CN1261519C - Polyurethane adhesive in use for composite nylon film - Google Patents
Polyurethane adhesive in use for composite nylon film Download PDFInfo
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- CN1261519C CN1261519C CN 200410034033 CN200410034033A CN1261519C CN 1261519 C CN1261519 C CN 1261519C CN 200410034033 CN200410034033 CN 200410034033 CN 200410034033 A CN200410034033 A CN 200410034033A CN 1261519 C CN1261519 C CN 1261519C
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- polyurethane adhesive
- solidifying agent
- nylon membrane
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Abstract
The present invention discloses a polyurethane adhesive for the compounding of nylon films, which is a bi-component polyurethane adhesive comprising a main agent and a solidifying agent, wherein the weight ratio of the main agent to the solidifying agent is as follows: the main agent to the solidifying agent is equal to 100:10 to 20. The main agent comprises the components of the following weight percentages: 30 to 75 wt% of polyurethane prepolymers, 0.1 to 3 wt% of polyamide and 20 to 50 wt% of organic solvent. The solidifying agent is an addition product of the rection of polyisocyanate and polyol according to the proportion of NCO/OH being about 2. The organic solvent is one or several kinds of ester, ketone or an aromatic hydrocarbon fluxing agent. The polyisocyanate is toluene diisocyanate, and the isocyanato value of the polyisocyanate is from 10 to 15%. The peeling strength and the flexibility of a nylon composite film can be enhanced by the polyurethane adhesive, and a nylon composite film product can meet the requirements for the nylon composite film product in production and life.
Description
Technical field:
The present invention relates to a kind of polyurethane adhesive, relate in particular to a kind of nylon membrane compound polyurethane adhesive that is used for.
Background technology:
Bi-component polyurethane adhesive is a most important big class in the polyurethane adhesive, and purposes is wide, and consumption is big.Usually be made up of two components of first, second, two components are separately to pack, and preparation by a certain percentage gets final product before the use.First component (host) is a hydroxy component, and second component (solidifying agent) is for containing the component of isocyanate groups.The host that also has is the base polyurethane prepolymer for use as of end group NCO, and solidifying agent is low molecular weight polyols or polyamine, and first component and second component are mixed the generation urethane resin by a certain percentage.
Bi-component polyurethane adhesive has following characteristics.
(1) belongs to reactive tackiness agent after two components are mixed, crosslinking reaction takes place, produce cured product.
When (2) preparing, can regulate the raw material of two components and form and molecular weight, making it at room temperature has suitable viscosity, can be made into high solids content or solvent-free two component adhesive.
(3) common ambient temperature curable can be regulated curing speed by raw material or the adding catalyzer of selecting the preparation tackiness agent.Generally, bi-component polyurethane adhesive has bigger first bounding force, and through being heating and curing, its final bond strength is bigger than monocomponent adhesive, can satisfy the requirement of sqtructural adhesive.
The consumption of (4) two components can be regulated within the specific limits, generally exists certain tolerance.The NCO/OH mol ratio of two components is in the ordinary course of things more than or equal to 1, when solidified, part NCO group participates in the curing reaction of glue, produce chemical adhesion power, unnecessary NCO group is when being heating and curing, also can produce allophanate, biuret etc., increase degree of crosslinking, improve the cohesive strength and the thermotolerance of glue-line.For solvent-free bi-component polyurethane adhesive, little because of each component starting molecule amount, in general the NCO/OH mol ratio is equal to or slightly greater than 1, helps completion of cure.And for the solvent-type double-component tackiness agent, its host molecular weight is bigger, and initial cohesiveness is better, and the consumption of two components can be regulated in a big way, and the NCO/OH mol ratio can be less than 1 or greater than 1 several times.When the excessive more occasion of NCO component (solidifying agent), the polyisocyanates autohemagglutination forms tough and tensile adhesive layer, is suitable for the bonding of hard material; In the few occasion of NCO amounts of components, then the glue-line softness can be used for the bonding of soft materials such as leather, fabric and various films.
