CN105111994A - Two-component alcohol-soluble polyurethane adhesive prepolymer for composite film and preparation method thereof - Google Patents
Two-component alcohol-soluble polyurethane adhesive prepolymer for composite film and preparation method thereof Download PDFInfo
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- CN105111994A CN105111994A CN201510581125.2A CN201510581125A CN105111994A CN 105111994 A CN105111994 A CN 105111994A CN 201510581125 A CN201510581125 A CN 201510581125A CN 105111994 A CN105111994 A CN 105111994A
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Abstract
Th invention relates to two-component alcohol-soluble polyurethane adhesive prepolymer for a composite film and a preparation method thereof. According to the adhesive prepolymer, polyether or polyester polyol, epoxy resin, compounds of isocyanate, dimethylolpropionic acid and other functional additives and alcohols solvents are adopted, and the prepolymer is prepared by conducting condensation polymerization on the materials. The preparation technology of the polyurethane adhesive prepolymer comprises the steps that 1, dihydric alcohol is reacted with isocyanate, and polyurethane prepolymer end-capped with the isocyanate is obtained; 2, an end-capping reaction is conducted on the polyurethane prepolymer through the epoxy resin; 3, micromolecular chain extender and cross-linking agents are added into a product end-capped with the epoxy resin, a chain-extension or cross-linking reaction is conducted for a period of time, and finally the target prepolymer is obtained. An adhesive composed of the alcohol-soluble prepolymer and alcohol-soluble curing agents according to a certain proportion is suitable for dry compound of plastic films of different structures, and the white dot problem occurring in an aluminizing film or aluminum foil compound technology can be effectively eliminated.
Description
Technical field
The present invention relates to a kind of laminated film two molten polyurethane adhesive performed polymer of component alcohol and preparation method thereof, this alcohol molten polyurethane adhesive performed polymer mixes with the molten polyurethane adhesive solidifying agent of alcohol and forms ethanol-soluble type polyurethane adhesive.This tackiness agent is applicable in flexible packaging industry, dry-lamination process between plastics film.
Background technology
It is the urethane (PU) of solvent that domestic dry type compound package material sticks with glue that agent generally uses with ethyl acetate, although its adhesiveproperties can meet the demands, but due to the free polyisocynate monomer that it contains higher isocyanate groups (-NCO) and severe toxicity, in applying glue operating process, there is great injury to human body.In storage and use procedure, also likely there is TDI hydrolysis, discharge tolylene diamine (TDA) and enter in food, and TDA be a kind of carcinogenic substance, has potential harm to human body in composite product.In addition, solvent ethyl acetate has certain toxicity and extremely strong pungency, very large to harm, also can pollute environment.
At present, at the tackiness agent that European and American developed countries' packaging industry uses, generally adopt environmentally friendly machine, in wherein used solvent-based adhesive, have the adhesive products of 95% to be alcosol stick.
The exploitation of domestic research in ethanol-soluble type laminating glue stick and product innovation, existing procucts come into the market, but the performance of product is still having some deficits, and such as its thermotolerance and content resistance are undesirable; Be clamminess after composite membrane slaking; Aluminize or after the slaking of alumina-base material laminated film, produce white point and rotary island effect etc.
Summary of the invention
The object of the invention is to the shortcoming existed for the molten polyurethane adhesive of current alcohol, according to the performance characteristic of alcoholic solvent, polyurethane molecular structure is designed, provide a kind of novel, be applicable to base polyurethane prepolymer for use as compatible with alcoholic solvent and preparation method thereof.
To achieve these goals, present invention employs following technical scheme:
The molten dual-component polyurethane adhesive performed polymer of laminated film alcohol, comprising:
Mass fraction be 100 parts polyethers or polyester diol;
The isocyanic ester of 2.0 ~ 5.0 times of the mol times of polyethers or polyester diol or oligomeric isocyanates;
The epoxy resin of 6 ~ 17 parts;
The linking agent of 0.85 ~ 1.25 part;
The chainextender of 1.5 ~ 4 parts (namely in system NCO mole number 2 ~ 3 times);
Mass percent is the neutralizing agent of 0.3 ~ 1.8%;
Mass percent is the catalyzer of 0.01 ~ 0.05%;
Mass percent is the coupling agent of 0.15 ~ 0.3%;
Mass percent is the solvent of 30 ~ 60%, wherein, solvent is one or more the mixture in ethanol, methyl alcohol, Virahol.
