CN103215006A - Low viscosity solvent-free polyurethane laminating adhesive and preparation method thereof - Google Patents
Low viscosity solvent-free polyurethane laminating adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low viscosity solvent-free polyurethane laminating adhesive, which includes component A and component B. The component A is an isocyanate terminated compound, and the component B is a hydroxyl terminated compound. The component A and the component B are mixed according to that the isocyanate terminated group and the hydroxyl are in a mole ratio of 1.3-1.75, thus obtaining the bicomponent polyurethane laminating adhesive. The invention also discloses a preparation method of the low viscosity solvent-free polyurethane laminating adhesive. The low viscosity solvent-free polyurethane laminating adhesive prepared by the invention has the advantages of low viscosity, fast curing speed, high peel strength and resistance to 100DEG C cooking.
Description
Technical field
The present invention relates to be applicable to the multiple film glue in composite soft packaging field, multiple film glue of particularly a kind of low-viscosity solvent-free type 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 to the wholesomeness of wrapping material and to the attention day by day of environment protection, the multiple film glue of the no-solvent type of environmental protection just progressively becomes the new lover in composite soft packaging field as the substitute of solvent-type film-covered adhesive.The no-solvent type polyurethane laminating adhesive has following several big advantage: do not have the solvent discharge problem, also do not have the dissolvent residual problem; Do not need complicated huge heating air blast, discarded air draft and emission-control equipment; Spread is few, thereby reduces energy consumption, saves cost; Can run up, enhance productivity.This some meet solvent-free compound typical " three do not have " technology, in conjunction with the excellent characteristic of tackiness agent itself, solvent-free polyurethane laminating adhesive becomes the ideal selection of advocating composite packaging field under the environmental protection epoch.
Yet solventless adhesive does not contain solvent because of it, so viscosity is bigger, the mobile and property operated the computer in the production process is relatively poor, causes various quality problems easily.For this reason, need to reduce the viscosity of tackiness agent, for the viscosity that makes tackiness agent reduces, have to make in the tackiness agent resinous molecular weight reduce.So, after solvent evaporates, promptly obtaining tack preferably than solvent-based adhesive, the tack of solventless adhesive is not high usually, and is especially relatively poor to the cohesiveness of the plastic film of evaporation metal and tinsel.And for hygienic requirements higher medical supplies packing and food product pack field, in order to satisfy the requirement of high temperature virus killing sterilization, high-temp resisting high-humidity resisting becomes the another target capabilities of solvent-free multiple film glue.
Therefore, the exploitation low viscosity, the no-solvent type polyurethane adhesive of high initial bonding strength and high-temp resisting high-humidity resisting becomes the research focus and the developing direction in compound package material field.
Summary of the invention
For the above-mentioned shortcoming that overcomes prior art with not enough, the object of the present invention is to provide the multiple film glue of a kind of low-viscosity solvent-free type polyurethane, possess that viscosity is low, curing speed is fast, the advantage of high-peeling strength and anti-100 ℃ of high temperature steamings.
Another object of the present invention is to provide the preparation method of the multiple film glue of above-mentioned low-viscosity solvent-free type polyurethane.
Purpose of the present invention is achieved through the following technical solutions:
The multiple film glue of a kind of low-viscosity solvent-free type polyurethane, this tackiness agent comprises A component and B component, the A component is isocyanate terminated based compound, the B component is the terminal hydroxy group compound, and A component and B component are by the isocyanate terminated base of NCO(): the OH(hydroxyl) mol ratio is 1.3～1.75 to mix and promptly get the multiple film glue of low-viscosity solvent-free type polyurethane.
The isocyanate terminated based compound of described A component is formed by polyisocyanates and polyol reaction, 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; Perhaps, this terminal hydroxy group compound is by vegetable oil polyol, and modified vegetable oil polyols and small molecules polyvalent alcohol are formed; Perhaps, this polyol is by vegetable oil polyol, modified vegetable oil polyols, and small molecules polyvalent alcohol and cohesive force promotor are formed.
The isocyanate group content of the isocyanate terminated based compound of described A component 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.
To account for the ratio of polyol hydroxyl mole total amount be 30～90% to vegetable oil polyol in the described A component; 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 A component and the B component is a castor oil polyhydric alcohol, the mixture of one or more in soybean oil polyvalent alcohol or the plam oil polyvalent alcohol.