Bi-component polyurethane adhesive owing to have advantages such as performance controllability, big, the bonding scope of bond strength are wide, has become the product that kind is maximum in the polyurethane adhesive, output is maximum since coming out.But when being used for nylon membrane and other base material formation matrix material, because existing polyurethane adhesive is not pointed on prescription composition and proportioning, caused the stripping strength of composite membrane of this structure not enough and snappiness is poor, be easy to generate composite membrane and peel off and rupture, do not satisfy in the productive life requirement this product.
Summary of the invention:
Technical problem to be solved by this invention provides a kind of polyurethane adhesive, and this polyurethane adhesive can improve the stripping strength and the snappiness of coextrusion nylon film, makes this composite membrane product can satisfy in the productive life requirement to it.
At above-mentioned technical problem, the invention provides following technical scheme: a kind of polyurethane adhesive, the dual-component polyurethane adhesive that it is made up of host and solidifying agent, wherein:
The weight ratio of host and solidifying agent is:
Host: solidifying agent=100: 10-20;
(1), the weight percent of the moiety of described host and each composition thereof is:
Polyurethane prepolymer: 30-75%
Polymeric amide: 0.1-3%
Organic solvent: 20-50%
(2), described solidifying agent be polyisocyanates and polyvalent alcohol according to:
The affixture of the ratio reaction of NCO/OH ≌ 2.
The hydroxyl value of described polyurethane prepolymer (OH) is: 5-30mgKOH/g.
Described polyisocyanates is a tolylene diisocyanate, and its isocyanic acid root is: 10-15%.
Described organic solvent is one or more in ester class, ketone or the arene flux, often is in ethyl acetate, methylethylketone, the toluene one or more.
The used polyvalent alcohol of described preparation solidifying agent is one or more in TriMethylolPropane(TMP), glycol ether or the 3-methylol pentanediol-2,4.
Described polyurethane prepolymer is the reaction product of polyesterols, polymeric amide and polyisocyanates.
Described polyesterols is one or more in polyethylene glycol adipate glycol (PEA), the polycondensate that gathers hexanodioic acid glycol ether esterdiol or polyprotonic acid and polyvalent alcohol.
Described polyisocyanates is tolylene diisocyanate, ditan-4, one or more in 4 '-vulcabond or the poly methylene poly phenyl poly isocyanate.
The polyesterols that being used to of relating among the present invention produced polyurethane prepolymer can utilize polyprotonic acid and polyol reaction to generate by the vacuum fusion method, the concrete grammar process of this vacuum fusion method is: according to the needed hydroxyl value of polyurethane prepolymer, pass through stoichiometric calculation, determine the ratio of polyvalent alcohol and polyprotonic acid and catalyzer, generally speaking, polyprotonic acid lacks 10-20% than the consumption of polyvalent alcohol according to molar ratio; Catalyzer is tetra-n-butyl titanate or zinc acetate, and its consumption is the 100-300ppm of reaction mass total amount.
Polyprotonic acid and polyvalent alcohol are added in the vacuum reactor; heating then; when waiting for raw material, this reaction mass is stirred, add catalyzer by solid-state liquefy; seal this vacuum reaction container; feed inert protective gas, gas generally commonly used is nitrogen, continues heat temperature raising; when the reaction vessel temperature reaches 150 ℃; isolate methyl alcohol or water, controlling fractionation tower temperature simultaneously is 100-102 ℃, keeps temperature in the vacuum reaction container like this under 220-250 ℃ situation; reacted 5-8 hour; after treating that methyl alcohol or water sepn finish, stop to feed nitrogen, begin then to vacuumize; vacuum tightness remains on 0.05Mpa; keeping temperature of reaction simultaneously is 220-230 ℃, continues reaction 6-8 hour again, slowly cools to 80 ℃ then; stop to vacuumize this moment, promptly finishes the preparation of polyesterols.