Further, the polyether Glycols used by performed polymer preparation is:
M
n=1000, hydroxyl value is the polyoxypropyleneglycol of 112 ± 5mgKOH/g; M
n=400, the polyoxypropyleneglycol of hydroxyl value: 280 ± 5mgKOH/g; M
n=2000, one or more compounds in the polyoxypropyleneglycol of hydroxyl value: 56 ± 5mgKOH/g, composite ratio will require to define according to concrete coating processes and use properties.
Further, described polyester diol is that at least one or more than one acid and at least one or more than one alcohol are reacted by fat polymerization and prepares, wherein acid is selected oneself diacid, phthalic acid, m-phthalic acid, terephthalic acid, alcohol is selected from neopentyl glycol, ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol.
Further, described isocyanic ester is: tolylene diisocyanate (TDI), liquefaction diphenylmethanediisocyanate (liquefied mdi), isofoer diisocyanate (IPDI), one or more compounds in hexamethylene diisocyanate (HDI) and oligopolymer, wherein, oligopolymer tolylene diisocyanate, liquefaction diphenylmethanediisocyanate, isofoer diisocyanate, the oligopolymer that hexamethylene diisocyanate any one and TriMethylolPropane(TMP) are formed, wherein, composite ratio will require to define according to concrete coating processes and use properties.
Further, described epoxy resin is: bisphenol A type epoxy resin (E-51) or 4,4-diaminodiphenylmethane epoxy resin (AG-80).
Further, chainextender is at least one in ethylene glycol, 1.4-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, TriMethylolPropane(TMP), glycerol, trolamine, dimethylol propionic acid, dimethylolpropionic acid or more than one compounds, described linking agent is ethylene glycol, 1.4-butyleneglycol, neopentyl glycol, 1, 6-hexylene glycol, TriMethylolPropane(TMP), glycerol, trolamine, dimethylol propionic acid, at least one in dimethylolpropionic acid or more than one compounds, and the material selected when ensureing that chainextender and linking agent use is inconsistent, namely, chainextender is consistent with the reagent the selected basis of linking agent, but in use, ensure that the selection of chainextender and the concrete reagent of linking agent has certain otherness again, and, composite ratio will require to define according to concrete coating processes and use properties.
Further, catalyzer is a kind of in dibutyl tin laurate (DBTDL), trolamine or both compounds, and composite ratio will require define according to concrete coating processes and use properties.
Further, described coupling agent is γ-aminopropyl triethoxysilane (KH550), γ-2, a kind of in 3-epoxypropyl Trimethoxy silane (KH560) or both compounds, composite ratio will require define according to concrete coating processes and use properties.
Further, described neutralizing agent is: triethylamine (TEA) or trolamine or the compound of the two, and composite ratio will require define according to concrete coating processes and use properties.
The molten dual-component polyurethane adhesive performed polymer of above-mentioned laminated film alcohol, preparation technology is:
A, in reactor, add a certain amount of polyethers or polyester diol, underpressure distillation at 110 ~ 120 DEG C of temperature, the moisture in removing polyethers or polyester diol;
B, be cooled to the temperature range of 50 ~ 70 DEG C, in a, add isocyanic ester or the oligomeric isocyanates of formula consumption, in the temperature range of 50 ~ 70 DEG C, be incubated 0.5 ~ 1 hour;
C, the material obtained in step to be heated up, to the temperature range of 75 ~ 85 DEG C, isothermal reaction 1.5 ~ 4 hours, the NCO% content in mensuration system;
The epoxy resin of formula consumption is added in d, the material that obtains to step c, after homo(io)thermism, isothermal reaction 0.5 ~ 1.5 hour;
E, material steps d obtained are warming up to the temperature range of 100 ~ 130 DEG C, isothermal reaction 0.5 ~ 2 hour;
Formula consumption catalyzer is dripped in f, the material that obtains to step e, after dropwising, isothermal reaction 0.5 ~ 2 hour; The NCO% content of mensuration system;
G, the material obtained by step f are cooled to 60 ~ 75 DEG C of temperature ranges, add linking agent and mixture of chain extenders in f, and its consumption is 1 ~ 3 times of NCO% mole number in f system, this temperature range isothermal reaction 0.5 ~ 1 hour, measure-OH the value of system;
The neutralizing agent of formula consumption is added, neutralization reaction 0.5 hour in h, the material that obtains to step g;
Add the coupling agent of formula consumption in I, the material that obtains to step I, constant temperature stirs 0.5 ~ 1 hour;
J, material step g obtained are cooled to 30 ~ 45 DEG C of temperature ranges, and add the solvent of formula consumption, constant temperature stirs 0.5 hour, and discharging sealing is preserved, and obtains the molten dual-component polyurethane adhesive performed polymer of laminated film alcohol.
