CN101597470B - Solvent free bi-component polyurethane adhesive and preparation method thereof - Google Patents
Solvent free bi-component polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN101597470B CN101597470B CN2008101142979A CN200810114297A CN101597470B CN 101597470 B CN101597470 B CN 101597470B CN 2008101142979 A CN2008101142979 A CN 2008101142979A CN 200810114297 A CN200810114297 A CN 200810114297A CN 101597470 B CN101597470 B CN 101597470B
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Abstract
The invention discloses solvent free bi-component polyurethane adhesive and a preparation method thereof, wherein the solvent free bi-component polyurethane adhesive relates to a compound soft package adhesive in the fields of food, medicine, and the like. The adhesive comprises a component A and a component B, wherein the component A is an isocyanate compound, the component B is polyol, and the adhesive is obtained in such a way that the component A and the component B are mixed according to the weight percent of 2:1. The adhesive solves the problem that the use effect is influenced and the use range is limited because of poor properties of transparency, viscosity, low-temperature coating and stripping strength, and boiling resistance existing in the prior solvent free adhesive. The adhesive is environmental-friendly without solvent because the component A and the component B of the adhesive both are transparent liquid, has low viscosity as well as better low-temperature coating and stripping strength, and keeps better stripping strength after being boiled, thereby being environmental-friendly adhesive, wherein the viscosity of the component A is 2000-5000mPa.s and the viscosity of the component b is 400-2000mPa.s below 25 DEG C.
Description
Technical field
The present invention relates to a kind of polyurethane adhesive, particularly a kind of bi-component polyurethane adhesive of environment-friendly solvent-free type of the squeegee that can be used as field composite soft packagings such as food, medicine.
Background technology
The solvent borne polyurethane tackiness agent is employed in the composite soft packaging industry widely, yet organic solvent is inflammable and explosive, volatile, smell is big, causes atmospheric pollution during use, and has toxicity more or less; Along with people's is more and more paid attention to the hygienic safety performance of packing, and under the situation that the pressure from public opinion of the environment of preserving our planet grows with each passing day, the solvent-free composite adhesive of environmental protection more and more receives people's attention as one of substitute of solvent-borne type composite adhesive.
Yet solventless adhesive is not because it contains the cause of solvent, and viscosity is very big, and the coating of glue is relatively poor in the production process, causes outward appearance or other quality problems easily.For guaranteeing its coating, the viscosity of tackiness agent is reduced, reach LV for making tackiness agent, compare with the solvent-based adhesive situation, make with regard to having in the tackiness agent resinous molecular weight diminish.If make in the tackiness agent resinous molecular weight diminish, then its bonding strength is particularly just sticking just very low, and is particularly relatively poor to the cementability of the plastic film of evaporation metal and tinsel.Therefore, the solvent-free glue of exploitation LV, high-peeling strength, anti-boiling is its developing direction.
In the CN1277894C patent, Japanese Toyo Ink company's use second-order transition temperature polyester polyol that polyester polyol, second-order transition temperature are low, number-average molecular weight is little, monofunctional alcohol, trifunctional isocyanates, multi-anhydride and silane coupling agent etc. high, that number-average molecular weight is big prepare solventless adhesive.This solventless adhesive can be used for food product pack, medical treatment product packing, toiletry bag package material etc., has excellent coating and binding property, and boiling or the long-time back adhesiveproperties that uses reduce seldom.Have the excellent coating that gets though in this invention, mention tackiness agent, mention in this inventive embodiment that 70 ℃ of following viscosity be 3000mPas, such viscosity is quite high under 25 ℃, and the low temperature coated property of this kind tackiness agent is poor.
In the CN1138077A patent; A kind of solventless adhesive is invented by Germany Morton International GmbH; This solventless adhesive preparation method is: at first in polyether glycol and/or polyester polyol, adopt free radical method to aggregate into corresponding polymer vinylacetate and/or Acrylic Acid Monomer, add the end capped base polyurethane prepolymer for use as of isocyanato (NCO) then.This solventless adhesive has the transparency and has lower viscosity simultaneously, is 2500mPas 100 ℃ of following viscosity.This tackiness agent also can only be at high temperature to be coated with, and the viscosity under 25 ℃ also is quite high.
In order to reach the purpose of LV, high-peeling strength, the investigator adopts polyester, polyethers mixed type to prepare polyurethane adhesive.As using fat/fragrant mixed dibasic acid and divalent alcohol; Synthesized the high-molecular weight polyester with melt-polycondensation; Behind this resin and polyether glycol and the different isocyanate reaction as the host of tackiness agent; Cooperation is with the synthetic solidifying agent, can be used as to mould/mould package compound and use solvent-free polyurethane adhesive.But prepared tackiness agent outward appearance is opaque.