Described polyprotonic acid (or ester) comprises hexanodioic acid, nonane diacid, sebacic acid, sebacic anhydride, Succinic Acid, m-phthalic acid, terephthalic acid, dimethyl terephthalate (DMT), maleic acid, Tetra hydro Phthalic anhydride or two or more mixtures, and preferred plan is: hexanodioic acid, sebacic acid, m-phthalic acid, dimethyl terephthalate (DMT), terephthalic acid or two or more mixtures;
Described polyvalent alcohol comprises: ethylene glycol, 1,2-propylene glycol, 1, the 4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, glycol ether, dipropylene glycol, TriMethylolPropane(TMP), methyl propanediol, 1,2,6-hexanetriol, glycerine, tetramethylolmethane, dihydroxyphenyl propane or its two or more mixture, preferred plan is: ethylene glycol, glycol ether, neopentyl glycol, 1,4-butyleneglycol or its two or more mixture.
The synthetic method of polyurethane prepolymer is: polyesterols and polymeric amide and polyisocyanates are dissolved in the organic solvent in proportion, 50-100 ℃ of reaction 2-4 hour, obtain the polyurethane prepolymer solution that hydroxyl value is 5-30mgKOH/g, i.e. tackiness agent host.
The weight percent of each component of host is:
Polyurethane prepolymer (hydroxyl value is 5-30mgKOH/g): 30-75%
Polymeric amide 0.1-3%
Organic solvent 20-50%
Solidifying agent of the present invention is that tolylene diisocyanate is through polyalcohol modified affixture, its preparation method is: with tolylene diisocyanate and the polyvalent alcohol ratio according to (NCO)/(OH) ≌ 2,40-100 ℃ the reaction 1-6 hour after, cool to 50-70 ℃, add organic solvent to make the isocyanic acid root be 10-15%, free toluene diisocyanate solidifying agent less than 0.5%;
Participate in this modification tolylene diisocyanate polyvalent alcohol can in TriMethylolPropane(TMP) or the glycol ether one or more.
Theoretical basis of the present invention is:
1, polyurethane adhesive provided by the present invention is from mechanical theory, and tackiness agent molecular weight provided by the present invention is less relatively, can infiltrate in the space on adherend surface, and get rid of the air that adsorbs on its interface, produces bonding effect.
2, from adsorption theory, tackiness agent provided by the present invention bonding to as if caused by contact of two storeroom molecules and interfacial force generation.The main source of bonding force is that Intermolecular Forces comprises hydrogen bond force and Van der Waals force.The wet processes of tackiness agent and adherend Continuous Contact promptly will make the wetting solid surface of tackiness agent, and the surface tension of tackiness agent should be less than the solid critical surface tension, and depression and space that tackiness agent immerses solid surface just form good wet.If tackiness agent is maked somebody a mere figurehead at the recess on surface, just reduced the real contact area of tackiness agent and adherend, thus the bonding strength of joint reduced.The surface tension of most solid adherends such as nylon is all less than the surface tension of tackiness agent.And the condition that will obtain good wet is to make tackiness agent lower than the surface tension of adherend, and Here it is adds tackiness agent behind the polymeric amide has all had fabulous cementability to various materials reason.
Closely contact with adherend by the wetting tackiness agent that makes, mainly be produce by Intermolecular Forces permanent bonding.The chemical bond that is comprised in adhesive power and force of cohesion has four types:
(1) ionic linkage
(2) covalent linkage
(3) metallic bond
(4) Van der Waals force
3,, bonding by molecular diffusion generation on tackiness agent and the adherend interface from diffusion theory.When tackiness agent and adherend all are that diffusion theory is suitable for substantially when having the long-chain macromolecule polymkeric substance that can move.After polyurethane adhesive provided by the invention adds polymeric amide, molecular weight to traditional polyurethane adhesive has correspondingly been made adjustment, itself and bonding object all have the feature of the long-chain macromolecule that can move, so this also is to add tackiness agent behind the polymeric amide to have improved reason to various material adhesives.
Comprehensive above-mentioned theory analysis, the coextrusion nylon film stripping strength height, the flexility that adopt polyurethane adhesive of the present invention to make are good.