The alcohol molten performed polymer outward appearance that the method is made is colourless to light yellow transparent liquid; Viscosity is 800 ~ 2000mPas, and solid content is 40 ~ 70%; After this performed polymer of the present invention mixes according to a certain percentage with the molten solidifying agent of alcohol, the alcosol stick of composition is applicable to the dry type compound of the different structure plastics films such as PET/PET, PET/PE, PET/VMCPP, OPP/CPP, OPP/VMCPP, PET/Al/NY.Be particularly useful for the compound of PET/Al, Al/Al, PET/VMCPP, OPP/Al structural membrane, effectively can eliminate the white point problem occurred in metallized film or aluminium foil recombining process.
Embodiment
Explain the present invention further below in conjunction with embodiment, but embodiment does not limit in any form to the present invention.
Example one:
This example provides a kind of laminated film alcohol molten polyurethane adhesive performed polymer preparation, after it coordinates by a certain percentage with the molten solidifying agent of alcohol, and composition urethane alcosol stick.This tackiness agent is applicable to the dry type compound of PET/PET, PET/PE, PET/VMCPP film.
The molten polyurethane adhesive performed polymer of a kind of laminated film alcohol, its formula consists of:
Polyether Glycols (DL1000) 100(mass parts)
The multiple of TDI4.0(dibasic alcohol mole number)
The percentage ratio of epoxy resin E5116%(dibasic alcohol quality)
The percentage ratio of dibutyl tin laurate (DBTDL) 0.02%(performed polymer quality)
The percentage ratio of TriMethylolPropane(TMP) (TMP) 1.2%(dibasic alcohol quality)
Dimethylol propionic acid (DMPA) 2.5%(dibasic alcohol mass percent)
The percentage ratio of triethylamine (TEA) 1.5%(performed polymer quality)
The percentage ratio of γ-aminopropyl triethoxysilane (KH550) 0.15%(performed polymer quality)
The percentage ratio of dehydrated alcohol 35%(performed polymer quality)
Preparation technology:
The DL1000 polyether glycol of 100 parts is added, underpressure distillation at 110 ~ 120 DEG C of temperature, the moisture in removing polyvalent alcohol in reactor; Be cooled to the temperature range of 65 DEG C, in underpressure distillation system, add the TDI of formula consumption, in the temperature range of 65 DEG C, be incubated 0.5 hour; Be warming up to the temperature range of 80 DEG C, isothermal reaction 1.5 ~ 2 hours, the NCO% content in mensuration system; Add the epoxy resin E51 of formula consumption, after homo(io)thermism, isothermal reaction 0.5 ~ 1.5 hour; Be warming up to the temperature range of 120 DEG C, isothermal reaction 0.5 hour; Drip formula consumption dibutyl tin laurate, after dropwising, isothermal reaction 1.5 hours; The NCO% content of mensuration system; Be cooled to 65 DEG C of temperature ranges, add TriMethylolPropane(TMP) and DMPA mixture, this temperature range isothermal reaction 0.5 hour, measure-OH the value of system; Add the TEA of formula consumption, neutralization reaction 0.5 hour; Add the KH550 of formula consumption, constant temperature stirs 0.5 ~ 1 hour; Be cooled to 30 ~ 45 DEG C of temperature ranges, add the dehydrated alcohol of formula consumption, constant temperature stirs 0.5 hour, and discharging sealing is preserved, and obtains the molten performed polymer of alcohol.And measure the viscosity of system, solid content.
The performance of this performed polymer is as follows: outward appearance: light yellow transparent liquid; Viscosity: 1200 ~ 1300mPas
Solid content: 65 ± 2%;
Dry type compound to PET/PET, PET/PE, PET/VMCPP film is mixed according to the mass ratio of 100 ︰ 80 with the molten solidifying agent of alcohol.The laminated film performance obtained is as shown in table 1.
Table 1 laminated film performance
Example two
This example provides a kind of laminated film alcohol molten polyurethane adhesive performed polymer preparation, after it coordinates by a certain percentage with the molten solidifying agent of alcohol, and composition urethane alcosol stick.This tackiness agent is applicable to the dry type compound of OPP/CPP, OPP/VMCPP film.
