CN103215006B - Multiple film glue of a kind of Low viscosity solvent-free polyurethane and preparation method thereof - Google Patents
Multiple film glue of a kind of Low viscosity solvent-free polyurethane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the multiple film glue of a kind of Low viscosity solvent-free polyurethane, comprise component A and B component, described component A is isocyanate terminated based compound, and described B component is terminal hydroxy group compound; Component A and B component are by terminal isocyanate group: the mol ratio of hydroxyl is 1.3 ~ 1.75 carry out mixing and obtaining bi-component polyurethane adhesive.The invention also discloses the preparation method of the multiple film glue of above-mentioned Low viscosity solvent-free polyurethane.The multiple film glue of Low viscosity solvent-free polyurethane prepared by the present invention, possesses that viscosity is low, curing speed fast, the advantage of high-peeling strength and resistance to 100 DEG C of high temperature steamings.
Description
Technical field
The present invention relates to the multiple film glue being applicable to composite soft packaging field, particularly multiple film glue of a kind of Low viscosity solvent-free polyurethane and preparation method thereof.
Background technology
There is not the problem of solvent evaporates in solvent-free polyurethane adhesive, is environmental-protection type adhesive, is one of new direction of tackiness agent development yet.Along with people are to the wholesomeness of wrapping material and the attention increasingly to environment protection, the multiple film glue of no-solvent type of environmental protection, as the substitute of solvent-type film-covered adhesive, just progressively becomes the new lover in composite soft packaging field.No-solvent type polyurethane laminating adhesive has following several large advantage: there is not solvent discharge problem, also there is not problem of solvent residual; Do not need complicated huge heat blowing, discarded air draft and emission-control equipment; Spread is few, thus reduces energy consumption, cost-saving; Can run up, enhance productivity.This some meet typical " three nothings " technique of solvent-free compound, in conjunction with the characteristic of tackiness agent excellence itself, solvent-free polyurethane laminating adhesive becomes the ideal chose advocating composite packaging field under the environmental protection epoch.
But solventless adhesive is not because it is containing solvent, therefore viscosity is comparatively large, the mobility in production process and the property operated the computer poor, easily cause various quality problems.For this reason, needing the viscosity reducing tackiness agent, in order to make the viscosity of tackiness agent reduce, having to the resiniferous molecular weight of institute in tackiness agent is reduced.So namely obtain good tack after evaporation of the solvent compared to solvent-based adhesive, the tack of solventless adhesive is usually not high, especially to the plastic film of evaporation metal and the cohesiveness of tinsel poor.And the medical supplies packaging higher for hygienic requirements and food packaging applications, in order to meet the requirement of high temperature exterminating bacterium, high-temp resisting high-humidity resisting becomes the another target capabilities of solvent-free multiple film glue.
Therefore, exploitation low viscosity, the no-solvent type polyurethane adhesive of high initial bonding strength and high-temp resisting high-humidity resisting becomes study hotspot and the developing direction in compound package material field.
Summary of the invention
In order to the above-mentioned shortcoming overcoming prior art is with not enough, the object of the present invention is to provide the multiple film glue of a kind of Low viscosity solvent-free polyurethane, possess that viscosity is low, curing speed fast, the advantage of high-peeling strength and resistance to 100 DEG C of high temperature steamings.
Another object of the present invention is to the preparation method that the multiple film glue of above-mentioned Low viscosity solvent-free polyurethane is provided.
Object of the present invention is achieved through the following technical solutions:
The multiple film glue of a kind of Low viscosity solvent-free polyurethane, this tackiness agent comprises component A and B component, component A is isocyanate terminated based compound, B component is terminal hydroxy group compound, and component A and B component are 1.3 ~ 1.75 carry out mixing and obtain the multiple film glue of Low viscosity solvent-free polyurethane by NCO (terminal isocyanate group): OH (hydroxyl) mol ratio.
