusion chromatography. The same applies to the following.
  • non-crystalline polylactic acid is used to mean that no crystal domain is observed with a polarizing microscope or the like after crystallization under appropriate conditions.
  • Amorphous polylactic acid is used to mean a copolymer of D-form lactic acid and L-form lactic acid (hereinafter referred to as “poly-DL lactic acid”).
  • the ratio of D-form and L-form can be any polymerization ratio as long as the above non-crystallinity is ensured.
  • Copolymerization ratio of D-lactic acid: L-lactic acid is 90: 10-10: 90. What is necessary is just to select and select suitably.
  • the form of the copolymer may be any of a block copolymer, a draft copolymer, a random copolymer, and the like.
  • non-crystalline includes other monomer units copolymerizable with lactic acid monomers such as aliphatic hydroxycarboxylic acid, aliphatic diol, and aliphatic dicarboxylic acid. Let's do it! / In the present invention, such a copolymer is also included in the amorphous polylactic acid.
  • the non-crystalline polylactic acid that can be used in the present invention has a weight average molecular weight (Mw) of 50,000 to; 1, 00,000, preferably (or 100-000-500,000.
  • Mw weight average molecular weight
  • Lashia H-280 Mitsubishi Chemicals Co., Ltd.
  • the amorphous polylactic acid is 50% by mass or less, preferably 33% by mass or less, more preferably 30% by mass or less, and still more preferably at least 50% by mass of the total amount of crystalline polylactic acid and amorphous polylactic acid. Use more than 5% by weight.
  • the crystal size, dispersibility, and crystallinity of the crystalline polylactic acid can be controlled. As a result, strength and flexibility can be controlled. Both of these characteristics can be achieved, transparency can be secured, and these characteristics can be maintained for a long time.
  • the plasticizer used in the present invention is not particularly limited as long as it is a compound that is added to a resin to impart flexibility.
  • the plasticizer of the present invention include a polybasic acid ester plasticizer, a polyester plasticizer, a polyhydric alcohol plasticizer, a phosphate ester plasticizer, an epoxy plasticizer, a fatty acid plasticizer, and a sulfonic acid. Can increase the power of plasticizers.
  • a preferred plasticizer is a polyhydric alcohol plasticizer.
  • polybasic acid ester plasticizer examples include dimethyl phthalate, jetyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, dihexyl sulfite.
  • Phthalate esters such as adipates of oxide adducts; di-2 (—ethylhexyl) azelate, diisooctylazelate, di-2-ethylhexyl, 4-thioazelate, di-n-hexylazelate, diisoptyla Azelaic acid esters
  • Sebacic acid esters such as dimethyl sebacate, jetyl sebacate, dibutyl sebacate, di (2-ethylhexyl) sebacate, diisooctyl sebacate; g-n-butyl malate, dimethyl malate, jetyl malate, di (2-ethinole Hexenoles) maleate estenolates such as malate and dinonino remaleate; fumaric acid esters such as dibutino olefumarate and di (2-ethylhexyl) fumarate.
  • Triechinorecitrate Tree n-Butylcitrate
  • Acetyllate examples thereof include citrate esters such as norecitrate, acetiltyl n butyl citrate, acetiltyl n octyl, n-decyl citrate, and acetiltyl (2-ethyl hexyl) citrate.
  • polyester plasticizer examples include an acid component such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, propylene glycolanol, 1,3-butanediole,
  • polyesters composed of diol components such as 1,4-butanediol, 1,6-hexanediol, ethylene glycol, and diethylene glycol
  • polyesters composed of hydroxycarboxylic acid such as poly-prolataton.
  • These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol! /, Or may be end-capped with an epoxy compound! /.
  • polyhydric alcohol plasticizer examples include ethylene glycol, diethylene glycol mononole, triethylene glycol nole, propylene glycol nole, dipropylene glycol nole, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4 butanediol, pentanediol, hexanediol, decanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, poly (ethylene oxide 'propylene oxide) block and / or random copolymer Coalesced, polytetramethyleneglycol monore, hi, 'sufenore, glycerin, diglycerin, polyglycerin, yurisri tonore, xylito monore, mannito nore, recbitonore, trimethyleneprono nore, Printers Ellis Rito
  • alkylene O sulfoxides addition polymers such as propylene O dimethylsulfoxide addition polymer can be cited.