The molten polyurethane adhesive performed polymer of a kind of laminated film alcohol, its formula consists of:
Polyether Glycols (DL1000) 100(mass parts)
The multiple of liquefied mdi 3.0(dibasic alcohol mole number)
The percentage ratio of epoxy resin AG-8012%(dibasic alcohol quality)
The percentage ratio of dibutyl tin laurate (DBTDL) 0.06%(performed polymer quality)
The percentage ratio of glycerol 1.5%(dibasic alcohol quality)
Dimethylol propionic acid (DMPA) 2%(dibasic alcohol mass percent)
The percentage ratio of triethylamine (TEA) 1.6%(performed polymer quality)
The percentage ratio of γ-aminopropyl triethoxysilane (KH550) 0.25%(performed polymer quality)
The percentage ratio of dehydrated alcohol 30%(performed polymer quality)
Preparation technology:
A adds the DL1000 polyether glycol of 100 parts in reactor, underpressure distillation at 110 ~ 120 DEG C of temperature, the moisture in removing polyvalent alcohol; Be cooled to the temperature range of 65 DEG C, in underpressure distillation system, add the liquefied mdi of formula consumption, in the temperature range of 65 DEG C, be incubated 0.5 hour; Be warming up to the temperature range of 85 DEG C, isothermal reaction 2 hours, the NCO% content in mensuration system; Add the epoxy resin AG-80 of formula consumption, after homo(io)thermism, isothermal reaction 0.5 ~ 1.5 hour; Be warming up to the temperature range of 120 DEG C, isothermal reaction 0.5 hour; Drip formula consumption dibutyl tin laurate, after dropwising, isothermal reaction 2 hours; The NCO% content of mensuration system; Be cooled to 65 DEG C of temperature ranges, add glycerol and DMPA mixture, this temperature range isothermal reaction 0.5 hour, measure-OH the value of system; Add the TEA of formula consumption, neutralization reaction 0.5 hour; Add the KH550 of formula consumption, constant temperature stirs 0.5 ~ 1 hour; Be cooled to 30 ~ 45 DEG C of temperature ranges, add the dehydrated alcohol of formula consumption, constant temperature stirs 0.5 hour, and discharging sealing is preserved, and obtains the molten performed polymer of alcohol.And measure the viscosity of system, solid content.
The performance of this performed polymer is as follows:
Outward appearance: light yellow transparent liquid;
Viscosity: 1000 ~ 1200mPas
Solid content: 70 ± 2%;
Dry type compound to OPP/CPP, OPP/VMCPP film is mixed according to the mass ratio of 100 ︰ 85 with the molten solidifying agent of alcohol.The laminated film performance obtained is as shown in table 2.
Table 2 laminated film performance
Example three
This example provides a kind of laminated film alcohol molten polyurethane adhesive performed polymer preparation, after it coordinates by a certain percentage with the molten solidifying agent of alcohol, and composition urethane alcosol stick.This tackiness agent is applicable to the dry type compound of AL/Al, PET/Al/NY film.
The molten polyurethane adhesive performed polymer of a kind of laminated film alcohol, its formula consists of:
Polyether Glycols (DL100060(mass parts)
Polyether Glycols (DL400) 40(mass parts)
The multiple of liquefied mdi 2.5(dibasic alcohol mole number)
The percentage ratio of epoxy resin E-5110%(dibasic alcohol quality)
The percentage ratio of dibutyl tin laurate (DBTDL) 0.06%(performed polymer quality)
The percentage ratio of TriMethylolPropane(TMP) 1.5%(dibasic alcohol quality)
Dimethylol propionic acid (DMPA) 1.8%(dibasic alcohol mass percent)
BDO (BDO) 1.2%(dibasic alcohol mass percent)
The percentage ratio of triethylamine (TEA) 1.6%(performed polymer quality)
The percentage ratio of γ-2,3-epoxypropyl Trimethoxy silane (KH560) 0.2%(performed polymer quality)
The percentage ratio of dehydrated alcohol 30%(performed polymer quality)
Preparation technology:
A adds the DL400 polyether glycol of 60 parts DL1000 and 40 part in reactor, underpressure distillation at 110 ~ 120 DEG C of temperature, the moisture in removing polyvalent alcohol; Be cooled to the temperature range of 65 DEG C, in underpressure distillation system, add the liquefied mdi of formula consumption, in the temperature range of 65 DEG C, be incubated 0.5 hour; Be warming up to the temperature range of 85 DEG C, isothermal reaction 2 hours, the NCO% content in mensuration system; Add the epoxy resin E-51 of formula consumption, after homo(io)thermism, isothermal reaction 0.5 ~ 1.5 hour; Be warming up to the temperature range of 110 DEG C, isothermal reaction 0.5 hour; Drip formula consumption dibutyl tin laurate, after dropwising, isothermal reaction 1.5 hours; The NCO% content of mensuration system; Be cooled to 65 DEG C of temperature ranges, add the mixture of TMP, DMPA and BDO, this temperature range isothermal reaction 0.5 hour, measure-OH the value of system; Add the TEA of formula consumption, neutralization reaction 0.5 hour; Add the KH560 of formula consumption, constant temperature stirs 0.5 ~ 1 hour; Be cooled to 30 ~ 45 DEG C of temperature ranges, add the dehydrated alcohol of formula consumption, constant temperature stirs 0.5 hour, and discharging sealing is preserved, and obtains the molten performed polymer of alcohol.And measure the viscosity of system, solid content.