The isocyanate terminated based compound of described component A is reacted by polyisocyanates and polyol and forms, and wherein, described polyol is made up of polyester polyol, polyether glycol and vegetable oil polyol;
Described B component terminal hydroxy group compound is made up of vegetable oil polyol; Or this terminal hydroxy group compound is by vegetable oil polyol, and modified vegetable oil polyols and small molecule polyol form; Or this polyol is by vegetable oil polyol, and modified vegetable oil polyols, small molecule polyol and cohesive force promotor form.
The isocyanate group content of the isocyanate terminated based compound of described component A is 7% ~ 14%, and preferred isocyanate base total amount content is 9% ~ 12%; Under low temperature coated condition, described isocyanate terminated based compound viscosity is 500 ~ 1500cP, and preferred viscosities is 700 ~ 1200cP.
In described component A, vegetable oil polyol accounts for the ratio of polyol hydroxyl mole total amount is 30 ~ 90%; The ratio that described polyether glycol accounts for polyol hydroxyl mole total amount is 10 ~ 90%; The ratio that described polyester polyol accounts for polyol hydroxyl mole total amount is 10 ~ 50%.
Vegetable oil polyol in described component A and B component is castor oil polyhydric alcohol, one or more the mixture in soybean oil polyol or plam oil polyvalent alcohol.
Polyether glycol in described component A and polyester polyol, its molecular weight ranges is 400 ~ 2000, preferably from polyethylene glycol adipate (PEA), poly-hexanodioic acid 1, one or more mixture in 4-butanediol ester (PBA), poly-hexanodioic acid 1,6-butyl ester (PHA), poly-epsilon-caprolactone (PCL), polyoxypropyleneglycol (PPG), polyoxyethylene glycol (PEG), polytetrahydrofuran diol (PTMG).
Described B component terminal hydroxy group compound by vegetable oil polyol, modified vegetable oil polyols, small molecule polyol and cohesive force promotor composition; Under low temperature coated condition, the viscosity of described B component terminal hydroxy group compound is 80 ~ 500cP, and preferred viscosities is 100 ~ 250cP.
The modified vegetable oil polyols of described B component is obtained through alcoholysis reaction by vegetable oil polyol and low molecular polylol, and wherein, vegetable oil polyol is one or more the mixture in claim 6; One or more the mixture of low molecular polylol preferably in ethylene glycol (EG), propylene glycol (PG), glycol ether (DEG), BDO (BD) or glycerine (GLY).
The small molecular alcohol of described B component is preferably from ethylene glycol (EG), propylene glycol (PG), 1, one or more mixture in 4-butyleneglycol (BD), neopentyl glycol, 1,6-hexylene glycol (HD), glycerine, glycol ether (DEG), Triethylene glycol.
Cohesive force promotor in described B component is made up of the silane coupling agent of modification, wherein, one or more the mixture of silane coupling agent preferably in γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyl triethoxysilane, γ glycidoxypropyl trimethoxy silane, phenylaminomethyl triethoxyl silane, phenylamino propyl-triethoxysilicane or phenylamino propyl trimethoxy silicane.
The preparation method of the multiple film glue of above-mentioned Low viscosity solvent-free polyurethane, comprises following step:
(1) by more than one polyester polyol, polyether glycol and more than one vegetable oil polyol under the vacuum condition of 105 DEG C ~ 120 DEG C dry 1 ~ 3 hour, make its water content lower than 0.05%; Then be cooled to 50 DEG C ~ 60 DEG C and add polyisocyanate compound, logical nitrogen is also warming up to 70 DEG C ~ 90 DEG C reactions 2 ~ 4 hours, obtains the isocyanate terminated based compound of component A;
(2) by vegetable oil polyol, the vacuum-drying 1 ~ 2 hour at 105 DEG C ~ 120 DEG C of modified vegetable oil polyols and small molecular alcohol, makes its water content lower than 0.05%; Then be cooled to 50 DEG C ~ 60 DEG C, add cohesive force promotor, stir and cool to room temperature, obtain B component terminal hydroxy group component;
(3) component A and B component are mixed in the ratio of NCO:OH=1.3 ~ 1.75, obtain low-viscosity solvent-free type bicomponent polyurethane laminating adhesive.
