CN1194279A - Resin composition and adhesive film made from said composition - Google Patents

Resin composition and adhesive film made from said composition Download PDF

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Publication number
CN1194279A
CN1194279A CN98100955A CN98100955A CN1194279A CN 1194279 A CN1194279 A CN 1194279A CN 98100955 A CN98100955 A CN 98100955A CN 98100955 A CN98100955 A CN 98100955A CN 1194279 A CN1194279 A CN 1194279A
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China
Prior art keywords
resin
tackiness agent
resin combination
tackifiers
aqueous
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Granted
Application number
CN98100955A
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Chinese (zh)
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CN1105144C (en
Inventor
舩桥信一郎
中岛顺司
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Kureha Corp
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Kureha Corp
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Publication of CN1194279A publication Critical patent/CN1194279A/en
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Publication of CN1105144C publication Critical patent/CN1105144C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions 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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/08Homopolymers or copolymers of vinylidene chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00Characterised by the use of unspecified polymers
    • C08J2300/22Thermoplastic resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesive Tapes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a composition of polymer resin and thin films, which are added a few amount of additives in the component, that can be enhance the adhesive strength. The compositions forming from thermoplastic resin adhesives and enhanced binders; adhesives and enhanced binders are incompatible in the resin, the enhanced binders at room temperature are liquid state at least, based on 100 weight% of thermoplastic resin, the adhesive thin film compositions of adhesives and enhanced binders are from 0.01 to 3 weight percents independently.