Embodiment:
In order to confirm the present invention and characteristic thereof, the present invention is described below by embodiment:
Example one:
With contract propylene glycol 1: 1: 1.5 in proportion of m-phthalic acid, hexanodioic acid, ethylene glycol, one: 1 adds reactor, and catalyzer metatitanic acid four butyl esters are 0.01% of total amount, prepares polyesterols by the molten method of vacuum.
Above-mentioned polyesterols cooling adding is accounted for the polymeric amide that contains total amount 0.16% admittedly, dash with vinyl acetic monomer and to be interpreted into 80% solution, add the tolylene diisocyanate that accounts for polyester and polymeric amide weight 5% again and reacted 3 hours down, again with the solution of vinyl acetic monomer its furnishing 70% at 78 ℃.Promptly get tackiness agent host, this host hydroxyl value is 30mgKOH/g.
3.1 molar tolylene diisocyanates are warming up to 100 ℃, add 1 molar TriMethylolPropane(TMP), reacted 3 hours, its product becomes 75% solution with dilution with toluene, promptly obtains the isocyanic acid root and be 15% solidifying agent.
Above-mentioned host and solidifying agent were mixed by 100: 10, be washed into 40% working fluid again, with the compound PA/PE film of dry compound machine, its stripping strength is 6.0N/15mm after the slaking, and have only 3.0N/15mm with universal tackiness agent stripping strength, folding 20 the no marks of break of composite membrane, and fold 5 existing marks of break with common glue.
Example two: will gather hexanodioic acid glycol ether ester 100 grams and polyamide 6 .8 gram and be dissolved in the 116.8 gram acetone, add 10 gram diphenylmethanediisocyanates, reacted 2.5 hours down, be host at 70 ℃, this host solid content is 50%, and hydroxyl value is 5mgKOH/g.
The 120g tolylene diisocyanate is mixed with the 150g vinyl acetic monomer, add 25g TriMethylolPropane(TMP) and 5g Diethylene Glycol down at 40 ℃-45 ℃, reacted 2 hours down at 70 ℃, obtain solid content 50%, the isocyanic acid root is 10% solidifying agent.
Above-mentioned host and solidifying agent were mixed by 100: 20, be washed into 25% working fluid again, with the compound PA/CPP film of dry compound machine, its stripping strength is that 7.2N/15mm uses the coventional type tackiness agent to have only 3.3N/15mm after the slaking, folding 20 the no marks of break of composite membrane, and fold 4 existing marks of break with coventional type.
Example three:
With terephthalic acid, sebacic acid, hexanodioic acid, ethylene glycol, new the eleventh of the twelve Earthly Branches glycol, Diethylene Glycol, by 1: 1: 1.5: add reactor at 1: 0.5: 2.5, catalyzer is a zinc acetate 0.03%, prepares polyesterols by the vacuum fusion method.
With above-mentioned polyesterols 100g and 3g polymeric amide, be dissolved in the mixed solvent of 58g methylethylketone-vinyl acetic monomer (1: 1), add isophorone diisocyanate 5g, reacted 4 hours down at 75 ℃, generate solid content 65%, the tackiness agent host of hydroxyl value 22mgKOH/g.
Above-mentioned host is mixed with 100: 15 with solidifying agent in the example 1, dash with vinyl acetic monomer and to be interpreted into 35% working fluid, with the compound PA/PE film of dry compound machine, its stripping strength is 6.8N/15mm after the slaking, can folding 20 no marks of break, and coventional type has only 3.0N/15mm, folding 5 existing marks of break.
Example four:
To gather m-phthalic acid hexanodioic acid binaryglycol ester 100g and 4g polymeric amide, be dissolved in the 50g vinyl acetic monomer, add the 12g tolylene diisocyanate, react 3 hours generation solid contents 70%, the host of hydroxyl value 15mgKOH/g down at 78 ℃.
Solidifying agent in above host and the example 2 is mixed with 30% working fluid to mix at 100: 10 with vinyl acetic monomer, with the compound PA/CPP film of dry compound machine, stripping strength is 8.2N/15mm after the slaking, collapsible 20 no marks of break.And medium-sizedly have only 3.3N/15mm, folding 4 times mark of break had both taken place.