Modified vegetable oil polyols in above-mentioned steps (2); its preparation method is 105 DEG C ~ 120 DEG C vacuum-dryings 1 ~ 2 hour by polyvalent alcohol; make the water content of polyvalent alcohol lower than 0.05%; then be cooled to 50 DEG C ~ 60 DEG C, add low molecular polylol fast, open and stir; pass into industrial nitrogen protection; be warming up to 120 DEG C ~ 220 DEG C to react, 3 ~ 5 hours terminate reaction, obtain modified vegetable oil polyols.
Above-mentioned low-viscosity solvent-free polyurethane laminating adhesive can be applicable to the bonding between various flexible package composite material, comprises the bonding of CPP, BOPP, PA, PET, PE, aluminium foil and aluminium plating film wherein any bi-material.
The component A of above-mentioned low-viscosity solvent-free polyurethane laminating adhesive and B component join glue coating compound by NCO:OH molar ratio 1.3 ~ 1.75 under the cold condition of 30 ~ 50 DEG C, and operable time is 3 ~ 10 hours, and spread is 1.1 ~ 2.5g/m
2.
Compared with prior art, the low-viscosity solvent-free polyurethane laminating adhesive that prepared by the present invention has the following advantages and beneficial effect:
Because the isocyanate terminated based compound of component A of the present invention is by vegetable oil polyol, polyether glycol and polyester polyol and polyisocyanate compound react gained, wherein the high functionality of vegetable oil polyol makes component A have comparatively high crosslink density, and the long side chain in molecular structure makes component A have lower viscosity and good hydrophobicity; Meanwhile, the reduction of tackiness agent viscosity and the raising of hydrophobic performance is also contributed to adding of polyether glycol; A certain proportion of polyester polyol then contributes to the raising of tackiness agent initial bonding strength.In B component, modified vegetable oil polyols is the alcoholysis product of vegetable oil polyol, not only increases the functionality of vegetable oil polyol, also improves its reactive behavior.In the present invention component A viscosity in 700 ~ 1200cP and B component viscosity at 100 ~ 250cP, there is good low temperature coated property and curing speed faster, in 30 ~ 50 DEG C of coating compounds, solidification in 24 ~ 36 hours, the multiple film sample after solidification has higher stripping strength and good boiling resistance energy.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
The multiple film glue of a kind of Low viscosity solvent-free polyurethane provided by the invention, this tackiness agent comprises component A and B component, component A is isocyanate terminated based compound, B component is terminal hydroxy group compound, and component A and B component are 1.3 ~ 1.75 carry out mixing and obtaining bicomponent polyurethane laminating adhesive by NCO:OH mol ratio.Wherein, the isocyanate terminated based compound of component A is reacted by polyisocyanates and polyol and forms, and polyhydroxy component is made up of polyester polyol, polyether glycol and vegetable oil polyol; B component terminal hydroxy group compound, is made up of vegetable oil polyol; Or this terminal hydroxy group compound is by vegetable oil polyol, and modified vegetable oil polyols and small molecule polyol form; Or this polyol is by vegetable oil polyol, and modified vegetable oil polyols, small molecule polyol and cohesive force promotor form.
In this tackiness agent, component A viscosity is at 700 ~ 1200cP, and B component viscosity, at 100 ~ 250cP, has good low temperature coated property; A, B two component press NCO:OH=1.3 ~ 1.75, join under the cold condition of 30 ~ 50 DEG C glue coating compound, through 24 ~ 36 hours solidification, the multiple film sample after solidification has higher stripping strength and good boiling resistance energy.