Description

Resin combination and the adhering thin film of making by said composition
Available resin combination when the present invention relates to the manufacturing of employed adhering thin film on the packing of food or industrial raw material etc.By the film that the present invention's resin combination is made, have superior tackiness voluntarily and, can invest higher resistance to air loss wrapping body to the tack of implements.
Employed bale packing film on the packing of food or industrial raw material, be to improve the bubble-tight purpose in the wrapping body, the bale packing film itself is invested tackiness, thermoplastic resin is invested the technology of tackiness, be common in polyolefin-based resins, independent or merging uses tackiness agent and tackifiers can reach purpose.
Film of the prior art for enough tackinesss, must add a large amount of tackiness agents.And want a large amount of tackiness agents of uniform mixing, and must be in advance with any means melting mixing, the toughness tackiness agent occurs so wait in expectation to adhere easily and can get powerful resin combination because of more difficult.
Japanese kokai publication sho 56-5842 communique discloses by polypropylene-based resin 100 weight parts, polyolefin rubber 3-20 weight part, polybutene 5-30 weight part, tackifiers 0.1-10 weight part and the polypropylene-based resin composition made.
Japanese kokai publication sho 53-8295 communique discloses by polyolefin-based resins, thermoplastic elastomer is aqueous, the thickness aliphatic hydrocarbon forms packaging tackiness.
The resin combination that the present invention's purpose is to provide easy manufacturing and contains a small amount of tackiness agent, and have the superior film of making by said composition of tackiness.
The inventor etc. find can effectively improve the tackiness of film with less tackiness agent usage quantity, thereby have finished the present invention by improving the tackiness agent concentration of film surface.
The present invention relates to the resin combination made by thermoplastic resin and tackiness agent inconsistent and/or tackifiers, reach by what this resin combination was made and have a higher adhesive film with it.According to the present invention, no matter the interpolation of a spot of tackiness agent and/or tackifiers all can have enough tackinesss voluntarily, to the film of the superior tack of implements.That is, the present invention's the 1st form, be to form by thermoplastic resin, tackiness agent and tackifiers, tackiness agent, tackifiers are incompatible in thermoplastic resin, at least tackifiers is aqueous at normal temperature, for to thermoplastic resin 100 weight parts, contain tackiness agent and the following resin combination of tackifiers 0.01-3 weight part separately; The present invention's the 2nd form, be by polyvinylidene chloride resin 100 weight parts that contain aqueous plasticizer and stablizer, and in polyvinylidene chloride resin under the inconsistent normal temperature aqueous tackiness agent and tackifiers the two be aggregated in the resin combination that forms below the 0.02-1 weight part, and contain polyvinylidene chloride resin 100 weight parts of aqueous plasticizer and stablizer, with any one resin combination that forms below the 0.01-1 weight part at least among tackiness agent aqueous under the inconsistent normal temperature in vinylidene resin, the tackifiers; The present invention's the 3rd form, provide by aforementioned resin form, 1 layer thickness is the following adhering thin film of 1.5-2.0 μ m.
Below describe the present invention in detail.
The used thermoplastic resin of the present invention, include polyester based resin, fluorine-containing be resin, polyamide-based resin, polyolefin-based resins etc.The resin that can be used as wrapping material, polyester based resin is arranged is polyglycolic acid, poly(lactic acid), poly-succinate, polycaprolactone, the acid of 3-hydroxyl butane and aromatic polyester resins such as the aliphatic polyester resin of the interpolymer of 3-hydroxyl pentane acid etc., polyphenyl dioctyl phthalate fourth diester, polyphenyl dioctyl phthalate second diester, especially is advisable with the dicarboxylic acid composition of terephthalic acid, isophthalic acid etc. and the polyester copolymerization resin of diol component.
As for fluorine-containing be resin, can enumerate poly(vinylidene fluoride) and interpolymer thereof, the polyvinyl chloride vinylidene resin then has polyvinylidene dichloride and interpolymer thereof etc.Vinylidene chloride is an interpolymer, is by vinylidene chloride 60~98 weight parts and the interpolymer that can form with at least a 2~40 weight parts of the monomer of vinylidene chloride copolymerization.As for can with the monomer of vinylidene chloride copolymerization, if copolymerizable monomer gets final product, precisely because representative person, can enumerate in respect of: vinylchlorid, alkyl are the vinyl ester, unsaturated aliphatic carboxylic acid of the acrylate of carbon number 1-8, methacrylic ester that alkyl is carbon number 1-8, aliphatic carboxylic acid etc., be than using with vinylchlorid, methyl acrylate, butyl acrylate only.