  • derivatives of these polyhydric alcohols can also be suitably used.
  • phosphoric ester plasticizer examples include triethyl phosphate, tributyl phosphate, tri-2-ethylenohexyl phosphate, trioctinole phosphate, triphenolate phosphate, diphenyl phosphate 2-ethyl ester.
  • Xyl trixyl phosphate, tricresyl phosphate, and the like.
  • epoxy plasticizer examples include butyl epoxy stearate, epoxy monoesterol, octinole epoxy stearate, epoxidized butinoreoleate, G (2-ethinole hexenole) 4, 5 epoxy cyclohexane 1 , 2 Carboxylate, Epoxidized semi-drying oil, Epoxidized triglyceride, Epoxy butyl stearate, Epoxy octyl stearate, Epoxy decyl stearate, Epoxidized soybean oil, Epoxidized flaxseed oil, Methyl epoxy hydrostearate, Glyceryl tri- ( Epoxyacetoxy systemate), isooctyl epoxy stearate, V-type epoxy resin mainly using bisphenol A and epichlorohydrin.
  • fatty acid plasticizer examples include methylolate, butyrate, methoxyethyl oleolate, tetrahydrofurfurolate, glyceryl monooleate, diethyleneglycol monoole monorate, methinorea cetinorelicinolate, butinorea cetinorelyl Sinolate, glyceryl monoricinoleate, diethylene glycol monoricinoleate, glyceryl tree (acetyl ricinolate), alkyl acetyl ricinoleate, n-butyl stearate, glyceryl monostearate, diethylene glycol distearate, stabilized pentachloromethyl stearate, Chlorinated methyl stearate, Chlorinated alkyl stearate, Diethylene glycol monolaurate, Diethylene glycolo-resperanolate, Triethylene glycol Norejipera Noregoneto, Buchiruse port cellosolve
  • sulfonic acid plasticizer examples include benzenesulfone butyramide, o toluenesulfonamide, p-toluenesulfonamide, N ethyl-p-toluenesulfonamide, o tolueneethylsulfonamide, p-toluene.
  • Ethylsulfonamide, N cyclo Examples include hexyl p-toluenesulfonamide, phenol and talesol alkylsulfonates, sulfonamidoformamide, and the like.
  • the plasticizer is 30% by mass or less, preferably 25% by mass or less, and at least 5% by mass based on the total amount (solid content) of the composition. If the content is too large, there are problems such as plasticizer predating, strength and film forming ability, and a decrease in transparency. If the content is too small, sufficient flexibility cannot be obtained. .
  • plasticizer at least one selected from the group consisting of the above plasticizers may be used.
  • the total amount thereof may be within the above range.
  • polylactic acid resin composition in the polylactic acid resin composition, other additives such as light absorbers such as ultraviolet rays, heat stabilizers, dyes and pigments, inorganic fillers, crystal nucleating agents, additives, and the like can be used as long as the objective effects of the present invention are not impaired.
  • Other substances having compatibility with polylactic acid and having desired characteristics, such as a dehydration inhibitor, an antistatic agent, an antiblocking agent, and an antifogging agent, may be appropriately selected and added.
  • the solvent constituting the polylactic acid adhesive of the present invention is not particularly limited as long as it can dissolve at least crystalline polylactic acid, amorphous polylactic acid, and plasticizer.
  • a solvent an organic solvent is usually used, for example, an aromatic solvent, a chlorine solvent, an ester solvent, a ketone solvent, an ether solvent, an alcohol solvent, an aliphatic hydrocarbon solvent and Examples include alicyclic hydrocarbon solvents.
  • a preferred solvent is a chlorinated solvent.
  • aromatic solvent examples include benzene, toluene, xylene and the like.
  • chlorinated solvents include methylene chloride, black mouth form, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, black mouth benzene, dichlorobenzene, etc. It is done.
  • ester solvent examples include ethyl acetate, methyl lactate, ethyl lactate, isophorone, ⁇ -petit-mouth rataton, and the like.