Embodiment 1
The preparation of A-1
Raw material and proportioning: polytetrahydrofuran diol (molecular weight 1000) 60g, refining castor oil polyvalent alcohol (hydroxyl value 162mgKOH/g) 100g, isofoer diisocyanate 150g;
Technique: by polytetrahydrofuran diol and refining castor oil polyvalent alcohol, load in reactor, be warming up to 105 DEG C of vacuum-dryings, 1 hour water content to polyvalent alcohol and be less than 0.05%, then 50 DEG C are cooled to, adding isofoer diisocyanate and strengthening stirring velocity makes it fully mix with polyvalent alcohol, pass into industrial nitrogen protection simultaneously, then be warming up to 70 DEG C of reactions 2 hours, obtain terminal isocyanate group base polyurethane prepolymer for use as component A;
The proterties of component A: be clear viscous liquid under room temperature, at 50 DEG C, viscosity is 900cP.
Embodiment 2
The preparation of A-2
Raw material and proportioning: polyoxypropyleneglycol (molecular weight 400) 50g, poly-hexanodioic acid 1,4-butanediol ester (molecular weight 1000) 50g, refining castor oil polyvalent alcohol (hydroxyl value 162mgKOH/g) 100g, isofoer diisocyanate 200g;
Technique: by polyoxypropyleneglycol, poly-hexanodioic acid 1,4-butanediol ester and refining castor oil polyvalent alcohol, load in reactor, be warming up to 120 DEG C of vacuum-dryings, 3 hours water content to polyvalent alcohol and be less than 0.05%, then be cooled to 60 DEG C, add isofoer diisocyanate and strengthen stirring velocity and make it fully mix with polyvalent alcohol, pass into industrial nitrogen protection simultaneously, be warming up to 90 DEG C of reactions 4 hours again, obtain terminal isocyanate group base polyurethane prepolymer for use as component A;
The proterties of component A: be clear viscous liquid under room temperature, at 50 DEG C, viscosity is 600cP.
The preparation of embodiment 3A-3
Raw material and proportioning: polyoxypropyleneglycol (molecular weight 1000) 100g, poly-hexanodioic acid 1,4-butanediol ester (molecular weight 1000) 50g, refining castor oil polyvalent alcohol (hydroxyl value 130mgKOH/g) 100g, isofoer diisocyanate 200g;
Technique: by polyoxypropyleneglycol, poly-hexanodioic acid 1,4-butanediol ester and soybean oil polyol, load in reactor, be warming up to 120 DEG C of vacuum-dryings, 2 hours water content to polyvalent alcohol and be less than 0.05%, then be cooled to 60 DEG C, add isofoer diisocyanate and strengthen stirring velocity and make it fully mix with polyvalent alcohol, pass into industrial nitrogen protection simultaneously, be warming up to 80 DEG C of reactions 2 ~ 4 hours again, obtain terminal isocyanate group base polyurethane prepolymer for use as component A;
The proterties of component A: be clear viscous liquid under room temperature, at 50 DEG C, viscosity is 1500cP.
Embodiment 4
The preparation of A-4
Raw material and proportioning: polyoxypropyleneglycol (molecular weight 1000) 100g, poly-hexanodioic acid 1,4-butanediol ester (molecular weight 1000) 50g, soybean oil polyol (hydroxyl value 130mgKOH/g) 100g, isofoer diisocyanate 200g;
Technique: by polyoxypropyleneglycol, poly-hexanodioic acid 1,4-butanediol ester and soybean oil polyol, load in reactor, be warming up to 120 DEG C of vacuum-dryings, 2 hours water content to polyvalent alcohol and be less than 0.05%, then be cooled to 60 DEG C, add isofoer diisocyanate and strengthen stirring velocity and make it fully mix with polyvalent alcohol, pass into industrial nitrogen protection simultaneously, be warming up to 80 DEG C of reactions 2 ~ 4 hours again, obtain terminal isocyanate group base polyurethane prepolymer for use as component A;
The proterties of component A: be clear viscous liquid under room temperature, at 50 DEG C, viscosity is 1300cP.