Polyether glycol and polyester polyol in the described A component, its molecular weight ranges is 400～2000, preferably from polyethylene glycol adipate (PEA), poly-hexanodioic acid 1,4-butanediol ester (PBA), poly-hexanodioic acid 1, the mixture of one or more in 6-butyl ester (PHA), poly-epsilon-caprolactone (PCL), polyoxypropyleneglycol (PPG), polyoxyethylene glycol (PEG), the polytetrahydrofuran diol (PTMG).
Described B component terminal hydroxy group compound is by vegetable oil polyol, modified vegetable oil polyols, and small molecules polyvalent alcohol and cohesive force promotor are formed; Under the 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 to be obtained through alcoholysis reaction by vegetable oil polyol and low molecular polylol, and wherein, vegetable oil polyol is one or more the mixture in the claim 6; Low molecular polylol is preferably from ethylene glycol (EG), propylene glycol (PG), glycol ether (DEG), 1, the mixture of one or more in 4-butyleneglycol (BD) or the glycerine (GLY).
The small molecular alcohol of described B component is preferably from ethylene glycol (EG), propylene glycol (PG), 1,4-butyleneglycol (BD), neopentyl glycol, 1, the mixture of one or more in 6-hexylene glycol (HD), glycerine, glycol ether (DEG), the Triethylene glycol.
Cohesive force promotor in the described B component is made up of the silane coupling agent of modification, wherein, the preferred mixture of one or more in γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-An Bingjisanyiyangjiguiwan, γ Racemic glycidol oxygen propyl trimethoxy silicane, phenylamino Union carbide A-162, phenylamino propyl-triethoxysilicane or phenylamino propyl trimethoxy silicane of silane coupling agent.
The preparation method of the multiple film glue of above-mentioned low-viscosity solvent-free type polyurethane comprises following step:
(1) with more than one polyester polyol, polyether glycol and more than one vegetable oil polyol under 105 ℃～120 ℃ vacuum condition dry 1～3 hour make its water content be lower than 0.05%; Be cooled to 50 ℃～60 ℃ then and add polyisocyanate compound, logical nitrogen also is warming up to 70 ℃～90 ℃ reactions 2～4 hours, promptly gets the isocyanate terminated based compound of A component;
(2) with vegetable oil polyol, modified vegetable oil polyols and small molecular alcohol make its water content be lower than 0.05% 105 ℃～120 ℃ following vacuum-dryings 1～2 hour; Be cooled to 50 ℃～60 ℃ then, add cohesive force promotor, stir and cool to room temperature, promptly get B component terminal hydroxy group component;
(3) A component 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 the above-mentioned steps (2); its preparation method is 105 ℃～120 ℃ vacuum-dryings 1～2 hour with polyvalent alcohol; make the water content of polyvalent alcohol be lower than 0.05%; be cooled to 50 ℃～60 ℃ then, add low molecular polylol fast, open and stir; the protection of feeding industrial nitrogen; be warming up to 120 ℃～220 ℃ and react, 3～5 hours finish reaction, promptly get modified vegetable oil polyols.
Above-mentioned low-viscosity solvent-free polyurethane laminating adhesive can be applicable to the bonding between the various flexible package composite materials, comprises the bonding of the wherein any two kinds of materials of CPP, BOPP, PA, PET, PE, aluminium foil and aluminium plating film.