  • ketone solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • ether solvents include jetyl ether, ethyl acetate sorb, butyl Examples thereof include cellosolve, tetrahydrofuran, and 1,4 dioxane.
  • alcohol solvent examples include methanol, ethanol, n propanol, isopropanol, and n butanol.
  • aliphatic hydrocarbon solvent examples include n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane, and nonane.
  • alicyclic hydrocarbon solvent examples include cyclopentane and cyclohexane.
  • the amount of the solvent used is not particularly limited as long as the object of the present invention is achieved.
  • the solid content concentration of the adhesive is 0 ⁇ ;! to 0 ⁇ 8g / ml, preferably 0 to 3 to 0.
  • the amount of the solvent is 7 g / ml.
  • At least one solvent selected from the group consisting of the above solvents may be used.
  • the solid content concentration of the adhesive only needs to be within the above range.
  • a film is formed from the polylactic acid-based adhesive of the present invention
  • preferred properties of the film are shown below.
  • the physical property value of a film is illustrated below, as for molded articles other than a film, those physical properties are reflected, and even if time passes, very high, flexibility and transparency, And, of course, maintaining strength!
  • the "film" to be measured for various physical properties contains crystalline polylactic acid, non-crystalline polylactic acid and a plasticizer.
  • the non-crystalline polylactic acid is composed of crystalline polylactic acid and non-crystalline polylactic acid.
  • the polylactic acid resin composition lOOmg contained at a ratio of 30% by mass or less of the total amount of the above is dissolved in 10 ml of a solvent (black mouth form) at room temperature, cast into a petri dish, dried at room temperature for 48 hours, and a diameter of 3 OOmm X (thickness) was formed by molding to 40 ⁇ m.
  • Crystal particles (crystallinity, crystallite diameter, spherulites)
  • Crystallinity after treatment for 1 hour at 60 ° C in atmospheric environment 42% or less, 22% or more, preferably 40% or more
  • the crystallinity (cry S talinit y ) (%) means the ratio of crystalline to the whole sample, and broad halos and crystals caused by amorphous matter from the diffraction pattern measured by an X-ray diffraction apparatus. The sharp peak area due to the crystal quality is calculated, and the ratio of the crystalline to the sum of the crystalline and amorphous peak areas is shown.
  • the degree of crystallinity greatly affects the tensile strength and flexibility in the present invention. As the value increases, the tensile strength increases but the flexibility decreases. On the other hand, if the value is too small, strength and heat resistance sufficient for practical use cannot be obtained.
  • the crystallite means the largest group that can be regarded as a single crystal, and the crystallite size (A) is the half-width from the diffraction peak obtained by X-ray diffraction.
  • D K ⁇ ⁇ / / 3 cos ⁇
  • D Crystallite size
  • ⁇ Measurement X-ray wavelength
  • ⁇ Half width
  • K Scherrer constant
  • Maximum spherulite diameter 15 m or less, preferably 4 to 10 m
  • the spherulite is a single crystal spherical aggregate, and the maximum spherulite size is measured and calculated by analyzing an image obtained by observation with a polarizing microscope using WinROOF.
  • the maximum spherulite diameter greatly affects the transparency in the present invention, and the greater the value, the lower the transparency.
  • the spherulite size distribution was measured and calculated by WinroorC analysis of an image obtained by observation with a polarizing microscope.
  • the spherulite diameter distribution greatly affects the transparency in the present invention, and the transparency increases as the distribution ratio of smaller spherulites increases.
  • HAZE means the percentage of the transmitted light that passes through the test piece that deviates by 2.5 ° or more from the incident light due to forward scattering, and is a standard value for evaluating transparency. . The higher the value, the more opaque the film, and the lower the value, the clearer the film.
  • the polylactic acid adhesive of the present invention has the same level of adhesiveness as a commercially available adhesive, but also has excellent transparency and strength, and compares such excellent adhesiveness and transparency. It can be maintained over the long term.
  • the polylactic acid adhesive of the present invention has an adhesive ability equivalent to that of a commercially available PVC adhesive Scotch (Catalog No. 6004 N; manufactured by 3M). For example, when the following adhesion test (reference example) was conducted with the Scotch adhesive, the tensile elastic modulus was 59.5 MPa, the tensile strength was 0.83 MPa, and the tensile maximum point elongation was 0.10 mm. Adhesives have the same or higher adhesive strength. Moreover, after curing, the polylactic acid-based adhesive of the present invention maintains the above-mentioned film characteristics as it is, and in particular, its transparency is maintained even in a long-term environment.