Embodiment 5
The preparation of B-1
Raw material and proportioning: refining castor oil polyvalent alcohol (hydroxyl value 162mgKOH/g) 100g, modified castor oil polyalcohol 5g; Technique: refining castor oil polyvalent alcohol and modified castor oil polyalcohol loaded in reactor, is warming up to that 120 DEG C of vacuum-drying 2 is little is less than 0.05% up to water content, stirs and cools to room temperature, obtaining B component;
The wherein formula of modified castor oil polyalcohol and technique:
The formula of properties-correcting agent: refining castor oil polyvalent alcohol 100g, glycerine 20g, sodium hydroxide 1g;
The technique of properties-correcting agent: by the vacuum-drying 1 ~ 2 hour at 120 DEG C of refining castor oil and glycerine; the water content of polyvalent alcohol is made to be less than 0.05%; then 50 DEG C ~ 60 DEG C are cooled to; add sodium hydroxide; accelerate stirring velocity; pass into industrial nitrogen protection, be warming up to 120 DEG C ~ 220 DEG C and react, be down to room temperature after question response terminates and obtain modified castor oil polyalcohol.
The proterties of B component: be clear viscous liquid under room temperature, at 50 DEG C, viscosity is 600cP.
Embodiment 6
The preparation of B-2
Raw material and proportioning: castor oil polyhydric alcohol (hydroxyl value 162mgKOH/g) 100g, modified castor oil polyalcohol 5g, cohesive force promotor 5g;
Technique: soybean oil polyol and modified castor oil polyalcohol loaded in reactor, is warming up to that 120 DEG C of vacuum-drying 2 is little is less than 0.05% up to water content; Then after being cooled to 60 DEG C, add cohesive force promotor, stir and cool to room temperature, obtaining B component;
Wherein cohesive force promotor is: the modified product 5g of γ-aminopropyl triethoxysilane;
The wherein formula of modified castor oil polyalcohol and technique:
The formula of properties-correcting agent: refining castor oil polyvalent alcohol 100g, glycerine 20g, sodium hydroxide 1g;
The technique of properties-correcting agent: by the vacuum-drying 1 ~ 2 hour at 120 DEG C of refining castor oil and glycerine; the water content of polyvalent alcohol is made to be less than 0.05%; then 50 DEG C ~ 60 DEG C are cooled to; add sodium hydroxide; accelerate stirring velocity; pass into industrial nitrogen protection, be warming up to 120 DEG C ~ 220 DEG C and react, be down to room temperature after question response terminates and obtain modified castor oil polyalcohol.
The proterties of B component: be clear viscous liquid under room temperature, at 50 DEG C, viscosity is 800cP.
Embodiment 7
The preparation of B-3
Raw material and proportioning: refining castor oil polyvalent alcohol (hydroxyl value 162mgKOH/g) 100g, cohesive force promotor 5g;
Technique: loaded in reactor by refining castor oil polyvalent alcohol, is warming up to that 105 DEG C of vacuum-drying 1 is little is less than 0.05% up to water content; Then after being cooled to 50 DEG C, add cohesive force promotor, stir and cool to room temperature, obtaining B component;
Wherein cohesive force promotor is: the modified product 5g of γ-aminopropyl triethoxysilane;
The proterties of B component: be clear viscous liquid under room temperature, at 50 DEG C, viscosity is 800cP.
