CN101210164B - Polyamide hot-melt adhesive and shoe bonded by the same - Google Patents

Polyamide hot-melt adhesive and shoe bonded by the same Download PDF

Info

Publication number
CN101210164B
CN101210164B CN2006101487299A CN200610148729A CN101210164B CN 101210164 B CN101210164 B CN 101210164B CN 2006101487299 A CN2006101487299 A CN 2006101487299A CN 200610148729 A CN200610148729 A CN 200610148729A CN 101210164 B CN101210164 B CN 101210164B
Authority
CN
China
Prior art keywords
polyamide
characterized
polyolefin elastomer
described
composition
Prior art date
Application number
CN2006101487299A
Other languages
Chinese (zh)
Other versions
CN101210164A (en
Inventor
祝爱兰
顾庆锋
王建平
Original Assignee
上海轻工业研究所有限公司
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 上海轻工业研究所有限公司 filed Critical 上海轻工业研究所有限公司
Priority to CN2006101487299A priority Critical patent/CN101210164B/en
Publication of CN101210164A publication Critical patent/CN101210164A/en
Application granted granted Critical
Publication of CN101210164B publication Critical patent/CN101210164B/en

Links

Abstract

The invention provides a polyamide hot melt adhesive, which contains, by total weight, 50 to 90wt% dimer acid polyamide resin with a softening point of 160 to 220 DEG C, 5 to 25wt% polyolefin elastomer and 5 to 25wt% polypropylene grafted and modified by unsaturated carboxylic acid. The hot melt adhesive has the advantages of high softening point, good low-temperature flexibility, high adhesion strength, moderate hardness and high curing speed, as well as used in a temperature range of -20 DEG C to 100 DEG C, and is particularly suitable for lasting adhesive applying machinery. The invention also relates to shoes adhered by the polyamide hot melt adhesive.

Description

Polyamide hot and with its bonding footwear

Technical field

The present invention relates to hot melt adhesive and application thereof, particularly relate to polyamide hot and with its bonding footwear.

Background technology

China is the super big producing country of world's footwear industry, produces the footwear amount per year and reaches 70~8,000,000,000 pairs.A lot of operations all will be used tackiness agent in the shoemaking, and the shoe last or hat block that stretches tight makes upper of a shoe and good bond of the interior end with hot melt adhesive exactly, and the middle back shoe last or hat block of helping to stretch tight mainly uses the strip polyamide hot.The strip adhesive tape is coated at melten gel between the middle back group and the interior end of upper of a shoe by the sebific duct of automatic gum coater, finishes bonding operation in the several seconds.Footwear with polymeric amide after group's glue require to have better comprehensive performance, comprise that higher softening temperature, good adhesive strength and low temperature flexibility, fast setting, hardness moderate (shore hardness is greater than 40) and melt viscosity are moderate etc.The back group glue that present Chinese shoe industry uses can't meet above-mentioned requirements fully, and price is very expensive.

Polymeric amide is obtained after polycondensation by diprotic acid and diamine, according to the different products with various softening temperatures that can be made into of diprotic acid and diamine kind.By dimeracid (is long-chain unsaturated fatty acid, be the dimer of vegetable fatty acid) polyamide resin that obtains with the diamine condensation, be commonly called as dimer acid type polyamide, has good bonding strength, it has advantages such as fusion range is wide, curing speed is fast as hot melt adhesive, is highly suitable for shoe-making industry.Yet there are shortcomings such as toughness is bad, low temperature embrittlement, the little not easy-formation of melt viscosity in this series products, must carry out the requirement that modification could be fit to back group glue to it.

At present, the improvement way of taking both at home and abroad mainly contains blending and modifying and modification by copolymerization.The example of blending and modifying such as US5548027, US4791164, US4374231, with dimeric acid type polyamide hot melt adhesive and ethylene copolymer such as ethylene-vinyl acetate copolymer (EVA) with low Tg and low-crystallinity, ethylene-ethyl acrylate-maleic anhydride copolymer (EEA) melt blending, make and have the flexible polyamide hot product of good low temperature, but adding along with the modifier of these low Tgs, the hardness of hot melt adhesive descends, if make the strip shoes-used glue, will not be difficult to send adhesive tape to automatic double surface gluer because there being enough hardness.As being main matrix with dimer acid type polyamide, with the EEA blend, the hot melt adhesive resistance to low temperature that obtains reaches-30 ℃, but shore hardness D is no more than 29.