The contriver finds that there is following problem at least in above-mentioned prior art: though above data has been carried out number of research projects for the no-solvent type polyurethane adhesive; But, can't reach the requirement of preparation LV, high-peeling strength solvent-free polyurethane adhesive from the aspects such as the transparency, LV, low temperature coated property, high-peeling strength and boiling resistance of system.
Summary of the invention
Embodiment of the present invention provides a kind of solvent free bi-component polyurethane adhesive and preparation method thereof; A kind of solvent free bi-component polyurethane adhesive with high transparent, LV, high-peeling strength and boiling resistance is provided, can be widely used in the package compound film in fields such as food, medicine.
The objective of the invention is to realize through following technical scheme:
Embodiment of the present invention provides a kind of solvent free bi-component polyurethane adhesive; This tackiness agent comprises: component A and B component; Component A is isocyanate terminated based compound, and B component is a polyol, component A with promptly get bi-component polyurethane adhesive after B component is mixed by 2: 1 weight ratio;
Wherein, having a kind of functionality of starting compound in the polyol of the isocyanate terminated based compound of said component A and/or B component at least is 2.5～3.0; At least aly in said component A and the B component include a kind of polyester polyol.
The isocyanate terminated based compound of said component A is formed by POLYMETHYLENE POLYPHENYLISOCYANATE and polyol reaction, and wherein, said polyol is made up of polyether glycol, the pure and mild small molecules polyvalent alcohol of polyester polyols;
The polyol of said B component is made up of polyether glycol; Perhaps, this polyol is made up of polyether glycol, the pure and mild lyotropy resin of polyester polyols; Perhaps, this polyol is made up of polyether glycol and hydroxy-containing compounds.
POLYMETHYLENE POLYPHENYLISOCYANATE among the said component A is selected from molecular weight more than or equal at least a in 220 diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), poly methylene poly phenyl poly isocyanate (polymeric MDI is claimed PAPI again), the liquefied mdi; Wherein, liquefied mdi is a ditan-4,4 '-vulcabond and ditan-2, at least a among the mixture of 4 '-vulcabond (blending MDI), low molecular polyether modification MDI (U-MDI) or the charing diimine modification MDI (C-MDI); Preferred blending MDI, C-MDI and the IPDI of adopting.
The NCO of the isocyanate terminated based compound of said component A (NCO%) weight content is 5%～12%, and preferred isocyanate basic weight amount content is 8%～10%; Said isocyanate terminated based compound viscosity is 1000～20000mPa.s under 25 ℃, and preferred viscosities is 2000～5000mPa.s;
In component A, the ratio that said polyether glycol accounts for the polyol gross weight is 5%～90%, and the ratio that said polyester polyol accounts for the polyol gross weight is 5%～90%; The ratio that said small molecules polyvalent alcohol accounts for the polyol gross weight is 0.5～10%.
The polyol of said B component is the polyol of hydroxyl value at 32～200mg KOH/g, and preferred hydroxyl value is the polyol of 48～120mg KOH/g; The polyol viscosity of said B component is 300～5000mPa.s under 25 ℃, and preferred viscosities is 400～2000mPa.s.
When the polyol of said B component was made up of polyether glycol and hydroxy-containing compounds, the compound of wherein said hydroxyl was at least a in polycaprolactone glycol, polycarbonate diol, Viscotrol C, epoxy resin, the polypropylene provided with hydroxyl group acid esters.
Said B component polyol is by polyether glycol, when the pure and mild lyotropy resin of polyester polyols is formed, and wherein said lyotropy resin is at least a in Gum Rosin, the modified rosin resin.
When the polyol of said B component was made up of the compound of polyether glycol, polyester polyol, hydroxyl and lyotropy resin, the weight ratio of each component was: 10～90 parts of polyether glycols, 10～90 parts of polyester polyols, 0.5～5 part of lyotropy resin;
When the polyol of said B component was made up of polyether glycol and hydroxy-containing compounds, the weight ratio of each component was: 50～99 parts of polyether glycols, 1～50 part of hydroxy-containing compounds.