As for polyamide-based resin, can enumerate: nylon 6, nylon 6-66, nylon MXD6 etc.As for polyolefin-based resins, can enumerate polyethylene, polypropylene and these interpolymer, poly 4-methylpene-1 etc., with these thermoplastic resins, and thermoplastic resin formed one-tenth through giving upgrading is thin and softish film like person system is applicable to bale packing film aspect.
The tackiness agent that the present invention uses is the polyvalent alcohol etc. of the ethylene series oligomer, polyoxyethylene glycol, Polyglycerine, polypropylene glycol etc. of polybutene, polyhutadiene, polypropylene etc., and what wherein adopt is to be aqueous tackiness agent at normal temperature (25 ℃).The viscosity that is preferably 25 ℃ is 1,000-50, and 000cps is preferably 1, and 500-20, the scope person of 000cps are suitable for using.The usage quantity of tackiness agent to thermoplastic resin 100 weight parts, below the 0.01-3 weight part, is preferably the 0.01-1.0 weight part, more is preferably below the 0.05-0.5 weight part.
Tackifiers system can invest the character person who adheres to easily to object, is aqueous person at normal temperature, is thermostability during by melt-shaping, and the viscosity at 25 ℃ of easy to handle viewpoint sight is preferably 10-100cps, in the 30-60cps scope for suitable especially.As for concrete tackifiers, can enumerate: Sorbitol Powder fatty acid ester, propylene glycol fatty acid ester, glycerol fatty acid ester, for example tensio-active agent, the aqueous stable hydrocarbon of alkane hydrocarbon system loop chain alkane system, for example treated oil of naphthene series, paraffin, the Liquid Paraffin etc. of Sorbitol Powder list (three) oleic acid ester, glycerine list (three) oleic acid ester etc.No matter simplification compound or mixture all can.The usage quantity of tackifiers is below the 0.01-3 weight part to thermoplastic resin 100 weight parts, is preferably below the 0.01-1.0 weight part, more is preferably the following scope of 0.05-0.5 weight part.
The addition of tackiness agent, tackifiers is too much, if when adding the too small person of viscosity, then press workability becomes abominable easily again.Film is sticky shape and demonstrates more difficult tendency, when viscosity is excessive, and the also easy variation of press workability, and unsuitable.
The present invention changes tackiness according to the combination of previous materials.That is, by with the inconsistent tackiness agent of thermoplastic resin, the resin combination that combination constituted of tackifiers can resultful acquisition tackiness.At this, incompatible with thermoplastic resin, mean assessment with consistency described later, find the situation that has fraction to ooze out.
The vinylidene chloride that employing contains aqueous plasticizer and stablizer is the situation of interpolymer as thermoplastic resin, for containing the resin combination below 0.02~1 weight part of adding up to that normal temperature incompatible in vinylidene chloride is interpolymer is aqueous tackiness agent and tackifiers, or be aqueous tackiness agent by containing normal temperature incompatible in vinylidene chloride is interpolymer, among the tackifiers at least any one below 0.01-1 weight, more suitable below the 0.05-0.5 weight part resin combination and suitable employing of film.Tackiness agent, tackifiers system can select aforementioned person arbitrarily and adopt.As for aqueous plasticizer and stablizer; can enumerate in respect of: dioctyl phthalate, citric acid acetyl three butyl ester, Uniflex DBS, dioctyl sebacate, diisobutyl adipate, ethanoyl direactive glyceride, hexanodioic acid are polyester (weight in average molecule 1; 000-4,000) epoxidized oil of etc. plasticizer, soybean oil, flaxseed wet goods and contain stablizer of epoxy group(ing) etc.
The thickness of the film that is got by the present invention's resin combination is preferably below the 1.5-20 μ m, is preferably below the 5-20 μ m.Making the lamination structure that resin combination thus forms also can.The formation of this situation not crispatura on film, for example, symmetry constitutes suitable.
The present invention's resin combination can be made by known method.For example,, give with nodulizer that method system such as an ingotization is normal to be used,, can adopt Han Su mixing machine, paddle blending machine, strap blending machine as for the blending machine method with mix each composition of thermoplastic resin, tackiness agent, tackifiers of extrusion machine.Be shaped as film, then adopt T-contour forming, blow molding etc. usually.Resin temperature during shaping according to used resin and different, carries out in the temperature range of being expected.Imposing the bale packing film that stretching step makes thermal contraction also can.The present invention's resin combination, again also as the material system that invests tackiness effectively to the shaping thing, these shaping things, for example, combination plate or injection molding thing and bale packing film are used also can.And, when shaping the present invention's resin combination, also can add known plasticizer, stablizer, lubricant, pigment etc.