The modification by copolymerization aspect mainly is by adding properties-correcting agent the dimer acid type polyamide matrix to be carried out grafting, crosslinked; Perhaps, by selecting the comonomer raw material to improve the low-temperature performance and the adhesiveproperties of dimeric acid type polyamide hot melt adhesive.As CN1080752C, CN1264894C etc. all is matrix with the dimer acid type polyamide, is aided with grafting, crosslinked, and the hot melt adhesive that obtains has good low-temperature toughness and bonding strength, but softening temperature and hardness are lower, is not suitable for making footwear and helps glue with the back.

It is 90~110 ℃ dimer acid type polyamide resin that US5922831 adopts the copolymerization mode to synthesize softening temperature, and with low molecular polarity wax and polyolefin elastomer to its blending and modifying, obtain a kind of hot melt adhesive that is applicable to the vamp typing, resistance to low temperature-5 ℃, but softening temperature is no more than 125 ℃, can not satisfy the requirement of back group glue equally.

Summary of the invention

The purpose of this invention is to provide a kind of stretch tight polyamide hot (being called for short back group glue) of shoe last or hat block operation of group behind the shoe industry that is used for.Not only softening temperature high and low temperature snappiness is good, bonding strength is high for this hot melt adhesive, and hardness is moderate, curing speed is fast, is particularly useful for the gluing machinery of the various shoe last or hat blocks that stretch tight, and can use in-20~100 ℃ of temperature ranges.

Polyamide thermosol composition of the present invention comprises in its gross weight:

1) 50~90wt% softening temperature be 160~220 ℃ dimer acid type polyamide resin and

2) polyolefin elastomer of 5~25wt% and

3) polypropylene of the unsaturated carboxylic acid graft modification of 5~25wt%.

The preparation method of polyamide hot of the present invention may further comprise the steps:

Melt extrude cooling and pelletizing with mixing in dimer acid type polyamide resin, polyolefin elastomer and the unsaturated carboxylic acid graft polypropylene adding mixing machine, adding in the twin screw extruder then;

2) the above-mentioned blend particle that obtains is put into the loft drier thorough drying after, place forcing machine to melt extrude into strips and cooling, through tractor adhesive tape is sent into up-coiler, make the adhesive tape of diameter 3.85 ± 0.15mm.

The invention still further relates to the bonding footwear of above-mentioned polyamide thermosol composition.

Embodiment:

Polyamide thermosol composition of the present invention amounts to its gross weight and comprises:

1) 50~90wt% softening temperature is 160~220 ℃ of dimer acid type polyamide resins;

2) 5~25wt%, preferred 5~20wt% polyolefin elastomer;

3) 5~25wt%, the polypropylene of preferred 5~20wt% unsaturated carboxylic acid graft modification.

Used dimer acid type polyamide resin is a copolyamide among the present invention, and it is the polycondensation product of di-carboxylic acid component and diamine component.

The mole ratio scope of above-mentioned di-carboxylic acid component and diamine component is 1: 1~1: 1.2, is preferably 1: 1~1: 1.1, more preferably 1: 1~1: 1.05.

Suitable di-carboxylic acid component can all be the dimeracid unit, also can be dimeracid unit and the unitary mixture of aliphatic dicarboxylic acid.Wherein the unitary mole ratio of dimeracid unit and aliphatic dicarboxylic acid is 1.00: 0.00~0.80: 0.20, is preferably 0.90: 0.10~0.80: 0.20, more preferably 0.90: 0.10~0.85: 0.15.

Above-mentioned dimeracid is two or more C 18Unsaturated fatty acids (as oleic acid, linolic acid) through polyreaction, is removed the diprotic acid that obtains after unreacted single acid in the presence of catalyzer, be with C 36Dimer is main mixture, wherein contains a small amount of tripolymer and part isomerization unconverted monomer.

