CN101597470A - A kind of solvent free bi-component polyurethane adhesive and preparation method thereof - Google Patents
A kind of solvent free bi-component polyurethane adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN101597470A CN101597470A CNA2008101142979A CN200810114297A CN101597470A CN 101597470 A CN101597470 A CN 101597470A CN A2008101142979 A CNA2008101142979 A CN A2008101142979A CN 200810114297 A CN200810114297 A CN 200810114297A CN 101597470 A CN101597470 A CN 101597470A
- Authority
- CN
- China
- Prior art keywords
- component
- polyol
- polyether glycol
- tackiness agent
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention discloses a kind of solvent free bi-component polyurethane adhesive and preparation method thereof, relate to a kind of field composite soft packagings such as food, medicine that are used for and stick with glue agent, this tackiness agent comprises: component A and B component, component A is isocyanate terminated based compound, B component is a polyol, component A with obtain this tackiness agent after B component is mixed by 2: 1 weight ratio.This tackiness agent has solved existing solventless adhesive because of in the transparency, viscosity, the deficiency that low temperature coated property and stripping strength and boiling resistance aspect exist, influence its result of use and the problem that limits its use range, the component A and the B component of this tackiness agent are transparent liquid, environment-friendly solvent-free, has low viscosity, under 25 ℃, A component viscosity can be at 2000～5000MPa.s, B component viscosity can be at 400～2000MPa.s, has good low temperature coated property, keeping good stripping strength after having good stripping strength and boiling, is a kind of tackiness agent of environment-friendly type.
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 widely in the composite soft packaging industry, 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 more and more pay attention to the hygienic safety performance of packing, 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 is subjected to 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 low viscosity 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 low viscosity, high-peeling strength, anti-boiling is its developing direction.
In the CN1277894C patent, Japanese Toyo Ink company uses second-order transition temperature height, preparation solventless adhesives such as the 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 that number-average molecular weight is big.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 mention tackiness agent in this invention, 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 adopt free radical method to aggregate into corresponding polymer in polyether glycol and/or polyester polyol 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 low viscosity, high-peeling strength, the investigator adopts polyester, polyethers mixed type to prepare polyurethane adhesive.As using fat/fragrant mixed dibasic acid and dibasic 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 can be used as and moulds/mould the package compound solvent-free polyurethane adhesive with the synthetic solidifying agent.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 low viscosity, high-peeling strength solvent-free polyurethane adhesive from the aspects such as the transparency, low viscosity, 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, low viscosity, 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 be achieved through the following technical solutions:
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 described component A and/or B component at least is 2.5～3.0; At least aly in described component A and the B component include a kind of polyester polyol.
The isocyanate terminated based compound of described component A is formed by polyisocyanates and polyol reaction, and wherein, described polyol is made up of polyether glycol, the pure and mild small molecules polyvalent alcohol of polyester polyols;
The polyol of described 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.
Polyisocyanates among the described 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 claims 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 isocyanate group of the isocyanate terminated based compound of described component A (NCO%) weight content is 5%～12%, and preferred isocyanate basic weight amount content is 8%～10%; Described isocyanate terminated based compound viscosity is 1000～20000mPa.s under 25 ℃, and preferred viscosities is 2000～5000mPa.s;
In component A, the ratio that described polyether glycol accounts for the polyol gross weight is 5%～90%, and the ratio that described polyester polyol accounts for the polyol gross weight is 5%～90%; The ratio that described small molecules polyvalent alcohol accounts for the polyol gross weight is 0.5～10%.
The polyol of described 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 described B component is 300～5000mPa.s under 25 ℃, and preferred viscosities is 400～2000mPa.s.
When the polyol of described 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, Resins, epoxy, the polypropylene provided with hydroxyl group acid esters.
Described 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 described 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 described 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 described 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 described component A and/or the B component is polymerized by small molecules polyprotonic acid and small molecules polyvalent alcohol; Wherein, described 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; Described small molecules polyvalent alcohol is by ethylene glycol, 1, at least a in 4-butyleneglycol, glycol ether, neopentyl glycol, the cyclohexanedimethanol with 1, and the 2-propylene glycol is formed, wherein, and 1,2-propylene glycol 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: polyisocyanates 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: described polyol is mixed down at 30～50 ℃, add polyisocyanates, 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, described 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, described 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 described 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.