It is 400～3000 polyether glycol that polyether glycol in said component A and/or the B component adopts molecular-weight average, and preferably adopting molecular weight is 600～2000 polyether glycol; This viscosity of polyether is 1000～2500mPa.s under 25 ℃;
The polyester polyol that adopts in said component A and/or the B component is polymerized by small molecules polyprotonic acid and small molecules polyvalent alcohol; Wherein, said small molecules polyprotonic acid is made up of at least a and m-phthalic acid and/or terephthalic acid in hexanodioic acid, the sebacic acid, and wherein, the consumption of m-phthalic acid and/or terephthalic acid accounts for 20～90% of small molecules polyprotonic acid gross weight; Said small molecules polyvalent alcohol is by terepthaloyl moietie, 1, at least a in 4-butyleneglycol, glycol ether, NSC 6366, the cyclohexanedimethanol with 1, and the 2-Ucar 35 is formed, wherein, and 1,2-Ucar 35 consumption accounts for 1%～50% of small molecules polyvalent alcohol gross weight.
Embodiment of the present invention also provides a kind of preparation method of solvent free bi-component polyurethane adhesive, and this method comprises:
Get each raw material of component A, B component by weight percentage:
Component A comprises: POLYMETHYLENE POLYPHENYLISOCYANATE and polyol;
B component comprises: polyether glycol; Perhaps, polyether glycol, the pure and mild lyotropy resin of polyester polyols; Perhaps, polyether glycol and hydroxy-containing compounds;
The isocyanate terminated based compound of preparation component A: said polyol is mixed down at 30～50 ℃, add POLYMETHYLENE POLYPHENYLISOCYANATE, reaction is 3～4 hours under 60～80 ℃, reduces to normal temperature and promptly gets component A;
The polyol of preparation B component:
(1) as if being raw material, said polyether glycol is mixed down at 30～50 ℃, be stirred to homogeneous transparent, prepare polyol with the polyether glycol;
Perhaps,
(2) if be raw material with polyether glycol, the pure and mild lyotropy resin of polyester polyols; Said polyether glycol and polyester polyol are mixed down at 30～50 ℃; Add the lyotropy resin, be heated to 90～100 ℃, insulated and stirred 1～2 hour to lyotropy resin dissolves fully; It is as clear as crystal that system is, and reduces to the polyol that normal temperature promptly gets B component; Wherein, first mixed temperature >=30 of lyotropy resin ℃;
Perhaps,
(3) as if being raw material with polyether glycol and hydroxy-containing compounds, then said polyether glycol and hydroxy-containing compounds are mixed down at 30～50 ℃, be stirred to homogeneous transparent, prepare polyol;
The B component that any method in the component A of above-mentioned preparation and (1), (2) or (3) is prepared is mixed by 2: 1 part by weight and is promptly got tackiness agent.
Technical scheme by the invention described above embodiment provides can be found out; The isocyanate terminated based compound of the component A that uses in the embodiment of the present invention and the polyol of B component are processed two component adhesive, because component A and B component are transparent liquid and solvent-free, have low viscosity; Under 25 ℃; A component viscosity can be at 2000～5000mPa.s, and B component viscosity can have good low temperature coated property at 400～2000mPa.s; With good stripping strength, and also keep good stripping strength after the boiling.This solvent free bi-component polyurethane adhesive is because solvent-free, and therefore, environment protecting is good, can be used as the composite soft packaging squeegee stick in fields such as food, medicine.
Embodiment
Embodiment of the present invention provides a kind of solvent free bi-component polyurethane adhesive and preparation method thereof; This tackiness agent can be used for the composite soft packaging squeegee stick in fields such as food, medicine; This tackiness agent comprises component A and B component, and wherein, component A is isocyanate terminated based compound; B component is a polyol; Component A with promptly obtain this tackiness agent after B component is mixed by 2: 1 weight ratio, wherein, having a kind of functionality of starting compound in the isocyanate terminated based compound of said component A and/or the polyol of B component at least is 2.5～3.0; At least aly in said component A and the B component include a kind of polyester polyol.
Solvent-free in component A and the B component in this tackiness agent, have low viscosity, under 25 ℃; A component viscosity can be at 2000～5000mPa.s; B component viscosity can have good low temperature coated property and good stripping strength at 400～2000mPa.s; And also keeping good stripping strength after the boiling, is a kind of tackiness agent of environment-friendly type.
For ease of understanding, will combine specific embodiment that implementation process of the present invention is described further below.