Above-mentioned aliphatic dicarboxylic acid can contain 4~22 carbon atoms.Concrete example comprises Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, tetradecane diacid, Thapsic acid, octadecane diacid, octadecane dicarboxylic acid or its mixture, preferred example comprises Succinic Acid, hexanodioic acid, sebacic acid or its mixture, and preferred example is hexanodioic acid, sebacic acid or its mixture.

Suitable diamine comprises aliphatic diamine, alicyclic diamine, aromatic diamine or its mixture.

Above-mentioned aliphatie diamine can contain 2~12 carbon atoms, its example comprises quadrol, propylene diamine, butanediamine, pentamethylene diamine, 2 methyl pentamethylenediamine, hexanediamine, octamethylenediamine, decamethylene diamine, dodecane diamines and composition thereof, preferred example comprises quadrol, propylene diamine, butanediamine, hexanediamine, decamethylene diamine and composition thereof, and preferred example is quadrol, propylene diamine, hexanediamine or its mixture.

Above-mentioned alicyclic diamine can contain 4~10 carbon atoms, preferably contains 5~8 carbon atoms.Concrete example comprises ring pentamethylene diamine, cyclohexanediamine, ring octamethylenediamine and composition thereof, and preferred example comprises cyclohexanediamine, and most preferred example is 1, the 4-cyclohexanediamine.

Above-mentioned aromatic diamine can contain the carbon aromatic ring diamines or the hetero-aromatic ring diamines of 5~10 carbon atoms.Concrete example comprises phenylenediamine, tolylene diamine, pyridine diamines and composition thereof, and preferred example comprises 1,4-phenylenediamine, 1,4-tolylene diamine and composition thereof.

Also can add an amount of polyamine such as diethylenetriamine, triethylene tetramine etc. in the above-mentioned diamine.

Above-mentioned diamine can all be a quadrol, also can be the mixture of quadrol and other diamine.The mole ratio of quadrol and other diamine was generally 1.00: 0.00~0.80: 0.20, was preferably 1.00: 0.00~0.90: 0.10, more preferably 0.99: 0.01~0.90: 0.10.

The softening temperature that is applicable to dimer acid type polyamide resin of the present invention is generally 160~220 ℃, is preferably 160~200 ℃, more preferably 160~190 ℃.

The weight-average molecular weight that is applicable to dimer acid type polyamide resin of the present invention is 1000~10000, is preferably 2000~8000, more preferably 3000~7000.

Be applicable to dimer acid type polyamide resin acid number of the present invention general<10mgKOH/g, be preferably<8mgKOH/g, more preferably<5mgKOH/g; The amine value is general<8mgHCl/g, be preferably<5mgHCl/g, more preferably<3mgHCl/g.

The content that is applicable to dimer acid type polyamide of the present invention is preferably 60~90wt%, 65~85wt% more preferably, 70~80wt% more preferably, in polyamide hot of the present invention with its gross weight.

Above-mentioned dimer acid type polyamide is commercially available or by method as known in the art preparation.For example referring to document: Encyclopadia of Polymer Science and Engineering, volume was 476~489 pages in 1987 the 11st.

Be applicable to that polyolefin elastomer of the present invention is ethene and the alpha-olefin multipolymer that polymerization obtains under metallocene catalyst, alpha-olefin comonomer contains 3-10 carbon atom, preferably contain 3-8 carbon atom, for example comprise propylene, butylene, hexene, octene and composition thereof, preferably include propylene and octene.The content of alpha-olefin is 20~40wt%, is preferably 20~30wt%, in the weight of polyolefin elastomer.The weight-average molecular weight that is applicable to polyolefin elastomer of the present invention is generally 3000 to 50000, is preferably 3000 to 30000.

The melting index that is applicable to polyolefin elastomer of the present invention is generally 0.5~100g/10min (190 ℃), is preferably 1~60g/10min, more preferably 3~30g/10min.

Above-mentioned polyolefin elastomer is the commercial goods, has lower density (0.86~0.90g/cm 3) and excellent low temperature kindliness, its preparation method can be referring to document Encyclopadia of Polymer Scienceand Engineering, nineteen ninety 106~127 pages of index volumes.

The content that is applicable to polyolefin elastomer of the present invention is preferably 8~20wt%, 10~15wt% more preferably, in polyamide hot of the present invention with its gross weight.