The A component of above-mentioned low-viscosity solvent-free polyurethane laminating adhesive and B component are joined glue coating by NCO:OH molar ratio 1.3～1.75 under 30～50 ℃ cold condition compound, 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 of the present invention's preparation has the following advantages and beneficial effect:
Because the isocyanate terminated based compound of A component of the present invention is by vegetable oil polyol, polyether glycol and polyester polyol and polyisocyanate compound reaction gained, wherein the high functionality of vegetable oil polyol has than high crosslink density component A, and the long side chain in the molecular structure makes the A component have lower viscosity and better hydrophobic; Simultaneously, the adding of polyether glycol also helps the reduction of tackiness agent viscosity and the raising of hydrophobic performance; A certain proportion of polyester polyol then helps the raising of tackiness agent initial bonding strength.Modified vegetable oil polyols is the alcoholysis product of vegetable oil polyol in the B component, has not only improved the functionality of vegetable oil polyol, has also improved its reactive behavior.Among the present invention A component viscosity in 700～1200cP and B component viscosity at 100～250cP, have good low-temperature coating and curing speed faster, compound in 30～50 ℃ of coatings, solidified in 24～36 hours, the multiple film sample after the curing 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 type polyurethane provided by the invention, this tackiness agent comprises A component and B component, component A is isocyanate terminated based compound, the B component is the terminal hydroxy group compound, and A component and B component are 1.3～1.75 to mix and promptly get bicomponent polyurethane laminating adhesive by the NCO:OH mol ratio.Wherein, the isocyanate terminated based compound of A component is formed by polyisocyanates and polyol reaction, 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; Perhaps, this terminal hydroxy group compound is by vegetable oil polyol, and modified vegetable oil polyols and small molecules polyvalent alcohol are formed; Perhaps, this polyol is by vegetable oil polyol, modified vegetable oil polyols, and small molecules polyvalent alcohol and cohesive force promotor are formed.
In this tackiness agent, A component viscosity is at 700～1200cP, and B component viscosity has the good low-temperature coating at 100～250cP; A, B two components are pressed NCO:OH=1.3～1.75, and it is compound to join glue coating under 30～50 ℃ cold condition, solidifies through 24～36 hours, and the multiple film sample after the curing 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 polyhydric alcohol (hydroxyl value 162mgKOH/g) 100g, isofoer diisocyanate 150g;
Technology: with polytetrahydrofuran diol and refining castor oil polyhydric alcohol, pack in the reactor, be warming up to 105 ℃ of vacuum-dryings 1 hour to the water content of polyvalent alcohol less than 0.05%, be cooled to 50 ℃ then, adding isofoer diisocyanate and strengthening stirring velocity fully mixes it with polyvalent alcohol, feed the industrial nitrogen protection simultaneously, be warming up to 70 ℃ of reactions 2 hours again, promptly get isocyanate terminated based polyurethanes performed polymer A component;
The proterties of A component: be the clear viscous liquid under the room temperature, under 50 ℃, 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 polyhydric alcohol (hydroxyl value 162mgKOH/g) 100g, isofoer diisocyanate 200g;
Technology: with polyoxypropyleneglycol, poly-hexanodioic acid 1,4-butanediol ester and refining castor oil polyhydric alcohol, pack in the reactor, be warming up to 120 ℃ of vacuum-dryings 3 hours to the water content of polyvalent alcohol less than 0.05%, be cooled to 60 ℃ then, add isofoer diisocyanate and strengthen stirring velocity it is fully mixed with polyvalent alcohol, feed industrial nitrogen protection simultaneously, be warming up to 90 ℃ of reactions 4 hours again, promptly get isocyanate terminated based polyurethanes performed polymer A component;
The proterties of A component: be the clear viscous liquid under the room temperature, under 50 ℃, viscosity is 600cP.
The preparation of embodiment 3 A-3
Raw material and proportioning: polyoxypropyleneglycol (molecular weight 1000) 100g, poly-hexanodioic acid 1,4-butanediol ester (molecular weight 1000) 50g, refining castor oil polyhydric alcohol (hydroxyl value 130mgKOH/g) 100g, isofoer diisocyanate 200g;
Technology: with polyoxypropyleneglycol, poly-hexanodioic acid 1,4-butanediol ester and soybean oil polyvalent alcohol, pack in the reactor, be warming up to 120 ℃ of vacuum-dryings 2 hours to the water content of polyvalent alcohol less than 0.05%, be cooled to 60 ℃ then, add isofoer diisocyanate and strengthen stirring velocity it is fully mixed with polyvalent alcohol, feed industrial nitrogen protection simultaneously, be warming up to 80 ℃ of reactions 2～4 hours again, promptly get isocyanate terminated based polyurethanes performed polymer A component;
The proterties of A component: be the clear viscous liquid under the room temperature, under 50 ℃, 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 polyvalent alcohol (hydroxyl value 130mgKOH/g) 100g, isofoer diisocyanate 200g;
Technology: with polyoxypropyleneglycol, poly-hexanodioic acid 1,4-butanediol ester and soybean oil polyvalent alcohol, pack in the reactor, be warming up to 120 ℃ of vacuum-dryings 2 hours to the water content of polyvalent alcohol less than 0.05%, be cooled to 60 ℃ then, add isofoer diisocyanate and strengthen stirring velocity it is fully mixed with polyvalent alcohol, feed industrial nitrogen protection simultaneously, be warming up to 80 ℃ of reactions 2～4 hours again, promptly get isocyanate terminated based polyurethanes performed polymer A component;
The proterties of A component: be the clear viscous liquid under the room temperature, under 50 ℃, viscosity is 1300cP.