Embodiment one
This enforcement provides a kind of solvent free bi-component polyurethane adhesive, and this tackiness agent comprises: component A and B component, and wherein, component A is that isocyanate terminated based compound, B component are polyol;
Said component A is formed by POLYMETHYLENE POLYPHENYLISOCYANATE and polyol reaction, and polyol is made up of polyether glycol, polyester polyol, small molecules polyvalent alcohol; The NCO weight content (NCO%) of the isocyanate terminated based compound of component A is in 5%～12% scope; Be preferably 8%～10%, 25 ℃ of following viscosity in 1000～20000mPa.s scope, be preferably 2000～5000mPa.s; In polyol gross weight among the component A is 100%; Polyether glycol ratio 5%～90%, polyester polyol ratio 5%～90%, small molecules polyvalent alcohol ratio 0.5～10%;
Said polyol is mixed down at 30～50 ℃, add POLYMETHYLENE POLYPHENYLISOCYANATE, reacted 3～4 hours down, reduce to normal temperature and promptly prepare the isocyanate terminated based compound of component A at 60～80 ℃;
Wherein, The hydroxyl value of the polyol of B component is at 32～200mg KOH/g, preferred 48～120mg KOH/g, and 25 ℃ of following viscosity are in 300～5000mPa.s scope; Be preferably 400～2000mPa.s; Can there be following three kinds of composition situation in this polyol: (1) is made up of polyether glycol, and perhaps, (2) are made up of polyether glycol, the pure and mild lyotropy resin of polyester polyols; Perhaps, (3) are made up of polyether glycol and hydroxy-containing compounds.
If the polyol of B component is only by polyether glycol (can be one or more polyether glycols) when forming, then the total consumption of polyether glycol is 100 weight parts;
If the polyol of B component is by polyether glycol, when the pure and mild lyotropy resin of polyester polyols is formed, the weight ratio of each component is: 10～90 parts of polyether glycols are preferably 20～50 parts; 10～90 parts of polyester polyols, preferred 50～80 parts; 0.5～5 part of lyotropy resin, preferred 0.5～3 part; In the reality, can also add small molecules polyvalent alcohol and hydroxy-containing compounds at polyether glycol, the pure and mild lyotropy resin of polyester polyols on each component basis, their concrete consumption is: 0～10 part of small molecules polyvalent alcohol, preferred 0.5～3 part; 0～10 part of hydroxy-containing compounds, preferred 0.5～3 part;
If when the polyol of B component was made up of polyether glycol and hydroxy-containing compounds, the weight ratio of each component was: 50～99 parts of polyether glycols, preferred 90～99 parts; 1～50 part of hydroxy-containing compounds, preferred 1～10 part.
The hybrid technique of B component also is divided into following three kinds of situation according to the difference of using raw material:
(1) as if being raw material, said one or more polyether glycols is mixed down at 30～50 ℃, be stirred to homogeneous transparent, prepare polyol with the polyether glycol;
Perhaps,
(2) if be raw material with polyether glycol, the pure and mild lyotropy resin of polyester polyols; Said polyether glycol and polyester polyol are mixed down at 30～50 ℃; Add the lyotropy resin, be heated to 90～100 ℃, insulated and stirred 1～2 hour to lyotropy resin dissolves fully; It is as clear as crystal that system is, and reduces to the polyol that normal temperature promptly gets B component; Wherein, first mixed temperature >=30 of lyotropy resin ℃;
Perhaps,
(3) as if being raw material with polyether glycol and hydroxy-containing compounds, then said polyether glycol and hydroxy-containing compounds are mixed down at 30～50 ℃, be stirred to homogeneous transparent, prepare polyol;
The B component that any method in the component A of above-mentioned preparation and (1), (2) or (3) is prepared is mixed by 2: 1 part by weight and is promptly got tackiness agent.
In the above-mentioned solvent free bi-component polyurethane adhesive, having a kind of starting compound functionality in described POLYMETHYLENE POLYPHENYLISOCYANATE and/or the polyol at least is 2.5～3.0; The compound that possesses this scope functionality can form cross-linking system in system, the tackiness agent after guaranteeing to solidify has the good mechanical performance, has good boiling resistance simultaneously.
In the above-mentioned solvent free bi-component polyurethane adhesive, use a kind of polyester polyol in component A and/or the B component at least, can give the good bonding force of tackiness agent through polyester polyol like this and promptly have very high stripping strength.
In the above-mentioned tackiness agent; POLYMETHYLENE POLYPHENYLISOCYANATE cyanate among the component A is selected from diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), poly methylene poly phenyl poly isocyanate (polymeric MDI; Claim PAPI again), in the liquefied mdi one or more; Wherein, Liquefied mdi can be a ditan-4,4 '-vulcabond and ditan-2, the mixture of 4 '-vulcabond (blending MDI), low molecular polyether modification MDI (U-MDI), charing diimine modification MDI (C-MDI); Preferentially select blending MDI, C-MDI and IPDI for use; Do not contain molecular weight and be lower than 220 POLYMETHYLENE POLYPHENYLISOCYANATE; Select the POLYMETHYLENE POLYPHENYLISOCYANATE of above type for use; Guarantee that adhesive system has low viscosity, so that give the good low temperature coated property of tackiness agent and obtain good coating quality, simultaneously; The POLYMETHYLENE POLYPHENYLISOCYANATE of selecting for use; Molecular weight all is higher than 220, and guarantee system does not have the big small molecules POLYMETHYLENE POLYPHENYLISOCYANATE of the very strong toxicity of volatility, has the feature of environmental protection.