Above-mentioned unsaturated carboxylic acid graft modified polypropene, can be unsaturated acid or acid anhydride-grafted polypropylene, for example be maleic anhydride, fumaric acid anhydride, acrylic or methacrylic acid grafted polypropylene, wherein the percentage of grafting of unsaturated carboxylic acid is 0.1~5%, be preferably 0.1~2%, more preferably 0.5~2%.

The preferred polypropylene that uses maleic anhydride graft among the present invention.

The polypropylene of above-mentioned unsaturated carboxylic acid graft modification has higher polarity and excellent flowing, and melting index is generally 0.1~200, is preferably 1~200, and more preferably 10~200.

The polyacrylic weight-average molecular weight that is applicable to unsaturated carboxylic acid graft modification of the present invention is 5000 to 80000, is preferably 5000 to 50000.

The polypropylene of above-mentioned unsaturated carboxylic acid graft modification is the commercial goods.

The polyacrylic content that is applicable to unsaturated carboxylic acid graft modification of the present invention is preferably 7~20wt%, and more preferably 10~15wt% uses polyamide hot with its gross weight in footwear of the present invention.

Except said components, footwear of the present invention also can add additive commonly used in this area according to actual needs with polyamide hot, as flow ability modifying agent, oxidation inhibitor, antiaging agent, photostabilizer, lubricant etc.

The object lesson of flow ability modifying agent is Gum Rosin commonly used in this area, terpine resin, paraffin, polyethylene wax, Microcrystalline Wax and composition thereof.

The consumption of flow ability modifying agent is generally 0~5wt%, is preferably 0.01~1wt%, and more preferably the gross weight with polyamide hot of the present invention is a benchmark.

The object lesson of oxidation inhibitor comprises four [β-(3; 5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester (be called for short 1010), β-(3; the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid (being called for short 1076), N; N '-two-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) hexanediamine (being called for short 1098), 2 propionyl); 6--di-tert-butyl-4-methy phenol (being called for short 264), triphenyl phosphite etc.; the consumption of oxidation inhibitor is generally 0~2wt%; being preferably 0.02~1wt%, is benchmark with the gross weight of polyamide hot of the present invention.

Good in above-mentioned ratio general, polyolefin elastomer, maleic anhydride grafted polymer weighing, in mixer, mix, in adding twin screw extruder, melt extrude, cooling, pelletizing, particle drying case oven dry back adds extruder for shaping, up-coiler is sent into by tractor in adhesive tape cooling back, make the adhesive tape of diameter 3.85 ± 0.15mm, promptly obtain polyamide hot of the present invention.

Polyamide hot of the present invention is specially adapted to bonding upper of a shoe.Not only softening temperature high and low temperature snappiness is good, bonding strength is high for it, and hardness is moderate, curing speed is fast, is particularly useful for the gluing machinery of the various shoe last or hat blocks that stretch tight, and uses in-20~100 ℃ of temperature ranges.

Embodiment

Each performance perameter is tested as follows among the embodiment:

Ring and ball softening point is tested according to standard GB/T 15332-1994.

Melt viscosity adopts the test of Brookfield DV-E type rotational viscosimeter, take by weighing the polyamide hot sample of 11.0g, selecting model is the rotor of S27, temperature is controlled at 200 ℃, and constantly regulate and rotate rotating speed, make its test value be positioned at 10~90% linearity range, stable back record observed value.

Shore hardness adopts the GB2411-80 test.

The anti-test of elongation rate of opening carries out rate of extension 50mm/min according to standard A STM D638-2003.

The test of resistance to low temperature is carried out according to standard A STM D3111, proof stick diameter 3.2mm, and the temperature that embrittlement does not take place with 80% sample is represented.

Stripping strength: adopt the GB2791-81 standard test, rate of extension 50mm/min.