The performance of this performed polymer is as follows:
Outward appearance: light yellow transparent liquid; Viscosity: 800 ~ 1100mPas solid content: 70 ± 2%;
Dry type compound to Al/Al, PET/Al/NY film is mixed according to the mass ratio of 100 ︰ 85 with the molten solidifying agent of alcohol.The laminated film performance obtained is as shown in table 3.
Table 3 laminated film performance
Example four
This example provides a kind of laminated film alcohol molten polyurethane adhesive performed polymer preparation, after it coordinates by a certain percentage with the molten solidifying agent of alcohol, and composition urethane alcosol stick.This tackiness agent is applicable to the dry type compound of PET/Al/NY, OPP/CPP, OPP/VMCPP film.
The molten polyurethane adhesive performed polymer of a kind of laminated film alcohol, its formula consists of:
Polyether Glycols (DL2000) 70(mass parts)
Polyether Glycols (DL400) 30(mass parts)
The multiple of liquefied mdi 2.5(dibasic alcohol mole number)
The percentage ratio of epoxy resin E-516%(dibasic alcohol quality)
The percentage ratio of dibutyl tin laurate (DBTDL) 0.04%(performed polymer quality)
Trolamine 0.02%(performed polymer mass percent)
The percentage ratio of TriMethylolPropane(TMP) 1.5%(dibasic alcohol quality)
Dimethylol propionic acid (DMPA) 1.5%(dibasic alcohol mass percent)
Neopentyl glycol 1.5%(dibasic alcohol mass percent)
The percentage ratio of triethylamine (TEA) 1.0%(performed polymer quality)
The percentage ratio of γ-2,3-epoxypropyl Trimethoxy silane (KH560) 0.2%(performed polymer quality)
The percentage ratio of dehydrated alcohol 40%(performed polymer quality)
Preparation technology:
A adds the DL400 polyether glycol of 70 parts DL2000 and 30 part in reactor, underpressure distillation at 110 ~ 120 DEG C of temperature, the moisture in removing polyvalent alcohol; Be cooled to the temperature range of 65 DEG C, in underpressure distillation system, add the liquefied mdi of formula consumption, in the temperature range of 65 DEG C, be incubated 0.5 hour; Be warming up to the temperature range of 85 DEG C, isothermal reaction 2 hours, the NCO% content in mensuration system; Add the epoxy resin E-51 of formula consumption, after homo(io)thermism, isothermal reaction 0.5 ~ 1.5 hour; Be warming up to the temperature range of 110 DEG C, isothermal reaction 0.5 hour; Drip formula consumption dibutyl tin laurate and triethanolamine mixture, after dropwising, isothermal reaction 1.5 hours; The NCO% content of mensuration system; Be cooled to 65 DEG C of temperature ranges, add the mixture of TMP, DMPA and neopentyl glycol, this temperature range isothermal reaction 0.5 hour, measure-OH the value of system; Add the TEA mixture of formula consumption, neutralization reaction 0.5 hour; Add the KH560 of formula consumption, constant temperature stirs 0.5 ~ 1 hour; Be cooled to 30 ~ 45 DEG C of temperature ranges, add the dehydrated alcohol of formula consumption, constant temperature stirs 0.5 hour, and discharging sealing is preserved, and obtains the molten performed polymer of alcohol.And measure the viscosity of system, solid content.