The molecular-weight average of the polyether glycol among the component A in the above-mentioned tackiness agent is 400～3000, is preferably 600～2000; Such average molecular weight range helps forming stable compatible system with polyester polyol, helps improving the transparency of tackiness agent, helps guaranteeing the quality and the stripping strength of tackiness agent simultaneously.
Polyester polyol is polymerized by small molecules polyprotonic acid and small molecules polyvalent alcohol among the component A of above-mentioned tackiness agent; Small molecules polyprotonic acid wherein is by at least a composition the in m-phthalic acid and/or terephthalic acid and hexanodioic acid, the sebacic acid; Wherein, M-phthalic acid and/or terephthalic acid weight ratio account for 20%～90% of small molecules polyprotonic acid gross weight; Thereby this m-phthalic acid and/or terephthalic acid proportional range help improving the cementability of tackiness agent obtains high stripping strength, thereby the crystallinity that helps reducing polyester polyol simultaneously makes tackiness agent obtain high transparent; Small molecules polyvalent alcohol wherein is by 1; 2-Ucar 35 and terepthaloyl moietie, 1, at least a composition in 4-butyleneglycol, glycol ether, NSC 6366, the cyclohexanedimethanol, wherein; 1; 2-Ucar 35 weight ratio accounts for 1%～50% of small molecules polyvalent alcohol gross weight, and 1 of unsymmetric structure makes tackiness agent obtain high transparent thereby the proportional range of 2-Ucar 35 helps reducing the crystallinity of polyester polyol; The polyester polyol molecular-weight average is 400～3000, is preferably 600～2000, thereby the consistency that the molecular weight ranges of polyester polyol helps improving with polyether glycol makes tackiness agent obtain high transparent and high-peeling strength; 25 ℃ of following viscosity are 1000～2500mPa.s, and the polyester polyol range of viscosities makes tackiness agent have LV and good coating; Functionality is 2.0.
Above-mentioned solvent free bi-component polyurethane adhesive, the polyether glycol molecular-weight average in the B component is 400～8000, is preferably 600～2000; Such average molecular weight range helps forming stable compatible system with polyester polyol, helps improving the transparency of tackiness agent, helps guaranteeing the quality and the stripping strength of tackiness agent simultaneously.
If the B component polyol is by polyether glycol, when the pure and mild lyotropy resin of polyester polyols is formed, polyester polyol wherein is identical with polyester polyol among the said components A; Wherein, said lyotropy resin can be Gum Rosin, modified rosin resin; Wherein, the adding of Gum Rosin helps promoting the compatibility of the pure and mild polyether glycol of polyester polyols, helps tackiness agent and obtains high transparent and stability.
If when the B component polyol was made up of polyether glycol and hydroxy-containing compounds, described hydroxy-containing compounds can be one or more in polycaprolactone glycol, polycarbonate diol, Viscotrol C, epoxy resin and the polypropylene provided with hydroxyl group acid esters.
In the above-mentioned solvent free bi-component polyurethane adhesive, component A and B component are transparent liquid; Environment-friendly solvent-free; Have low viscosity, under 25 ℃, A component viscosity can be at 2000～5000mPa.s, and B component viscosity can be at 400～2000mPa.s; Has good low temperature coated property; Keep good stripping strength after having good stripping strength and boiling; This solvent free bi-component polyurethane adhesive can be used as the composite soft packaging squeegee stick in fields such as food, medicine.
Embodiment two
Present embodiment provides a kind of preparation method of solvent-free bi-component polyurethane adhesive, and is specific as follows:
The raw material of polyester polyol and ratio:
M-phthalic acid/hexanodioic acid/terepthaloyl moietie/1,2-Ucar 35=1/2/3/0.6 (mol ratio);
The raw material of component A and ratio:
Polyester polyol 100g, polypropylene glycol ether (2000 molecular weight) 500g, 1,4-butyleneglycol 5g, MDI 350g, IPDI 30g;
Proterties: transparent liquid, under 25 ℃, viscosity 4000mPa.s.
The raw material of B component, ratio and technology:
Polyester polyol 720g, polypropylene glycol ether (1000 molecular weight) 250g, Viscotrol C 10g, Gum Rosin 10g;
Polypropylene glycol ether, the pure and mild Viscotrol C of polyester polyols mix down at 40 ℃, add Gum Rosin, are heated to 90～100 ℃, and insulated and stirred 2 hours is dissolved to Gum Rosin fully, and whole B component is as clear as crystal, cooling.