Embodiment 1

With 4620 gram dimer acid type polyamide (170 ℃ of softening temperatures, lower temperature resistance-10 ℃, trade(brand)name KINGMIDE H-170HV, available from Taiwan three plying part company limiteds), (trade(brand)name Engage 8200 for 720 gram polyolefin elastomers, available from LG-DOW company), polypropylene (the trade(brand)name BONP GPM200A of 660 gram maleic anhydride grafts, available from Ningbo NengZhiGuang New Materials Science Co., Ltd) and 20 gram antioxidant 1010s adding mixing machine (model GF300, available from the logical company of moulding in Zhangjiagang), after mixing 1 hour with the stirring velocity of 70 commentaries on classics/min, add twin screw extruder (model TES-35 again, available from Nanjing Rhea company) in, control screw zones Heating temperature is about 175 ℃, extrude through screw rod, cooling, pelletizing obtains the hot melt adhesive section.Section is put into 100 ℃ of baking ovens after dry 4 hours, adds single screw extrusion machine and melt extrudes, and the adhesive tape cooling of extruding promptly obtains the footwear polyamide hot bar of diameter 3.85 ± 0.15mm after tractor is sent into up-coiler.Every index of test adhesive tape the results are shown in Table 1.

Embodiment 2

With 3900 gram dimer acid type polyamide (172 ℃ of softening temperatures, lower temperature resistance-5 ℃, trade(brand)name TOHMIDE170, change into Co., Ltd. available from Japanese fuji), 600 gram polyolefin elastomer (trade(brand)name Exact3024, available from Exxon Mobil Corporation), 500 the gram maleic anhydride grafts polypropylene (trade(brand)name BONP GPM200B, available from Ningbo NengZhiGuang New Materials Science Co., Ltd) and 15 gram antioxidant 264s, with with embodiment 1 in identical equipment and technology, make the footwear polyamide hot bar of diameter 3.85 ± 0.15mm.Every index of test adhesive tape the results are shown in Table 1.

Embodiment 3

With 4000 gram dimer acid type polyamide resin (171 ℃ of softening temperatures, lower temperature resistance-10 ℃, trade(brand)name LR-PA-170, Liri Chemical New Materials Co., Ltd. Shanghai's production), 600 gram polyolefin elastomer (trade(brand)name Tafmer DF740, available from Mitsui company), 500 the gram maleic anhydride grafts polypropylene (trade(brand)name KTJ-1A, available from logical plastic cement Science and Technology Ltd. of Shenyang section) and 20 gram antioxidant 1010s, with with embodiment 1 in identical equipment and technology, make the footwear polyamide hot bar of diameter 3.85 ± 0.15mm.Every index of test adhesive tape the results are shown in Table 1.

Embodiment 4

With 3300 gram dimer acid type polyamide (172 ℃ of softening temperatures, lower temperature resistance-5 ℃, trade(brand)name TOHMIDE170, change into Co., Ltd. available from Japanese fuji), 1500 gram polyolefin elastomer (trade(brand)name Exact3024, available from Exxon Mobil Corporation), 1200 the gram maleic anhydride grafts polypropylene (trade(brand)name BONP GPM200B, available from Ningbo NengZhiGuang New Materials Science Co., Ltd) and 15 gram antioxidant 264s, with with embodiment 1 in identical equipment and technology, make the footwear polyamide hot bar of diameter 3.85 ± 0.15mm.Every index of test adhesive tape the results are shown in Table 1.

Embodiment 5

With 3600 gram dimer acid type polyamide resin (170 ℃ of softening temperatures, lower temperature resistance-10 ℃, trade(brand)name KINGMIDE H-170HV, available from Taiwan three plying part company limiteds), 1000 gram polyolefin elastomer (trade(brand)name Tafmer DF740, available from Mitsui company), acrylic acid-grafted polypropylene (the trade(brand)name KTJ-3B of 1000 grams, available from logical plastic cement Science and Technology Ltd. of Shenyang section) and 20 gram antioxidant 1010s, with with embodiment 1 in identical equipment and technology, make the footwear polyamide hot bar of diameter 3.85 ± 0.15mm.Every index of test adhesive tape the results are shown in Table 1.

Table 1

By above-mentioned data as seen, polyamide hot of the present invention has high softening temperature, good low temperature flexibility, high bonding strength, moderate hardness, fast curing speed are particularly useful for the gluing machinery of the various shoe last or hat blocks that stretch tight, and use in-20~100 ℃ of temperature ranges.