Claims (7)
1, a kind of nylon membrane compound polyurethane adhesive that is used for, it be is characterized in that by the two-component adhesive that host and solidifying agent are formed:
The weight ratio of host and solidifying agent is:
Host: solidifying agent=100: 10-20;
Wherein:
(1), the weight percent of the moiety of described host and each composition thereof is:
Polyurethane prepolymer: 30-75%, this polyurethane prepolymer are the reaction product of polyesterols, polymeric amide and polyisocyanates;
Polymeric amide: 0.1-3%;
Organic solvent: 20-50%, this organic solvent are one or more in ester class, ketone or the aromatic hydrocarbon solvent;
Each weight percentages of components sum is 100%;
(2), described solidifying agent be polyisocyanates and polyvalent alcohol according to:
The affixture of the ratio reaction of NCO/OH ≌ 2.
2, the nylon membrane compound polyurethane adhesive that is used for as claimed in claim 1, it is characterized in that: the hydroxyl value of described polyurethane prepolymer is: 5-30mg KOH/g.
3, the nylon membrane compound polyurethane adhesive that is used for as claimed in claim 1, it is characterized in that: described polyisocyanates is a tolylene diisocyanate, its isocyanic acid root is: 10-15%.
4, the nylon membrane compound polyurethane adhesive that is used for as claimed in claim 1, it is characterized in that: described organic solvent is one or more in ethyl acetate, methylethylketone, the toluene.
5, the nylon membrane compound polyurethane adhesive that is used for as claimed in claim 1 is characterized in that: described polyvalent alcohol is one or more in TriMethylolPropane(TMP), glycol ether or the 3-methylol pentanediol-2,4.
6, the nylon membrane compound polyurethane adhesive that is used for as claimed in claim 1 is characterized in that: described polyesterols is one or more in polyethylene glycol adipate glycol, the polycondensate that gathers hexanodioic acid glycol ether esterdiol or polyprotonic acid and polyvalent alcohol.
7, the nylon membrane compound polyurethane adhesive that is used for as claimed in claim 1, it is characterized in that: described polyisocyanates is tolylene diisocyanate, ditan-4, one or more in 4 '-vulcabond or the poly methylene poly phenyl poly isocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410034033 CN1261519C (en) | 2004-04-22 | 2004-04-22 | Polyurethane adhesive in use for composite nylon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410034033 CN1261519C (en) | 2004-04-22 | 2004-04-22 | Polyurethane adhesive in use for composite nylon film |
Publications (2)
| Publication Number | Publication Date |
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| CN1563241A CN1563241A (en) | 2005-01-12 |
| CN1261519C true CN1261519C (en) | 2006-06-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200410034033 Expired - Fee Related CN1261519C (en) | 2004-04-22 | 2004-04-22 | Polyurethane adhesive in use for composite nylon film |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107267106A (en) * | 2017-07-10 | 2017-10-20 | 吴凡 | A kind of product glue and adhesive tape |
| CN109321193B (en) * | 2018-08-07 | 2021-04-27 | 中国乐凯集团有限公司 | Adhesive and preparation method and application thereof |
| CN114250054B (en) * | 2021-12-22 | 2024-02-09 | 广州白云科技股份有限公司 | Reactive polyurethane hot melt adhesive for nylon bonding and preparation method thereof |
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| CN1563241A (en) | 2005-01-12 |
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Owner name: HUZHOU OUMEI CHEMICAL CO., LTD. Free format text: FORMER OWNER: MOYIKE TECH CO., LTD., BEIJING Effective date: 20060120 |
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Effective date of registration: 20060120 Address after: 313000 No. 25 Fenghuang West Zone, Huzhou Economic Development Zone, Zhejiang Applicant after: Huzhou Europe and America Chemistry Co., Ltd. Address before: 100023 Beijing city Chaoyang District Wang Fuxing organic chemical factory Applicant before: Beijing Moyike Science & Technology Co., Ltd. |
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