Proterties: transparent liquid, under 25 ℃, viscosity 1900mPa.s.
Use: with component A and B component according to 100/50 weight ratio mixed at room temperature, compound BOPP/PE film, room temperature cure was tested stripping strength after 7 days, stripping strength can reach 3.0N.Behind 135 ℃ of boiling 1h, stripping strength reduces less than 5%.
Embodiment three
Present embodiment provides a kind of preparation method of solvent-free bi-component polyurethane adhesive, and is specific as follows:
The raw material of polyester polyol and ratio:
M-phthalic acid/hexanodioic acid/terepthaloyl moietie/1,2-Ucar 35=1/2/3/0.6 (mol ratio).
The raw material of component A and ratio:
Polyester polyol 100g, polypropylene glycol ether (2000 molecular weight) 500g, 1.4-butyleneglycol 6g, blending MDI 350g, IPDI 30g;
Proterties: transparent liquid, under 25 ℃, viscosity 3500mPa.s.
The raw material of B component, ratio and technology:
Polyester polyol 720g, polypropylene glycol ether (1000 molecular weight) 250g, Viscotrol C 10g, epoxy resin 10g, Gum Rosin 10g;
Polypropylene glycol ether, polyester polyol, Viscotrol C and epoxy resin mix down at 40 ℃, add Gum Rosin, are heated to 90～100 ℃, and insulated and stirred 2 hours is dissolved to Gum Rosin fully, and whole B component is as clear as crystal, cooling.
Proterties: transparent liquid, under 25 ℃, viscosity 1800mPa.s.
Use: with component A and B component according to 100/50 weight ratio mixed at room temperature, compound BOPP/PE film, room temperature cure was tested stripping strength after 7 days, stripping strength can reach 3.0N.Behind 135 ℃ of boiling 1h, stripping strength reduces less than 5%.
Embodiment four
Present embodiment provides a kind of preparation method of solvent-free bi-component polyurethane adhesive, and is specific as follows:
The raw material of polyester polyol and ratio:
M-phthalic acid/hexanodioic acid/terepthaloyl moietie/1,2-Ucar 35=1/2/3/0.6 (mol ratio).
The raw material of component A and ratio:
Polyester polyol 100g, polypropylene glycol ether (2000 molecular weight) 500g, 1,4-butyleneglycol 5g, C-MDI 350g, IPDI 30g;
Proterties: transparent liquid, under 25 ℃, viscosity 3000mPa.s.
The raw material of B component, ratio and technology:
Polyester polyol 720g, polypropylene glycol ether (1000 molecular weight) 250g, polyglycerol ether (3000 molecular weight) 10g, Gum Rosin 10g;
Polypropylene glycol ether, polyglycerol ether, polyester polyol mix down at 40 ℃, add Gum Rosin, are heated to 90～100 ℃, and insulated and stirred 2 hours is dissolved to Gum Rosin fully, and whole B component is as clear as crystal, cooling.
Proterties: transparent liquid, under 25 ℃, viscosity 2000mPa.s.
Use: with component A and B component according to 100/50 weight ratio mixed at room temperature, compound BOPP/PE film, room temperature cure was tested stripping strength after 7 days, stripping strength can reach 3.0N.Behind 135 ℃ of boiling 1h, stripping strength reduces less than 5%.
Embodiment five
Present embodiment provides a kind of preparation method of solvent-free bi-component polyurethane adhesive, and is specific as follows:
The raw material of polyester polyol and ratio:
M-phthalic acid/hexanodioic acid/terepthaloyl moietie/NSC 6366/1,2-Ucar 35=1/2/1/2/0.6 (mol ratio).
The raw material of component A and ratio:
Polyester polyol 100g, polypropylene glycol ether (2000 molecular weight) 500g, MDI 350g, IPDI30g;
Proterties: transparent liquid, under 25 ℃, viscosity 4000mPa.s.
The raw material of B component, ratio and technology:
Polyester polyol 720g, polypropylene glycol ether (1000 molecular weight) 250g, Viscotrol C 10g, Gum Rosin 10g;
Polypropylene glycol ether, the pure and mild Viscotrol C of polyester polyols mix down at 40 ℃, add Gum Rosin, are heated to 90～100 ℃, and insulated and stirred 2 hours is dissolved to Gum Rosin fully, and whole B component is as clear as crystal, cooling.
Proterties: transparent liquid, under 25 ℃, viscosity 1900mPa.s.