Claims (10)

1. polyamide thermosol composition comprises in its gross weight:
1) 50~90wt% softening temperature be 160~220 ℃ dimer acid type polyamide resin and
2) 5~25wt% polyolefin elastomer and
3) polypropylene of 5~25wt% unsaturated carboxylic acid graft modification.
2. polyamide thermosol composition as claimed in claim 1 is characterized in that it comprises:
1) 60~85wt% softening temperature is 160~200 ℃ a dimer acid type polyamide resin,
2) 8~20wt% polyolefin elastomer and
3) polypropylene of 7~20wt% unsaturated carboxylic acid graft modification.
3. polyamide thermosol composition as claimed in claim 1 or 2 is characterized in that, the weight-average molecular weight of described dimer acid type polyamide is 1000~10000.
4. polyamide thermosol composition as claimed in claim 3 is characterized in that, the acid number<10mgKOH/g of described dimer acid type polyamide, amine value<8mgHCl/g.
5. polyamide thermosol composition as claimed in claim 1 or 2 is characterized in that, described polyolefin elastomer is ethene and α-C 3-10The alkene multipolymer that polymerization obtains under metallocene catalyst.
6. polyamide thermosol composition as claimed in claim 5 is characterized in that, α-C in the described polyolefin elastomer 3-10The content of alkene is 20~40wt%, in the weight of polyolefin elastomer.
7. polyamide thermosol composition as claimed in claim 5 is characterized in that, 190 ℃ of melting index of described polyolefin elastomer are 0.5~100g/10min, weight average molecular weight range 3000~50000.
8. polyamide thermosol composition as claimed in claim 1 or 2 is characterized in that, the polypropylene of described unsaturated carboxylic acid graft modification is the polypropylene of modified by maleic acid anhydride graft, and percentage of grafting is 0.1~5%.
9. polyamide thermosol composition as claimed in claim 8 is characterized in that, the polyacrylic weight-average molecular weight of described unsaturated carboxylic acid graft modification is 5000~80000.
10. use as the bonding footwear of each described polyamide thermosol composition among the claim 1-9.
CN2006101487299A 2006-12-30 2006-12-30 Polyamide hot-melt adhesive and shoe bonded by the same CN101210164B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2006101487299A CN101210164B (en) 2006-12-30 2006-12-30 Polyamide hot-melt adhesive and shoe bonded by the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2006101487299A CN101210164B (en) 2006-12-30 2006-12-30 Polyamide hot-melt adhesive and shoe bonded by the same

Publications (2)

Publication Number Publication Date
CN101210164A CN101210164A (en) 2008-07-02
CN101210164B true CN101210164B (en) 2011-04-20

Family

ID=39610421

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2006101487299A CN101210164B (en) 2006-12-30 2006-12-30 Polyamide hot-melt adhesive and shoe bonded by the same

Country Status (1)

Country Link
CN (1) CN101210164B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102559128A (en) * 2010-12-20 2012-07-11 深圳市宏商材料科技股份有限公司 Formula of oil-resistant hot melt adhesive and production process of hot melt adhesive
CN102924712A (en) * 2012-10-18 2013-02-13 上海天洋热熔胶有限公司 Low-melting-point polyamide hot melt adhesive with high weather resistance and preparation method thereof
CN103524731A (en) * 2013-10-16 2014-01-22 上海天洋热熔胶有限公司 Preparation method of polyamide hot melt adhesive with low surface energy for hot drills
CN104804659B (en) * 2015-05-11 2017-08-29 上海天洋热熔粘接材料股份有限公司 A kind of hot melt adhesive film for being used for bonded metal and non-polar material and preparation method thereof
CN106433550A (en) * 2016-09-21 2017-02-22 东莞市舜天实业有限公司 Polyamide hot-melt adhesive