The performance of this performed polymer is as follows:
Outward appearance: light yellow transparent liquid; Viscosity: 1300 ~ 1500mPas; Solid content: 60 ± 2%;
Dry type compound to PET/PET, PET/Al/NY, OPP/CPP, OPP/VMCPP film is mixed according to the mass ratio of 100 ︰ 85 with the molten solidifying agent of alcohol.The laminated film performance obtained is as shown in table 4.
Table 4 laminated film performance
Example five
This example provides a kind of laminated film alcohol molten polyurethane adhesive performed polymer preparation, after it coordinates by a certain percentage with the molten solidifying agent of alcohol, and composition urethane alcosol stick.This tackiness agent is applicable to the dry type compound of OPP/Al, OPP/VMCPP, Al/Al film.
The molten polyurethane adhesive performed polymer of a kind of laminated film alcohol, its formula consists of:
Polyester diol (molecular weight is 1000) 100(mass parts)
The multiple of liquefied mdi 3.0(dibasic alcohol mole number)
The percentage ratio of epoxy resin E-5110%(dibasic alcohol quality)
The percentage ratio of dibutyl tin laurate (DBTDL) 0.05%(performed polymer quality)
The percentage ratio of glycerol 1.5%(dibasic alcohol quality)
Dimethylol propionic acid (DMPA) 3.0%(dibasic alcohol mass percent)
The percentage ratio of triethylamine (TEA) 1.4%(performed polymer quality)
Trolamine 0.2%(performed polymer mass percent)
The percentage ratio of γ-aminopropyl triethoxysilane (KH550) 0.3%(performed polymer quality)
The percentage ratio of dehydrated alcohol 40%(performed polymer quality)
Preparation technology:
A adds 100 parts of polyester polyols in reactor, underpressure distillation at 110 ~ 120 DEG C of temperature, the moisture in removing polyvalent alcohol; Be cooled to the temperature range of 65 DEG C, in underpressure distillation system, add the liquefied mdi of formula consumption, in the temperature range of 65 DEG C, be incubated 0.5 hour; Be warming up to the temperature range of 80 DEG C, isothermal reaction 2 hours, the NCO% content in mensuration system; Add the epoxy resin E-51 of formula consumption, after homo(io)thermism, isothermal reaction 0.5 ~ 1.5 hour; Be warming up to the temperature range of 120 DEG C, isothermal reaction 0.5 hour; Drip formula consumption dibutyl tin laurate, after dropwising, isothermal reaction 2 hours; The NCO% content of mensuration system; Be cooled to 65 DEG C of temperature ranges, add glycerol and DMPA mixture, this temperature range isothermal reaction 0.5 hour, measure-OH the value of system; Add TEA and the triethanolamine mixture of formula consumption, neutralization reaction 0.5 hour; Add the KH550 of formula consumption, constant temperature stirs 0.5 ~ 1 hour; Be cooled to 30 ~ 45 DEG C of temperature ranges, add the dehydrated alcohol of formula consumption, constant temperature stirs 0.5 hour, and discharging sealing is preserved, and obtains the molten performed polymer of alcohol.And measure the viscosity of system, solid content.
The performance of this performed polymer is as follows:
Outward appearance: light yellow transparent liquid;
Viscosity: 1800 ~ 2000mPas
Solid content: 60 ± 2%;
Dry type compound to OPP/Al, OPP/VMCPP, Al/Al film is mixed according to the mass ratio of 100 ︰ 80 with the molten solidifying agent of alcohol.The laminated film performance obtained is as shown in table 5.
Table 5 laminated film performance
Example six
This example provides a kind of laminated film alcohol molten polyurethane adhesive performed polymer preparation, after it coordinates by a certain percentage with the molten solidifying agent of alcohol, and composition urethane alcosol stick.This tackiness agent is applicable to the dry type compound of PET/Al, Al/Al, PET/VMCPP film.