Embodiment 5
The preparation of B-1
Raw material and proportioning: refining castor oil polyhydric alcohol (hydroxyl value 162mgKOH/g) 100g, modified castor oil polyvalent alcohol 5g;
Technology: refining castor oil polyhydric alcohol and modified castor oil polyvalent alcohol are packed in the reactor, be warming up to 120 ℃ of vacuum-dryings 2 hours to water content less than 0.05%, stir and cool to room temperature, obtain the B component;
The wherein prescription of modified castor oil polyvalent alcohol and technology:
The prescription of properties-correcting agent: refining castor oil polyhydric alcohol 100g, glycerine 20g, sodium hydroxide 1g;
The technology of properties-correcting agent: with refining Viscotrol C and glycerine 120 ℃ of following vacuum-dryings 1～2 hour; the water content that makes polyvalent alcohol is less than 0.05%; be cooled to 50 ℃～60 ℃ then; add sodium hydroxide; accelerate stirring velocity; the protection of feeding industrial nitrogen is warming up to 120 ℃～220 ℃ and reacts, and reduces to room temperature after question response finishes and obtains the modified castor oil polyvalent alcohol.
The proterties of B component: be the clear viscous liquid under the room temperature, under 50 ℃, 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 polyvalent alcohol 5g, cohesive force promotor 5g;
Technology: soybean oil polyvalent alcohol and modified castor oil polyvalent alcohol are packed in the reactor, be warming up to 120 ℃ of vacuum-dryings 2 hours to water content less than 0.05%; After being cooled to 60 ℃ then, add cohesive force promotor, stir and cool to room temperature, obtain the B component;
Wherein cohesive force promotor is: the modified product 5g of γ-An Bingjisanyiyangjiguiwan;
The wherein prescription of modified castor oil polyvalent alcohol and technology:
The prescription of properties-correcting agent: refining castor oil polyhydric alcohol 100g, glycerine 20g, sodium hydroxide 1g;
The technology of properties-correcting agent: with refining Viscotrol C and glycerine 120 ℃ of following vacuum-dryings 1～2 hour; the water content that makes polyvalent alcohol is less than 0.05%; be cooled to 50 ℃～60 ℃ then; add sodium hydroxide; accelerate stirring velocity; the protection of feeding industrial nitrogen is warming up to 120 ℃～220 ℃ and reacts, and reduces to room temperature after question response finishes and obtains the modified castor oil polyvalent alcohol.
The proterties of B component: be the clear viscous liquid under the room temperature, under 50 ℃, viscosity is 800cP.
Embodiment 7
The preparation of B-3
Raw material and proportioning: refining castor oil polyhydric alcohol (hydroxyl value 162mgKOH/g) 100g, cohesive force promotor 5g;
Technology: the refining castor oil polyhydric alcohol is packed in the reactor, be warming up to 105 ℃ of vacuum-dryings 1 hour to water content less than 0.05%; After being cooled to 50 ℃ then, add cohesive force promotor, stir and cool to room temperature, obtain the B component;
Wherein cohesive force promotor is: the modified product 5g of γ-An Bingjisanyiyangjiguiwan;
The proterties of B component: be the clear viscous liquid under the room temperature, under 50 ℃, viscosity is 800cP.