Embodiment 8
The preparation of B-4
Raw material and proportioning: soybean oil polyol (hydroxyl value 162mgKOH/g) 100g, modified castor oil polyalcohol 10g, cohesive force promotor 5g;
Technique: refining castor oil polyvalent alcohol and modified castor oil polyalcohol loaded in reactor, is warming up to that 120 DEG C of vacuum-drying 2 is little is less than 0.05% up to water content; Then after being cooled to 60 DEG C, add cohesive force promotor, stir and cool to room temperature, obtaining B component;
Wherein cohesive force promotor is: the modified product 5g of γ-aminopropyl triethoxysilane;
The wherein formula of modified castor oil polyalcohol and technique:
The formula of properties-correcting agent: refining castor oil polyvalent alcohol 100g, BDO 20g, sodium hydroxide 1g;
The technique of properties-correcting agent: by refining castor oil and 1; the vacuum-drying 1 ~ 2 hour at 120 DEG C of 4-butyleneglycol; the water content of polyvalent alcohol is made to be less than 0.05%; then 50 DEG C ~ 60 DEG C are cooled to; add sodium hydroxide, accelerate stirring velocity, pass into industrial nitrogen protection; be warming up to 120 DEG C ~ 220 DEG C to react, be down to room temperature after question response terminates and obtain modified castor oil polyalcohol.
The proterties of B component: be clear viscous liquid under room temperature, at 50 DEG C, viscosity is 800cP.
Embodiment 9
The A-1 of 130 parts is carried out fully mixing joining glue with the B-1 of 100 parts at 50 DEG C, its initial viscosity of Simultaneously test, curing speed and the stripping strength to thin-film material.Coating and compound are carried out at normal temperatures, and the film that compound is good solidifies 48 and as a child measured its T stripping strength in the baking oven of 50 ~ 60 DEG C, and test speed is 100mm/min.
Joining the initial viscosity after glue is 800cP, reacts solidification substantially in 12 hours;
Stripping strength between BOPP/Al is 4.2N/25mm; 100 DEG C of boiling water boilings after 3 hours stripping strength be 3.6N/25mm.
Stripping strength between PET/Al paper tinsel is 6N/25mm; 100 DEG C of boiling water boilings after 3 hours stripping strength be 5.6N/25mm.
Embodiment 10
The A-2 of 130 parts is carried out fully mixing joining glue with the B-1 of 100 parts at 60 DEG C, its initial viscosity of Simultaneously test, curing speed and the stripping strength to thin-film material.Coating and compound are carried out at normal temperatures, and the film that compound is good solidifies 48 and as a child measured its T stripping strength in the baking oven of 50 ~ 60 DEG C, and test speed is 100mm/min.
Joining the initial viscosity after glue is 500cP, reacts solidification substantially in 12 hours;
Stripping strength between BOPP/Al is 6.2N/25mm; 100 DEG C of boiling water boilings after 3 hours stripping strength be 5.8N/25mm.
Stripping strength between PET/Al paper tinsel is 7.5N/25mm; 100 DEG C of boiling water boilings after 3 hours stripping strength be 7.2N/25mm.
Embodiment 11
The A-3 of 130 parts is carried out fully mixing joining glue with the B-1 of 100 parts at 50 ~ 60 DEG C, its initial viscosity of Simultaneously test, curing speed and the stripping strength to thin-film material.Coating and compound are carried out at normal temperatures, and the film that compound is good solidifies 48 and as a child measured its T stripping strength in the baking oven of 50 ~ 60 DEG C, and test speed is 100mm/min.
Joining the initial viscosity after glue is 800cP, reacts solidification substantially in 12 hours;
Stripping strength between BOPP/Al is 4.4N/25mm; 100 DEG C of boiling water boilings after 3 hours stripping strength be 3.6N/25mm.
Stripping strength between PET/Al paper tinsel is 6N/25mm; 100 DEG C of boiling water boilings after 3 hours stripping strength be 5.2N/25mm.
Embodiment 12
The A-4 of 130 parts is carried out fully mixing joining glue with the B-1 of 100 parts at 50 ~ 60 DEG C, its initial viscosity of Simultaneously test, curing speed and the stripping strength to thin-film material.Coating and compound are carried out at normal temperatures, and the film that compound is good solidifies 48 and as a child measured its T stripping strength in the baking oven of 50 ~ 60 DEG C, and test speed is 100mm/min.
Joining the initial viscosity after glue is 1000cP, reacts solidification substantially in 12 hours;
Stripping strength between BOPP/Al is 5.4N/25mm; 100 DEG C of boiling water boilings after 3 hours stripping strength be 4.9N/25mm.