  • a rectangular parallelepiped piece of wood (24mm x 14mm x 8mm) is washed with methanol, dried at 150 ° C for 2 hours, coated with the Scotch adhesive (50mg) and the surface of two pieces of wood (14mm x 8mm)
  • the sample was sandwiched between the layers, pressurized with a weight (150 g) for 5 minutes, and then dried at room temperature for 24 hours.
  • a bow I tension tester (Orientec; RTC 1310) equipped with a 10k N load cell, the tensile modulus, tensile strength, and maximum tensile elongation of the adhesive layer between two pieces of wood were measured. .
  • the tensile modulus is the ratio of stress to strain (strain between 0.01 mm and 0.02 mm), the tensile strength is the bow I tension stress at the maximum stress point, and the bow I tension maximum point elongation is the elongation corresponding to the tensile strength.
  • the test was conducted with an initial gauge length of 10 mm and a crosshead speed of 0.5 mm / sec. Each adhesive was measured 5 times, and an average value was obtained. [0046] [Continuous Adhesion Test]
  • test piece prepared under the same conditions as in the adhesion experiment was dried and stored for 3 months at a temperature of 20 ° C and a humidity of 65%, a tensile test was performed in the same manner to measure the tensile strength retention rate.
  • the total light transmittance is the ratio of the total transmitted light flux to the parallel incident light flux of the test piece. The higher the total light transmittance, the higher the transparency of the test piece.
  • DGTA diglycerol tetraacetate
  • AMGX Riquema Monore PL -019 manufactured by Riken Vitamin Co., Ltd.
  • PLLA, PDLLA, DGTA and AMG were dissolved in methylene chloride at the composition ratio shown in Table 1 to prepare an adhesive. All adhesives had a solid content concentration of 0.5 g / ml.
  • the tensile elastic modulus is preferably 30 MPa or more, preferably 40 MPa or more, and more preferably 50 MPa or more, within a range where there is no practical problem.
  • the tensile strength is 0.660 MPa or more within a range where there is no practical problem, preferably 0.80 MPa or more.
  • the tensile maximum point elongation is 0.05 mm or more within a range in which there is no practical problem, preferably 0.0.
  • the transparency is preferable because it is transparent enough to distinguish characters and the like.
  • the polylactic acid-based adhesive of the present invention is useful as, for example, a woodworking adhesive, a cloth adhesive, and a paper adhesive, and is particularly preferably used as a woodworking adhesive.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention concerne un adhésif à base d'acide polylactique biodégradable présentant une excellente capacité d'adhésion et une excellente transparence sur une longue période de temps. L'invention concerne particulièrement un adhésif à base d'acide polylactique contenant une composition de résine d'acide polylactique qui est essentiellement formée d'un acide polylactique cristallin, d'un acide polylactique non cristallin et d'un plastifiant. Dans la composition de résine d'acide polylactique, l'acide polylactique non cristallin est contenu en une quantité de 5-33 % en masse du total de l'acide polylactique cristallin et de l'acide polylactique non cristallin, et le plastifiant est contenu en une quantité inférieure ou égale à 30 % en masse par rapport à la masse totale de la composition.