Embodiment 8
The preparation of B-4
Raw material and proportioning: soybean oil polyvalent alcohol (hydroxyl value 162mgKOH/g) 100g, modified castor oil polyvalent alcohol 10g, cohesive force promotor 5g;
Technology: refining castor oil polyhydric alcohol and modified castor oil polyvalent alcohol are packed in the reactor, be warming up to 120 ℃ of vacuum-dryings 2 hours to water content less than 0.05%; After being cooled to 60 ℃ then, add cohesive force promotor, stir and cool to room temperature, obtain the B component;
Wherein cohesive force promotor is: the modified product 5g of γ-An Bingjisanyiyangjiguiwan;
The wherein prescription of modified castor oil polyvalent alcohol and technology:
The prescription of properties-correcting agent: refining castor oil polyhydric alcohol 100g, 1,4-butyleneglycol 20g, sodium hydroxide 1g;
The technology of properties-correcting agent: with refining Viscotrol C and 1; the 4-butyleneglycol was 120 ℃ of following vacuum-dryings 1～2 hour; the water content that makes polyvalent alcohol is less than 0.05%; be cooled to 50 ℃～60 ℃ then; add sodium hydroxide, accelerate stirring velocity, feed the industrial nitrogen protection; be warming up to 120 ℃～220 ℃ and react, reduce to room temperature after question response finishes and obtain the modified castor oil polyvalent alcohol.
The proterties of B component: be the clear viscous liquid under the room temperature, under 50 ℃, viscosity is 800cP.
Embodiment 9
The B-1 of 130 parts A-1 and 100 parts is carried out thorough mixing join glue under 50 ℃, measure its initial viscosity simultaneously, curing speed and the stripping strength of thin-film material.Coating and compoundly carry out at normal temperatures, compound good film solidifies 48 in 50～60 ℃ baking oven as a child measured its T stripping strength, and test speed is 100mm/min.
The initial viscosity of joining behind the glue is 800cP, reacts 12 hours basic curing;
Stripping strength between the BOPP/Al is 4.2N/25mm; 100 ℃ of boiling water boilings after 3 hours stripping strength be 3.6N/25mm.
Stripping strength between the PET/Al paper tinsel is 6N/25mm; 100 ℃ of boiling water boilings after 3 hours stripping strength be 5.6N/25mm.
Embodiment 10
The B-1 of 130 parts A-2 and 100 parts is carried out thorough mixing join glue under 60 ℃, measure its initial viscosity simultaneously, curing speed and the stripping strength of thin-film material.Coating and compoundly carry out at normal temperatures, compound good film solidifies 48 in 50～60 ℃ baking oven as a child measured its T stripping strength, and test speed is 100mm/min.
The initial viscosity of joining behind the glue is 500cP, reacts 12 hours basic curing;
Stripping strength between the BOPP/Al is 6.2N/25mm; 100 ℃ of boiling water boilings after 3 hours stripping strength be 5.8N/25mm.
Stripping strength between the PET/Al paper tinsel is 7.5N/25mm; 100 ℃ of boiling water boilings after 3 hours stripping strength be 7.2N/25mm.
Embodiment 11
The B-1 of 130 parts A-3 and 100 parts is carried out thorough mixing join glue under 50～60 ℃, measure its initial viscosity simultaneously, curing speed and the stripping strength of thin-film material.Coating and compoundly carry out at normal temperatures, compound good film solidifies 48 in 50～60 ℃ baking oven as a child measured its T stripping strength, and test speed is 100mm/min.
The initial viscosity of joining behind the glue is 800cP, reacts 12 hours basic curing;
Stripping strength between the BOPP/Al is 4.4N/25mm; 100 ℃ of boiling water boilings after 3 hours stripping strength be 3.6N/25mm.
Stripping strength between the PET/Al paper tinsel is 6N/25mm; 100 ℃ of boiling water boilings after 3 hours stripping strength be 5.2N/25mm.
Embodiment 12
The B-1 of 130 parts A-4 and 100 parts is carried out thorough mixing join glue under 50～60 ℃, measure its initial viscosity simultaneously, curing speed and the stripping strength of thin-film material.Coating and compoundly carry out at normal temperatures, compound good film solidifies 48 in 50～60 ℃ baking oven as a child measured its T stripping strength, and test speed is 100mm/min.
The initial viscosity of joining behind the glue is 1000cP, reacts 12 hours basic curing;
Stripping strength between the BOPP/Al is 5.4N/25mm; 100 ℃ of boiling water boilings after 3 hours stripping strength be 4.9N/25mm.
Stripping strength between the PET/Al paper tinsel is 6N/25mm; 100 ℃ of boiling water boilings after 3 hours stripping strength be 5.6N/25mm.