Use: with component A and B component according to 100/50 weight ratio mixed at room temperature, compound BOPP/PE film, room temperature cure was tested stripping strength after 7 days, stripping strength can reach 3.0N.Behind 135 ℃ of boiling 1h, stripping strength reduces less than 5%.
Embodiment six
Present embodiment provides a kind of preparation method of solvent-free bi-component polyurethane adhesive, and is specific as follows:
The raw material of polyester polyol and ratio:
M-phthalic acid/hexanodioic acid/terepthaloyl moietie/NSC 6366/1,2-Ucar 35=1/2/1/2/0.6 (mol ratio);
The raw material of component A and ratio:
Polyester polyol 100g, polypropylene glycol ether (2000 molecular weight) 500g, MDI 350g, IPDI30g.
Proterties: transparent liquid, under 25 ℃, viscosity 4000mPa.s.
The raw material of B component, ratio and technology:
Polyester polyol 720g, polypropylene glycol ether (1000 molecular weight) 250g, Viscotrol C 10g, Gum Rosin 10g;
Polypropylene glycol ether, the pure and mild Viscotrol C of polyester polyols mix down at 40 ℃, add Gum Rosin, are heated to 90～100 ℃, and insulated and stirred 2 hours is dissolved to Gum Rosin fully, and whole B component is as clear as crystal, cooling.
Proterties: transparent liquid, under 25 ℃, viscosity 1900mPa.s.
Use: with component A and B component according to 100/50 weight ratio mixed at room temperature, compound BOPP/PE film, room temperature cure is after 7 days
The test stripping strength, stripping strength can reach 3.0N.Behind 135 ℃ of boiling 1h, stripping strength reduces less than 5%.
In sum, the isocyanate terminated based compound of the moity of the tackiness agent of the embodiment of the invention (component A), polyol (B component) are transparent liquid and environment-friendly solvent-free; Have low viscosity, under 25 ℃, A component viscosity can be at 2000～5000mPa.s; B component viscosity can be at 400～2000mPa.s; Having good low temperature coated property, have and keep good stripping strength after good stripping strength and the boiling, is a kind of tackiness agent of environment-friendly type.
The above; Be merely the preferable embodiment of the present invention; Because of the relation of the succession between each embodiment causes any restriction, protection scope of the present invention is not limited thereto yet, and any technician who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (8)
1. solvent free bi-component polyurethane adhesive; It is characterized in that: this tackiness agent comprises: component A and B component; Component A is isocyanate terminated based compound, and B component is a polyol, component A with promptly get bi-component polyurethane adhesive after B component is mixed by 2: 1 weight ratio;
Wherein, having a kind of functionality of starting compound in the polyol of the isocyanate terminated based compound of said component A and/or B component at least is 2.5～3.0; At least aly in said component A and the B component include a kind of polyester polyol;
The isocyanate terminated based compound of said component A is formed by POLYMETHYLENE POLYPHENYLISOCYANATE and polyol reaction, and wherein, said polyol is made up of polyether glycol, the pure and mild small molecules polyvalent alcohol of polyester polyols;
POLYMETHYLENE POLYPHENYLISOCYANATE among the said component A is selected from molecular weight more than or equal at least a in 220 isophorone diisocyanate, poly methylene poly phenyl poly isocyanate, the liquefied mdi; Wherein, liquefied mdi is a ditan-4,4 '-vulcabond and ditan-2, at least a among the mixture of 4 '-vulcabond, low molecular polyether modification MDI or the charing diimine modification MDI;
The NCO weight content of the isocyanate terminated based compound of said component A is 5%～12%, and said isocyanate terminated based compound viscosity is 1000～20000mPa.s under 25 ℃;
In component A, the ratio that said polyether glycol accounts for the polyol gross weight is 5%～90%, and the ratio that said polyester polyol accounts for the polyol gross weight is 5%～90%; The ratio that said small molecules polyvalent alcohol accounts for the polyol gross weight is 0.5～10%;
The polyol of said B component is made up of polyether glycol; Perhaps, this polyol is made up of polyether glycol, the pure and mild lyotropy resin of polyester polyols; Perhaps, this polyol is made up of polyether glycol and hydroxy-containing compounds; The compound of described hydroxyl is at least a in polycaprolactone glycol, polycarbonate diol, Viscotrol C, epoxy resin, the polypropylene provided with hydroxyl group acid esters;
The polyol of said B component is the polyol of hydroxyl value at 32～200mg KOH/g, and the polyol viscosity of 25 ℃ of following said B component is 300～5000mPa.s;
Polyether glycol employing molecular-weight average in said component A and/or the B component is 400～3000 polyether glycol, and this viscosity of polyether is 1000～2500mPa.s under 25 ℃;
The polyester polyol that adopts in said component A and/or the B component is polymerized by small molecules polyprotonic acid and small molecules polyvalent alcohol.