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1054392A (en) * 1990-02-06 1991-09-11 希蒙特公司 The method of repairing plastic coatings on metal tubing
US5922831A (en) * 1996-04-04 1999-07-13 Heinrich; Dwight D. Method of manufacturing an upper for a shoe
US6013373A (en) * 1997-10-20 2000-01-11 Hoechst Celanese Corporation Adhesives for making multilayer films comprising liquid crystalline polymer and polypropylene
JP2001139911A (en) * 1999-10-29 2001-05-22 Three M Innovative Properties Co Hot-melt adhesive composition for bonding polyolefin
CN1363465A (en) * 2000-12-23 2002-08-14 德古萨公司 Multi-layer composite material with polyamide/polyolefine as base
JP4081484B2 (en) * 1995-04-27 2008-04-23 アメリカ合衆国 Antiviral protein, its DNA coding sequence and use thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1054392A (en) * 1990-02-06 1991-09-11 希蒙特公司 The method of repairing plastic coatings on metal tubing
JP4081484B2 (en) * 1995-04-27 2008-04-23 アメリカ合衆国 Antiviral protein, its DNA coding sequence and use thereof
US5922831A (en) * 1996-04-04 1999-07-13 Heinrich; Dwight D. Method of manufacturing an upper for a shoe
US6013373A (en) * 1997-10-20 2000-01-11 Hoechst Celanese Corporation Adhesives for making multilayer films comprising liquid crystalline polymer and polypropylene
JP2001139911A (en) * 1999-10-29 2001-05-22 Three M Innovative Properties Co Hot-melt adhesive composition for bonding polyolefin
CN1363465A (en) * 2000-12-23 2002-08-14 德古萨公司 Multi-layer composite material with polyamide/polyolefine as base

Also Published As

Publication number Publication date
CN101210164A (en) 2008-07-02

Similar Documents

Publication Publication Date Title
DE502005008522C5 (en) Use of polyolefin waxes in hotmelt compositions
KR101544236B1 (en) Hot melt adhesive
CN103781840B (en) Hot-melt adhesive
CN101006147B (en) Water-based primer composition
US5889114A (en) Thermoplastic elastomeric compositions
EP1592756B1 (en) Hot melt adhesive composition
JP5430941B2 (en) Hot melt adhesive composition
EP1493792B1 (en) Hot melt adhesive
EP0188542B1 (en) Blends of polyamides and ethylene polymers carboxylic acid groups
US5929145A (en) Bitumen backed carpet tile
DE69818496T2 (en) Thermoplastic marking compositions
CN101914252B (en) Low-cost environment-friendly injection-molding high heat-resistant high impact-resistant rigid polyvinyl chloride composite and preparation method thereof
CN1079812C (en) Solid sheared polymer blends and process for their preparation
JP4762468B2 (en) Hot melt adhesives based on blends of EPR and / or EPDM with semi-crystalline olefin polymers
KR20010077954A (en) Hot melt adhesive composition comprising homogeneous ethylene interpolymer and block copolymer
US3626026A (en) Hotmelt adhesive compositions
CA2504696C (en) Powder coating compositions
CN102585753B (en) Polyurethane hot-melt adhesive for bonding and preparation method thereof
US20070135563A1 (en) Adhesives comprising olefin copolymers
US20100130677A1 (en) Polyamide-based thermoplastic polymer compositions
CN103797081A (en) Hot melt adhesive
CN103391982B (en) Hotmelt
CN103755876B (en) Unformed poly-alpha olefins of a kind of polar monomer graft modification and preparation method thereof
CN102433087B (en) High-temperature-resistant paper-plastic laminating adhesive and preparation method thereof
AU2011310639B2 (en) Bonding using hot-melt adhesives

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract

Assignee: Liri Chemical New Materials Co., Ltd. Shanghai

Assignor: Shanghai Light Industry Research Institute Co., Ltd.

Contract record no.: 2011310000086

Denomination of invention: Polyamide hot-melt adhesive and shoe bonded by the same

Granted publication date: 20110420

License type: Exclusive License

Open date: 20080702

Record date: 20110621

TR01 Transfer of patent right

Effective date of registration: 20170605

Address after: 200031 Shanghai City Baoqing Road No. 20

Co-patentee after: Liri Chemical New Materials Co., Ltd. Shanghai

Patentee after: Shanghai Light Industry Research Institute Co., Ltd.

Address before: 200031 Shanghai City Baoqing Road No. 20

Patentee before: Shanghai Light Industry Research Institute Co., Ltd.

TR01 Transfer of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20110420

Termination date: 20171230

CF01 Termination of patent right due to non-payment of annual fee