Embodiment 13
The B-2 of 130 parts A-2 and 100 parts is carried out thorough mixing join glue under 50～60 ℃, measure its initial viscosity simultaneously, curing speed and the stripping strength of thin-film material.Coating and compoundly carry out at normal temperatures, compound good film solidifies 48 in 50～60 ℃ baking oven as a child measured its T stripping strength, and test speed is 100mm/min.
The initial viscosity of joining behind the glue is 600cP, reacts 12 hours basic curing;
Stripping strength between the BOPP/Al is 7N/25mm; 100 ℃ of boiling water boilings after 3 hours stripping strength be 7.2N/25mm.
Stripping strength between the PET/Al paper tinsel is 8N/25mm; 100 ℃ of boiling water boilings after 3 hours stripping strength be 8.6N/25mm.
Embodiment 14
The B-3 of 130 parts A-2 and 100 parts is carried out thorough mixing join glue under 50～60 ℃, measure its initial viscosity simultaneously, curing speed and the stripping strength of thin-film material.Coating and compoundly carry out at normal temperatures, compound good film solidifies 48 in 50～60 ℃ baking oven as a child measured its T stripping strength, and test speed is 100mm/min.
The initial viscosity of joining behind the glue is 600cP, reacts 24 hours basic curing;
Stripping strength between the BOPP/Al is 5.5N/25mm; 100 ℃ of boiling water boilings after 3 hours stripping strength be 6.0N/25mm.
Stripping strength between the PET/Al paper tinsel is 6.7N/25mm; 100 ℃ of boiling water boilings after 3 hours stripping strength be 7.2N/25mm.
Comparative Examples 1
Embodiment 9, and the difference of embodiment 10 and embodiment 11 is the different of three A component polyether glycol, embodiment 10 but different molecular weight similar with embodiment 11 selected polyether glycols, and embodiment 10 has adopted the polyether glycol of lower molecular weight.By more as can be known, the initial viscosity of embodiment 10 is significantly less than embodiment 11, and stripping strength is greater than embodiment 11.
Comparative Examples 2
The difference of embodiment 10 and embodiment 13 is that the B component of embodiment 10 is not added cohesive force promotor, and the B component of embodiment 13 has been added cohesive force promotor.By more as can be known, the stripping strength of embodiment 10 is starkly lower than embodiment 13, and the stripping strength after the boiling descends to some extent, and improves on the contrary after the stripping strength boiling of embodiment 13, has improved the boiling resistance of polyurethane laminating adhesive.
Comparative Examples 3
The difference of embodiment 13 and embodiment 14 is that the B component of embodiment 14 is not added modified vegetable oil polyols, and the B component of embodiment 13 has been added modified vegetable oil polyols.By more as can be known, the stripping strength of embodiment 13 is apparently higher than embodiment 14, and set time is short, has shortened the cycle of compound production.
As can be seen from the above embodiments, the isocyanate terminated based compound of solvent-free polyurethane laminating adhesive A component of the present invention is by vegetable oil polyol, polyether glycol and polyester polyol and polyisocyanate compound reaction gained, the B component is mainly said by vegetable oil polyol and alcoholysis modified product thereof and is formed, two components all do not contain solvent, and have than low viscosity, be easy to low temperature coated.It is fast that this tackiness agent is joined glue after fixing speed, solidified in 12～24 hours, and the multiple film sample after the curing has higher stripping strength and good boiling resistance energy, the plastic-aluminum combined stripping strength that can keep more than the 5.0N/25mm.
Multiple film glue of the present invention is mainly used in to be moulded compound (refer to can be applicable to CPP, BOPP, PE, PET, etc. soft compound between any two kinds of base materials in the plastics film), plastic-aluminum combined (comprise between the plastics films such as aluminium foil and CPP, BOPP, PE, PET, PA soft compound).
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not limited by the examples; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the multiple film glue of low-viscosity solvent-free type polyurethane is characterized in that comprise A component and B component, described A component is isocyanate terminated based compound, and described B component is the terminal hydroxy group compound; A component and B component are by isocyanate terminated base: the mol ratio of hydroxyl is 1.3～1.75 to mix and promptly get the multiple film glue of low-viscosity solvent-free type polyurethane.