The molten polyurethane adhesive performed polymer of a kind of laminated film alcohol, its formula consists of:
Polyester diol (molecular weight is 1000) 60(mass parts)
Polyether Glycols (DL400) 40(mass parts)
The multiple of liquefied mdi 3.0(dibasic alcohol mole number)
The percentage ratio of epoxy resin E-5110%(dibasic alcohol quality)
The percentage ratio of dibutyl tin laurate (DBTDL) 0.03%(performed polymer quality)
The percentage ratio of trolamine 0.02%(performed polymer quality)
The percentage ratio of TriMethylolPropane(TMP) (TMP) 1.8%(dibasic alcohol quality)
The percentage ratio of dimethylol propionic acid (DMPA) 3.5%(dibasic alcohol quality)
The percentage ratio of triethylamine (TEA) 1.3%(performed polymer quality)
Trolamine 0.3%(performed polymer mass percent)
The percentage ratio of γ-2,3-epoxypropyl Trimethoxy silane (KH560) 0.4%(performed polymer quality)
The percentage ratio of dehydrated alcohol 40%(performed polymer quality)
Preparation technology:
A adds the DL400 of 60 parts of polyester polyols and 40 parts in reactor, underpressure distillation at 110 ~ 120 DEG C of temperature, the moisture in removing polyvalent alcohol; Be cooled to the temperature range of 65 DEG C, in underpressure distillation system, add the liquefied mdi of formula consumption, in the temperature range of 65 DEG C, be incubated 0.5 hour; Be warming up to the temperature range of 80 DEG C, isothermal reaction 2 hours, the NCO% content in mensuration system; Add the epoxy resin E-51 of formula consumption, after homo(io)thermism, isothermal reaction 0.5 ~ 1.5 hour; Be warming up to the temperature range of 120 DEG C, isothermal reaction 0.5 hour; Drip the mixture of formula consumption dibutyl tin laurate and trolamine, after dropwising, isothermal reaction 2 hours; The NCO% content of mensuration system; Be cooled to 65 DEG C of temperature ranges, add TMP and DMPA mixture, this temperature range isothermal reaction 0.5 hour, measure-OH the value of system; Add TEA and the triethanolamine mixture of formula consumption, neutralization reaction 0.5 hour; Add the KH560 of formula consumption, constant temperature stirs 0.5 ~ 1 hour; Be cooled to 30 ~ 45 DEG C of temperature ranges, add the dehydrated alcohol of formula consumption, constant temperature stirs 0.5 hour, and discharging sealing is preserved, and obtains the molten performed polymer of alcohol.And measure the viscosity of system, solid content.
The performance of this performed polymer is as follows:
Outward appearance: light yellow transparent liquid;
Viscosity: 1500 ~ 1700mPas
Solid content: 60 ± 2%;
Dry type compound to PET/Al, Al/Al, PET/VMCPP film is mixed according to the mass ratio of 100 ︰ 80 with the molten solidifying agent of alcohol.The laminated film performance obtained is as shown in table 6.
Table 6 laminated film performance
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that the common engineering technical personnel in this area do technical scheme of the present invention and improvement, all should fall within protection domain that claims of the present invention determines.
Claims (10)
1. the molten dual-component polyurethane adhesive performed polymer of laminated film alcohol, is characterized in that, comprising:
Mass fraction be 100 parts polyethers or polyester diol;
The isocyanic ester of 2.0 ~ 5.0 times of the mol times of polyethers or polyester diol or oligomeric isocyanates;
The epoxy resin of 6 ~ 17 parts;
The linking agent of 0.85 ~ 1.25 part;
The chainextender of 1.5 ~ 4 parts;
Mass percent is the neutralizing agent of 0.3 ~ 1.8%;
Mass percent is the catalyzer of 0.01 ~ 0.05%;
Mass percent is the coupling agent of 0.15 ~ 0.3%;
Mass percent is the solvent of 30 ~ 60%, and wherein, solvent is one or more the mixture in ethanol, methyl alcohol, Virahol.
2. the molten dual-component polyurethane adhesive performed polymer of laminated film alcohol as claimed in claim 1, is characterized in that, the polyether Glycols used by performed polymer preparation is:
M
n=1000, hydroxyl value is the polyoxypropyleneglycol of 112 ± 5mgKOH/g; M
n=400, the polyoxypropyleneglycol of hydroxyl value: 280 ± 5mgKOH/g; M
n=2000, one or more compounds in the polyoxypropyleneglycol of hydroxyl value: 56 ± 5mgKOH/g.
3. the molten dual-component polyurethane adhesive performed polymer of laminated film alcohol as claimed in claim 1, it is characterized in that, described polyester diol is that at least one or more than one acid and at least one or more than one alcohol are reacted by fat polymerization and prepares, wherein acid is selected oneself diacid, phthalic acid, m-phthalic acid, terephthalic acid, alcohol is selected from neopentyl glycol, ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol.