Stripping strength between PET/Al paper tinsel is 6N/25mm; 100 DEG C of boiling water boilings after 3 hours stripping strength be 5.6N/25mm.
Embodiment 13
The A-2 of 130 parts is carried out fully mixing joining glue with the B-2 of 100 parts at 50 ~ 60 DEG C, its initial viscosity of Simultaneously test, curing speed and the stripping strength to thin-film material.Coating and compound are carried out at normal temperatures, and the film that compound is good solidifies 48 and as a child measured its T stripping strength in the baking oven of 50 ~ 60 DEG C, and test speed is 100mm/min.
Joining the initial viscosity after glue is 600cP, reacts solidification substantially in 12 hours;
Stripping strength between BOPP/Al is 7N/25mm; 100 DEG C of boiling water boilings after 3 hours stripping strength be 7.2N/25mm.
Stripping strength between PET/Al paper tinsel is 8N/25mm; 100 DEG C of boiling water boilings after 3 hours stripping strength be 8.6N/25mm.
Embodiment 14
The A-2 of 130 parts is carried out fully mixing joining glue with the B-3 of 100 parts at 50 ~ 60 DEG C, its initial viscosity of Simultaneously test, curing speed and the stripping strength to thin-film material.Coating and compound are carried out at normal temperatures, and the film that compound is good solidifies 48 and as a child measured its T stripping strength in the baking oven of 50 ~ 60 DEG C, and test speed is 100mm/min.
Joining the initial viscosity after glue is 600cP, reacts solidification substantially in 24 hours;
Stripping strength between BOPP/Al is 5.5N/25mm; 100 DEG C of boiling water boilings after 3 hours stripping strength be 6.0N/25mm.
Stripping strength between PET/Al paper tinsel is 6.7N/25mm; 100 DEG C of boiling water boilings after 3 hours stripping strength be 7.2N/25mm.
Comparative example 1
Embodiment 9, the difference of embodiment 10 and embodiment 11 is differences of three's component A polyether glycol, and the similar but different molecular weight of polyether glycol selected by embodiment 10 and embodiment 11, embodiment 10 have employed the polyether glycol of lower molecular weight.By more known, the initial viscosity of embodiment 10 is significantly less than embodiment 11, and stripping strength is greater than embodiment 11.
Comparative example 2
The difference of embodiment 10 and embodiment 13 is that the B component of embodiment 10 does not add cohesive force promotor, and the B component of embodiment 13 with the addition of cohesive force promotor.By more known, the stripping strength of embodiment 10 is starkly lower than embodiment 13, and the stripping strength after boiling declines to some extent, and improves on the contrary after the stripping strength boiling of embodiment 13, improves the boiling resistance of polyurethane laminating adhesive.
Comparative example 3
The difference of embodiment 13 and embodiment 14 is that the B component of embodiment 14 does not add modified vegetable oil polyols, and the B component of embodiment 13 with the addition of modified vegetable oil polyols.By more known, the stripping strength of embodiment 13 is apparently higher than embodiment 14, and set time is short, shortens the cycle of laminating production.
As can be seen from the above embodiments, the isocyanate terminated based compound of solvent-free polyurethane laminating adhesive component A of the present invention is by vegetable oil polyol, polyether glycol and polyester polyol and polyisocyanate compound react gained, B component says composition primarily of vegetable oil polyol and alcoholysis modified product thereof, two components are not all containing solvent, and there is comparatively low viscosity, be easy to low temperature coated.It is fast that glue after fixing speed joined by this tackiness agent, and solidification in 12 ~ 24 hours, the multiple film sample after solidification has higher stripping strength and good boiling resistance energy, the plastic-aluminum combined stripping strength that can keep more than 5.0N/25mm.