2. the multiple film glue of low-viscosity solvent-free type polyurethane according to claim 1 is characterized in that the isocyanate group content of described isocyanate terminated based compound is 7%～14%; Described isocyanate terminated based compound is formed by polyisocyanates and polyol reaction; Described polyol is made up of polyester polyol, polyether glycol and vegetable oil polyol.
3. the multiple film glue of low-viscosity solvent-free type polyurethane according to claim 2 is characterized in that described vegetable oil polyol is a castor oil polyhydric alcohol, the mixture of one or more in soybean oil polyvalent alcohol and the plam oil polyvalent alcohol.
4. the multiple film glue of low-viscosity solvent-free type polyurethane according to claim 1 is characterized in that described terminal hydroxy group compound is made up of vegetable oil polyol; Perhaps, described terminal hydroxy group compound is by vegetable oil polyol, and modified vegetable oil polyols and small molecules polyvalent alcohol are formed; Perhaps, described polyol is by vegetable oil polyol, modified vegetable oil polyols, and small molecules polyvalent alcohol and cohesive force promotor are formed.
5. the multiple film glue of low-viscosity solvent-free type polyurethane according to claim 3 is characterized in that, described modified vegetable oil polyols is to be obtained through alcoholysis reaction by vegetable oil polyol and low molecular polylol; Described low molecular polylol is ethylene glycol, propylene glycol, glycol ether, 1, the mixture of one or more in 4-butyleneglycol and the glycerine.
6. according to claim 4 or the multiple film glue of 5 described low-viscosity solvent-free type polyurethanes, it is characterized in that described vegetable oil polyol is a castor oil polyhydric alcohol, the mixture of one or more in soybean oil polyvalent alcohol and the plam oil polyvalent alcohol.
7. the multiple film glue of low-viscosity solvent-free type polyurethane according to claim 4, it is characterized in that, described small molecules polyvalent alcohol is ethylene glycol, propylene glycol, 1,4-butyleneglycol, neopentyl glycol, 1, the mixture of one or more in 6-hexylene glycol, glycerine, glycol ether, the Triethylene glycol.
8. the multiple film glue of low-viscosity solvent-free type polyurethane according to claim 2 is characterized in that described binding agent is made up of the silane coupling agent of modification; Described silane coupling agent is one or more the mixture in γ-An Bingjisanyiyangjiguiwan (KH550), γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl)-γ-An Bingjisanyiyangjiguiwan, γ Racemic glycidol oxygen propyl trimethoxy silicane, phenylamino Union carbide A-162, phenylamino propyl-triethoxysilicane or the phenylamino propyl trimethoxy silicane.
9. the preparation method of the multiple film glue of low-viscosity solvent-free type polyurethane is characterized in that, may further comprise the steps:
(1) with polyester polyol, polyether glycol and vegetable oil polyol under 105 ℃～120 ℃ vacuum condition dry 1～3 hour make its water content be lower than 0.05%; Be cooled to 50 ℃～60 ℃ then and add polyisocyanate compound, logical nitrogen also is warming up to 70 ℃～90 ℃ reactions 2～4 hours, promptly gets the isocyanate terminated based compound of A component;
(2) with vegetable oil polyol, modified vegetable oil polyols and small molecular alcohol make its water content be lower than 0.05% 105 ℃～120 ℃ following vacuum-dryings 1～2 hour; Be cooled to 50 ℃～60 ℃ then, add cohesive force promotor, stir and cool to room temperature, promptly get B component terminal hydroxy group component;
(3) with A component and B component in isocyanate terminated base: the ratio of hydroxyl=1.3～1.75 is mixed, and obtains low-viscosity solvent-free type bicomponent polyurethane laminating adhesive.
10. answer the preparation method of film glue according to the described low-viscosity solvent-free type polyurethane of claim 9; it is characterized in that; the described modified vegetable oil polyols of step (2); its preparation method is 105 ℃～120 ℃ vacuum-dryings 1～2 hour with polyvalent alcohol; make the water content of polyvalent alcohol be lower than 0.05%; be cooled to 50 ℃～60 ℃ then; add low molecular polylol fast; open and stir; the protection of feeding industrial nitrogen; be warming up to 120 ℃～220 ℃ and react, 3～5 hours finish reaction, promptly get modified vegetable oil polyols.
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