PCT/JP2007/069603 2006-10-06 2007-10-05 Adhésif à base d'acide polylactique WO2008044651A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015030814A (ja) * 2013-08-05 2015-02-16 株式会社リコー ポリ乳酸及びその製造方法
WO2017055045A1 (fr) 2015-10-01 2017-04-06 Purac Biochem Bv Adhésif thermofusible non réactif avec résine spécifique
EP3214106A1 (fr) * 2016-03-03 2017-09-06 PURAC Biochem BV Adhésif thermofusible non réactif avec un copolymère de lactide

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JPH11302521A (ja) * 1998-04-23 1999-11-02 Shimadzu Corp ポリ乳酸組成物およびその成型品
JPH11323113A (ja) * 1998-05-08 1999-11-26 Shimadzu Corp ポリ乳酸系組成物
JP2000186877A (ja) * 1998-12-21 2000-07-04 Mk Seiko Co Ltd ワイン貯蔵庫

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JPH07502069A (ja) * 1992-10-29 1995-03-02 ナショナル　スターチ　アンド　ケミカル　インベストメント　ホールディング　コーポレイション ポリラクチド含有ホットメルト接着剤
JPH09505615A (ja) * 1993-10-15 1997-06-03 エイチ．ビイ．フラー ライセンシング アンド ファイナンシング インク 乳酸のポリエステルを含む生物分解性／肥料化可能なホットメルト接着剤
JPH11302521A (ja) * 1998-04-23 1999-11-02 Shimadzu Corp ポリ乳酸組成物およびその成型品
JPH11323113A (ja) * 1998-05-08 1999-11-26 Shimadzu Corp ポリ乳酸系組成物
JP2000186877A (ja) * 1998-12-21 2000-07-04 Mk Seiko Co Ltd ワイン貯蔵庫

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015030814A (ja) * 2013-08-05 2015-02-16 株式会社リコー ポリ乳酸及びその製造方法
US10407599B2 (en) 2015-10-01 2019-09-10 Purac Biochem B.V. Non-reactive hot-melt adhesive with set time improver
WO2017055045A1 (fr) 2015-10-01 2017-04-06 Purac Biochem Bv Adhésif thermofusible non réactif avec résine spécifique
WO2017055044A1 (fr) * 2015-10-01 2017-04-06 Purac Biochem Bv Adhésif thermofusible non réactif avec agent améliorant le temps de prise
US11008489B2 (en) 2015-10-01 2021-05-18 Purac Biochem Bv Non-reactive hot-melt adhesive with specific resin
EA035805B1 (ru) * 2015-10-01 2020-08-13 ПУРАК Биокем БВ Химически инертный термоплавкий клей, способ его производства и способ расположения субстратов в закрепленном положении друг относительно друга
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
CN108026427A (zh) * 2015-10-01 2018-05-11 普拉克生化公司 具有特定树脂的非反应性热熔粘合剂
US20200216727A1 (en) * 2015-10-01 2020-07-09 Purac Biochem Bv Non-reactive hot-melt adhesive with specific resin
EA033746B1 (ru) * 2015-10-01 2019-11-21 Purac Biochem Bv Химически инертный термоплавкий клей с улучшителем времени схватывания
JP2018532845A (ja) * 2015-10-01 2018-11-08 ピュラック バイオケム ビー． ブイ． セットタイム改良剤を含む非反応性ホットメルト接着剤
JP2019512030A (ja) * 2016-03-03 2019-05-09 ピュラック バイオケム ビー． ブイ． ラクチド系コポリマーを含む非反応性ホットメルト接着剤
AU2017226933B2 (en) * 2016-03-03 2019-07-04 Purac Biochem Bv Non-reactive hot-melt adhesive with lactide-based copolymer
KR20180117173A (ko) * 2016-03-03 2018-10-26 푸락 바이오켐 비.브이. 락타이드계 코폴리머를 갖는 비반응성 핫멜트 접착제
EA035024B1 (ru) * 2016-03-03 2020-04-17 ПУРАК Биокем БВ Химически инертный термоплавкий клей с сополимером на основе лактида
US10626302B2 (en) 2016-03-03 2020-04-21 Purac Biochem Bv Non-reactive hot-melt adhesive with lactide-based copolymer
CN108699223A (zh) * 2016-03-03 2018-10-23 普拉克生化公司 包含基于丙交酯的共聚物的非反应性热熔粘合剂
WO2017149019A1 (fr) * 2016-03-03 2017-09-08 Purac Biochem Bv Adhésif thermofusible non réactif présentant un copolymère à base de lactide
KR102161038B1 (ko) 2016-03-03 2020-10-05 푸락 바이오켐 비.브이. 락타이드계 코폴리머를 갖는 비반응성 핫멜트 접착제
EP3214106A1 (fr) * 2016-03-03 2017-09-06 PURAC Biochem BV Adhésif thermofusible non réactif avec un copolymère de lactide

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