4. the molten dual-component polyurethane adhesive performed polymer of laminated film alcohol as claimed in claim 1, it is characterized in that, described isocyanic ester is: one or more compounds in tolylene diisocyanate, liquefaction diphenylmethanediisocyanate, isofoer diisocyanate, hexamethylene diisocyanate and oligopolymer, wherein, the oligopolymer that formed of oligopolymer tolylene diisocyanate, liquefaction diphenylmethanediisocyanate, isofoer diisocyanate, hexamethylene diisocyanate any one and TriMethylolPropane(TMP).
5. the molten dual-component polyurethane adhesive performed polymer of laminated film alcohol as claimed in claim 1, it is characterized in that, described epoxy resin is: bisphenol A type epoxy resin or 4,4-diaminodiphenylmethane epoxy resin.
6. the molten dual-component polyurethane adhesive performed polymer of laminated film alcohol as claimed in claim 1, it is characterized in that, described chainextender is at least one in ethylene glycol, 1.4-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, TriMethylolPropane(TMP), glycerol, trolamine, dimethylol propionic acid, dimethylolpropionic acid or more than one compounds; Described linking agent is ethylene glycol, 1.4-butyleneglycol, neopentyl glycol, 1, at least one in 6-hexylene glycol, TriMethylolPropane(TMP), glycerol, trolamine, dimethylol propionic acid, dimethylolpropionic acid or more than one compounds, and the material selected when ensureing that chainextender and linking agent use is inconsistent.
7. the as claimed in claim 1 molten dual-component polyurethane adhesive performed polymer of laminated film alcohol, is characterized in that, catalyzer is a kind of in dibutyl tin laurate, trolamine or both compounds.
8. the as claimed in claim 1 molten dual-component polyurethane adhesive performed polymer of laminated film alcohol, is characterized in that, described coupling agent is γ-aminopropyl triethoxysilane, γ-(a kind of in 2,3-epoxypropyl Trimethoxy silane or both compounds.
9. the as claimed in claim 2 molten dual-component polyurethane adhesive performed polymer of laminated film alcohol, it is characterized in that, described neutralizing agent is: triethylamine or trolamine or the compound of the two.
10. the molten dual-component polyurethane adhesive performed polymer of the laminated film alcohol described in claims 1 ~ 9, it is characterized in that, preparation technology is:
A, in reactor, add a certain amount of polyethers or polyester diol, underpressure distillation at 110 ~ 120 DEG C of temperature, the moisture in removing polyethers or polyester diol;
B, be cooled to the temperature range of 50 ~ 70 DEG C, in a, add isocyanic ester or the oligomeric isocyanates of formula consumption, in the temperature range of 50 ~ 70 DEG C, be incubated 0.5 ~ 1 hour;
C, the material obtained in step to be heated up, to the temperature range of 75 ~ 85 DEG C, isothermal reaction 1.5 ~ 4 hours, the NCO% content in mensuration system;
The epoxy resin of formula consumption is added in d, the material that obtains to step c, after homo(io)thermism, isothermal reaction 0.5 ~ 1.5 hour;
E, material steps d obtained are warming up to the temperature range of 100 ~ 130 DEG C, isothermal reaction 0.5 ~ 2 hour;
Formula consumption catalyzer is dripped in f, the material that obtains to step e, after dropwising, isothermal reaction 0.5 ~ 2 hour; The NCO% content of mensuration system;
G, the material obtained by step f are cooled to 60 ~ 75 DEG C of temperature ranges, add linking agent and mixture of chain extenders in f, and its consumption is 1 ~ 3 times of NCO% mole number in f system, this temperature range isothermal reaction 0.5 ~ 1 hour, measure-OH the value of system;
The neutralizing agent of formula consumption is added, neutralization reaction 0.5 hour in h, the material that obtains to step g;
Add the coupling agent of formula consumption in I, the material that obtains to step I, constant temperature stirs 0.5 ~ 1 hour;
J, material step g obtained are cooled to 30 ~ 45 DEG C of temperature ranges, and add the solvent of formula consumption, constant temperature stirs 0.5 hour, and discharging sealing is preserved, and obtains the molten dual-component polyurethane adhesive performed polymer of laminated film alcohol.
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| CN201510581125.2A CN105111994A (en) | 2015-09-14 | 2015-09-14 | Two-component alcohol-soluble polyurethane adhesive prepolymer for composite film and preparation method thereof |
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| CN201510581125.2A CN105111994A (en) | 2015-09-14 | 2015-09-14 | Two-component alcohol-soluble polyurethane adhesive prepolymer for composite film and preparation method thereof |
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