2. tackiness agent according to claim 1 is characterized in that: the POLYMETHYLENE POLYPHENYLISOCYANATE among the said component A adopts ditan-4,4 '-vulcabond and ditan-2, the mixture of 4 '-vulcabond, charing diimine modification MDI and IPDI.
3. tackiness agent according to claim 1 is characterized in that: the NCO weight content of the isocyanate terminated based compound of said component A is that 8%～10%, 25 ℃ of following viscosity are 2000～5000mPa.s.
4. tackiness agent according to claim 1 is characterized in that: the hydroxyl value of the polyol of said B component is 48～120mg KOH/g; The polyol viscosity of said B component is 400～2000mPa.s under 25 ℃.
5. tackiness agent according to claim 1; It is characterized in that: said B component polyol is made up of polyether glycol, the pure and mild lyotropy resin of polyester polyols, and wherein said lyotropy resin is at least a in Gum Rosin, the modified rosin resin.
6. tackiness agent according to claim 1; It is characterized in that: the polyol of said B component is made up of polyether glycol, the pure and mild lyotropy resin of polyester polyols, and the weight ratio of each component is: 10～90 parts of polyether glycols, 10～90 parts of polyester polyols, 0.5～5 part of lyotropy resin;
The polyol of said B component is made up of polyether glycol and hydroxy-containing compounds, and the weight ratio of each component is: 50～99 parts of polyether glycols, 1～50 part of hydroxy-containing compounds; The compound of described hydroxyl is at least a in polycaprolactone glycol, polycarbonate diol, Viscotrol C, epoxy resin, the polypropylene provided with hydroxyl group acid esters.
7. tackiness agent according to claim 1 is characterized in that: the polyether glycol employing molecular weight in said component A and/or the B component is 600～2000 polyether glycol;
In the polyester polyol that adopts in said component A and/or the B component; Said small molecules polyprotonic acid is made up of at least a and m-phthalic acid and/or terephthalic acid in hexanodioic acid, the sebacic acid; Wherein, the consumption of m-phthalic acid and/or terephthalic acid accounts for 20～90% of small molecules polyprotonic acid gross weight; Said small molecules polyvalent alcohol is by terepthaloyl moietie, 1, at least a in 4-butyleneglycol, glycol ether, NSC 6366, the cyclohexanedimethanol with 1, and the 2-Ucar 35 is formed, wherein, and 1,2-Ucar 35 consumption accounts for 1%～50% of small molecules polyvalent alcohol gross weight.
8. the preparation method of a solvent free bi-component polyurethane adhesive is characterized in that, this method comprises:
Get each raw material of component A, B component by each prescription of claim 1-7:
Component A comprises: POLYMETHYLENE POLYPHENYLISOCYANATE and polyol;
B component comprises: polyether glycol; Perhaps, polyether glycol, the pure and mild lyotropy resin of polyester polyols; Perhaps, polyether glycol and hydroxy-containing compounds; The compound of described hydroxyl is at least a in polycaprolactone glycol, polycarbonate diol, Viscotrol C, epoxy resin, the polypropylene provided with hydroxyl group acid esters;
The isocyanate terminated based compound of preparation component A: said polyol is mixed down at 30～50 ℃, add POLYMETHYLENE POLYPHENYLISOCYANATE, reaction is 3～4 hours under 60～80 ℃, reduces to normal temperature and promptly gets component A;
The polyol of preparation B component:
(1) with the polyether glycol is raw material, said polyether glycol is mixed down at 30～50 ℃, be stirred to homogeneous transparent, prepare polyol;
Perhaps,
(2) be raw material with polyether glycol, the pure and mild lyotropy resin of polyester polyols; Said polyether glycol and polyester polyol are mixed down at 30～50 ℃; Add the lyotropy resin, be heated to 90～100 ℃, insulated and stirred 1～2 hour to lyotropy resin dissolves fully; It is as clear as crystal that system is, and reduces to the polyol that normal temperature promptly gets B component; Wherein, first mixed temperature >=30 of lyotropy resin ℃;
Perhaps,
(3) be raw material with polyether glycol and hydroxy-containing compounds, said polyether glycol and hydroxy-containing compounds are mixed down at 30～50 ℃, be stirred to homogeneous transparent, prepare polyol;
The B component that any method in the component A of above-mentioned preparation and (1), (2) or (3) is prepared is mixed by 2: 1 part by weight and is promptly got tackiness agent.
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Cited By (1)
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