Embodiment
Below specify the present invention with embodiment, only the present invention is subjected to these qualification persons.(appraisal procedure) be uncompatibility 1.: in thermoplastic resin 100 weight parts of the object resin of assessing uncompatibility, add aqueous test portion 1 weight part of desire assessment consistency, the resin combination that preparation has been mixed, die forming, the plate of making thickness 200 μ m.Observation is placed in the plate state of 40 ℃ of environment during one week with this plate.
(zero): if during with the surface of medicated napkin wiping plate, the interpolation test portion does not almost ooze out into meal
On the towel paper.
(*): if during with the surface of medicated napkin wiping plate, the interpolation test portion oozes out into medicated napkin
On.In this assessment, be incompatible as this aqueous test portion with the object resin with (*).2. viscosity: utilize Brookfield viscometer (JIS) to measure.3. tackiness voluntarily: fit on the surface with two bale packing films (width 25mm) of charging and attacking with the imitative adhesive tape of match Lopa Nationality, pressing with the roller of weight 2kg, with pulling from this pressed surface.
Zero: the adhesion of appropriateness
△: inadhesion
*: the tack of 4. pairs of implements of adhesion: after being coated on chinaware tea making bowl with the bale packing film, add the framework of 5mm by the teacup diameter after, the situation that viewing film is broken away from by teacup.
Zero: the adhesion of appropriateness
△: inadhesion
*: the sense of touch of the 5. bale packing films of adhering: the bale packing film that will make by inflation process, after leaving standstill 10 days under the environment of 400C, 50%RH, the feel on the surface of viewing film.
Zero: feel pleasant (well)
△: feel sticky shape (bad a little)
*: too sticky shape (bad) reference example
Appraisal procedure according to consistency, (terephthalic acid/isophthalic acid (90/10 weight ratio) and polyoxyethylene glycol (clock spins limited-liability company and makes) and vinylidene chloride are the uncompatibility between interpolymer and tackiness agent/tackifiers to assessment interpolymer polyester, and it the results are shown in table 1 and table 2.Table 1: tackiness agent/tackifiers and vinylidene chloride are the uncompatibility between interpolymer
Trade(brand)name Chemical name Viscosity (CPS) Uncompatibility
??HV-50 ??LP-280 ??PEG400 Polybutene-A Liquid Paraffin polyoxyethylene glycol ????17,000 ????????40 ????????80 × × ×
Table 2: the uncompatibility between tackiness agent/tackifiers and interpolymer polyester
Trade(brand)name Chemical name Viscosity (CPS) Uncompatibility
??HV-15 ??BF-1000 ??LP-280 ??DOA Polybutene-B polyhutadiene Liquid Paraffin Octyl adipate ????2,000 ????31,300 ????40 ????370 × × × ○
(embodiment 1-2 and comparative example 1-3)
The interpolymer polyester that adopts reference example adds tackiness agent, composes tackiness agent (unit is a weight part) with the ratio shown in the table 3 as thermoplastic resin 100 weight parts, utilizes double-shafted extruder to make an ingot shape resin combination.With this ingot in the T-contour forming machine-processed the film of thickness 15 μ m.Assess the tackiness voluntarily of this film,, the results are shown in table 3 tack of implements and the sense of touch of film.(embodiment 3-6 and comparative example 4-7)
Adopting inclined to one side two vinyl chlorides of thermoplastic resin is that (Wu Yu chemistry limited-liability company makes resin and forms interpolymer 100 weight parts: vinylidene chloride/vinyl chloride=88/22) additive A TBC (citric acid acetyl three butyl ester) 3 weight parts; DOA (Octyl adipate) 2.3 weight parts; epoxidised linseed oil 1.3 weight parts; mixed by the blade blending machine; it is biaxially oriented to utilize the single shaft extrusion machine to make with the inflation forming mode, and gets the film of thickness 10 μ m.Assess the tackiness voluntarily of this film,, the results are shown in table 3 tack of implements and the sense of touch of film.Table 3
Resin combination A B C
Tackiness agent Tackifiers
Embodiment 1 embodiment 2 ?HV-50????2.0 ?HV-50????3.0 ?LP-280????2.0 ?PEG400????3.0 ○ ○ ○ ○ ○ ○
Comparative example 1 comparative example 2 comparative examples 3 ?HV-50????3.0 ????????- ????????- ????????- ?PEG400????2.0 ????????- △ △ △ △ △ × × △ ○
Embodiment 3 embodiment 4 embodiment 5 embodiment 6 ?HV-15????0.05 ?HV-15????0.1 ????????- ?HV-15????0.1 ?LP-280????0.05 ?LP-280????0.1 ?LP-280????0.1 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
Comparative example 4 comparative examples 5 comparative examples 6 comparative examples 7 ?HV-15????4.0 ?BF1000???0.5 ????????- ????????- ????????- ????????- ????????- ?DOA???????0.5 × △ △ △ △ × × × × △ ○ ○
A: tackiness B voluntarily: to the tack C of implements: the sense of touch of film
As above-mentioned, by the film that the present invention's resin combination forms, be with a spot of tackiness agent and 1 or the addition of composing tackiness agent show superior tackiness voluntarily, have superior tack simultaneously to implements.