Multiple film glue of the present invention be mainly used in moulding compound (refer to can be applicable to CPP, BOPP, PE, PET, etc. the soft compound in plastics film between any two kinds of base materials), plastic-aluminum combined (comprising the soft compound between the plastics film such as aluminium foil and CPP, BOPP, PE, PET, PA).
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. a preparation method for the multiple film glue of Low viscosity solvent-free polyurethane, is characterized in that, comprise the following steps:
(1) by polyester polyol, polyether glycol and vegetable oil polyol under the vacuum condition of 105 DEG C ~ 120 DEG C dry 1 ~ 3 hour, make its water content lower than 0.05%; Then be cooled to 50 DEG C ~ 60 DEG C and add polyisocyanate compound, logical nitrogen is also warming up to 70 DEG C ~ 90 DEG C reactions 2 ~ 4 hours, obtains component A terminal isocyanate group component;
(2) by vegetable oil polyol, the vacuum-drying 1 ~ 2 hour at 105 DEG C ~ 120 DEG C of modified vegetable oil polyols and small molecule polyol, makes its water content lower than 0.05%; Then be cooled to 50 DEG C ~ 60 DEG C, add cohesive force promotor, stir and cool to room temperature, obtain B component terminal hydroxy group component;
Described modified vegetable oil polyols, its preparation method is 105 DEG C ~ 120 DEG C vacuum-dryings 1 ~ 2 hour by vegetable oil polyol, make the water content of vegetable oil polyol lower than 0.05%, then be cooled to 50 DEG C ~ 60 DEG C, add low molecular polylol fast, open and stir, pass into industrial nitrogen protection, be warming up to 120 DEG C ~ 220 DEG C to react, 3 ~ 5 hours terminate reaction, obtain modified vegetable oil polyols;
(3) by component A and B component in terminal isocyanate group: the ratio of hydroxyl=1.3 ~ 1.75 mixes, and obtains low-viscosity solvent-free type bicomponent polyurethane laminating adhesive.
2. the preparation method of the multiple film glue of Low viscosity solvent-free polyurethane according to claim 1, it is characterized in that, the isocyanate group content of described terminal isocyanate group component is 7% ~ 14%; Described terminal isocyanate group component is reacted by polyisocyanates and polyol and is formed; Described polyol is made up of polyester polyol, polyether glycol and vegetable oil polyol.
3. the preparation method of the multiple film glue of Low viscosity solvent-free polyurethane according to claim 1, it is characterized in that, described vegetable oil polyol is castor oil polyhydric alcohol, one or more the mixture in soybean oil polyol and plam oil polyvalent alcohol.
4. the preparation method of the multiple film glue of Low viscosity solvent-free polyurethane according to claim 1, it is characterized in that, described low molecular polylol is one or more the mixture in ethylene glycol, propylene glycol, glycol ether, BDO and glycerine.
5. the preparation method of the multiple film glue of Low viscosity solvent-free polyurethane according to claim 4, it is characterized in that, described vegetable oil polyol is castor oil polyhydric alcohol, one or more the mixture in soybean oil polyol and plam oil polyvalent alcohol.
6. the preparation method of the multiple film glue of Low viscosity solvent-free polyurethane according to claim 4, it is characterized in that, described small molecule polyol is ethylene glycol, propylene glycol, 1, one or more mixture in 4-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, glycerine, glycol ether, Triethylene glycol.
7. the preparation method of the multiple film glue of Low viscosity solvent-free polyurethane according to claim 1, it is characterized in that, described cohesive force promotor is made up of the silane coupling agent of modification; Described silane coupling agent is one or more the mixture in γ-aminopropyl triethoxysilane (KH550), γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyl triethoxysilane, γ-glycidoxypropyl trimethoxy silane, phenylaminomethyl triethoxyl silane, phenylamino propyl-triethoxysilicane or phenylamino propyl trimethoxy silicane.
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| CN116041769A (en) * | 2022-12-08 | 2023-05-02 | 中国科学院长春应用化学研究所 | Polyurethane coating for auxiliary adhesion of film surface, preparation method and application thereof |
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