Claims (10)

1. resin combination, be by thermoplastic resin, the composition that tackiness agent and tax tackiness agent form, tackiness agent, tax tackiness agent are incompatible in thermoplastic resin, at least tackiness agent is aqueous at normal temperature, for to thermoplastic resin 100 weight parts, contain tackiness agent separately and the person of forming below the tackifiers 0.01-3 weight part.
2. as the resin combination of claim 1, be, contain tackiness agent separately and below the tackifiers 0.01-1.0 weight part thermoplastic resin 100 weight parts.
3. as the resin combination of claim 1 or 2, wherein, the viscosity of tackiness agent is 1 at 25 ℃, 000-50,000cps.
4. as the resin combination of claim 1 or 2, wherein, the viscosity of tackiness agent is 10-100cps at 25 ℃.
5. as the resin combination of claim 1, wherein, tackiness agent is polybutene or polyhutadiene.
6. as the resin combination of claim 1, wherein, tackifiers is Liquid Paraffin or table interface promoting agent.
7. as the resin combination of claim 1, wherein, thermoplastic resin is a polyester based resin, and fluorine-containing is resin, polyamide-based resin.
8. resin combination is by the person of forming below the total 0.02-1 weight part that is aqueous tackiness agent and tackifiers under vinylidene resin 100 weight parts that contain aqueous plasticizer and stablizer and the normal temperature incompatible with vinylidene resin.
9. resin combination, system is by vinylidene resin 100 weight parts to containing aqueous plasticizer and stablizer, contains among the tackiness agent that is aqueous under the normal temperature incompatible with vinylidene chloride, the tackifiers any one person of forming below 0.01~1 weight part at least.
10. adhering thin film is each the resin combination person of forming by the claim 7 to 9 below the film thickness 1.5-20 μ m of one deck.
CN98100955A 1997-03-25 1998-03-25 Resin composition and adhesive film made from said composition Expired - Lifetime CN1105144C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP090317/1997 1997-03-25
JP9031797 1997-03-25

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CNB021223513A Division CN1312210C (en) 1997-03-25 1998-03-25 Resin compsn. and adhering thin film made by same

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CN1194279A true CN1194279A (en) 1998-09-30
CN1105144C CN1105144C (en) 2003-04-09

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CN98100955A Expired - Lifetime CN1105144C (en) 1997-03-25 1998-03-25 Resin composition and adhesive film made from said composition
CNB021223513A Expired - Lifetime CN1312210C (en) 1997-03-25 1998-03-25 Resin compsn. and adhering thin film made by same

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105745259B (en) * 2013-08-27 2018-12-28 株式会社吴羽 Vinylidene chloride resin film and its manufacturing method

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102675465B1 (en) * 2022-04-06 2024-06-17 조웅현 Hot melt adhesive composition for automobile seat for improved creep properties and eco-friendliness and manufacturing method thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4212910A (en) * 1979-04-30 1980-07-15 National Starch & Chemical Corporation PET Bottle assemblies produced by using a hot melt adhesive comprising a block copolymer and a tackifying resin
JPS565842A (en) * 1979-06-29 1981-01-21 Idemitsu Petrochem Co Ltd Polypropylene-based resin composition
DD214851A1 (en) * 1983-04-27 1984-10-24 Leuna Werke Walter Ulbricht Fo COATING POLYMER COMBINATIONS
JPS63135472A (en) * 1986-11-27 1988-06-07 Mitsui Toatsu Chem Inc Restrippable pressure-sensitive adhesive
JPH0675702B2 (en) * 1988-09-22 1994-09-28 ダイハツ工業株式会社 Adhesive application method
JPH0743036B2 (en) * 1990-02-22 1995-05-15 アイシン化工株式会社 Gasket composition
JP2791396B2 (en) * 1991-08-29 1998-08-27 東亞合成株式会社 Flexible disk and hot melt adhesive for the disk

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105745259B (en) * 2013-08-27 2018-12-28 株式会社吴羽 Vinylidene chloride resin film and its manufacturing method

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CN1105144C (en) 2003-04-09
TW467935B (en) 2001-12-11
CN1446847A (en) 2003-10-08
CN1312210C (en) 2007-04-25
KR19980080545A (en) 1998-11-25
KR100260990B1 (en) 2000-07-01

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Granted publication date: 20030409