The technical scheme that is provided by the invention described above embodiment as can be seen, 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 made two component adhesive, because component A and B component are transparent liquid and solvent-free, has low viscosity, under 25 ℃, A component viscosity can be at 2000～5000mPa.s, B component viscosity can be at 400～2000mPa.s, has good low temperature coated property, 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, 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 polyol of the isocyanate terminated based compound of described component A and/or B component at least is 2.5～3.0; At least aly in described 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, has 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, implementation process of the present invention is described further below in conjunction with specific embodiment.
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;
Described component A is formed by polyisocyanates and polyol reaction, and polyol is made up of polyether glycol, polyester polyol, small molecules polyvalent alcohol; The isocyanate group 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 are 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%;
Described polyol is mixed down at 30～50 ℃, add polyisocyanates, 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, 25 ℃ of following viscosity are in 300～5000mPa.s scope, be preferably 400～2000mPa.s, can there be following three kinds of composition situations 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 situations according to the difference of using raw material:
(1) as if being raw material, described 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, described 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 described 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 polyisocyanates 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 by polyester polyol like this and promptly have very high stripping strength.
In the above-mentioned tackiness agent, polyisocyanates 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 polyisocyanates; Select the polyisocyanates 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 polyisocyanates of selecting for use, molecular weight all is higher than 220, and guarantee system does not have the big small molecules polyisocyanates 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-propylene glycol and ethylene glycol, 1, at least a composition in 4-butyleneglycol, glycol ether, neopentyl glycol, the cyclohexanedimethanol, wherein, 1,2-propylene glycol 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-propylene glycol 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 low viscosity 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, described 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, Resins, epoxy 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/ethylene glycol/1,2-propylene glycol=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 fully to Gum Rosin, 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/ethylene glycol/1,2-propylene glycol=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, Resins, epoxy 10g, Gum Rosin 10g;
Polypropylene glycol ether, polyester polyol, Viscotrol C and Resins, epoxy mix down at 40 ℃, add Gum Rosin, are heated to 90～100 ℃, and insulated and stirred 2 hours is dissolved fully to Gum Rosin, 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/ethylene glycol/1,2-propylene glycol=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 fully to Gum Rosin, 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/ethylene glycol/neopentyl glycol/1,2-propylene glycol=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 fully to Gum Rosin, 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/ethylene glycol/neopentyl glycol/1,2-propylene glycol=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 fully to Gum Rosin, 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 moiety 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; only be the preferable embodiment of the present invention; do not cause any restriction because of the relation of the succession between each embodiment; protection scope of the present invention also is not limited thereto; anyly be familiar with those skilled in the art 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 (10)
1, a kind of 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 described component A and/or B component at least is 2.5～3.0; At least aly in described component A and the B component include a kind of polyester polyol.
2, tackiness agent according to claim 1, it is characterized in that, the isocyanate terminated based compound of described component A is formed by polyisocyanates and polyol reaction, and wherein, described polyol is made up of polyether glycol, the pure and mild small molecules polyvalent alcohol of polyester polyols;
The polyol of described 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.
3, tackiness agent according to claim 2, it is characterized in that: the polyisocyanates among the described 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 claims 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.
4, tackiness agent according to claim 1 and 2 is characterized in that: the isocyanate group of the isocyanate terminated based compound of described component A (NCO%) weight content is 5%～12%, and preferred isocyanate basic weight amount content is 8%～10%; Described isocyanate terminated based compound viscosity is 1000～20000mPa.s under 25 ℃, and preferred viscosities is 2000～5000mPa.s;
In component A, the ratio that described polyether glycol accounts for the polyol gross weight is 5%～90%, and the ratio that described polyester polyol accounts for the polyol gross weight is 5%～90%; The ratio that described small molecules polyvalent alcohol accounts for the polyol gross weight is 0.5～10%.
5, tackiness agent according to claim 1 and 2 is characterized in that: the polyol of described B component is the polyol of hydroxyl value at 32～200mg KOH/g, and preferred hydroxyl value is the polyol of 48～120mgKOH/g; The polyol viscosity of described B component is 300～5000mPa.s under 25 ℃, and preferred viscosities is 400～2000mPa.s.
6, tackiness agent according to claim 2, it is characterized in that: when the polyol of described 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, Resins, epoxy, the polypropylene provided with hydroxyl group acid esters.
7, tackiness agent according to claim 2, it is characterized in that: described 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.
8, tackiness agent according to claim 2, it is characterized in that: when the polyol of described 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 described 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.
9, tackiness agent according to claim 2 is characterized in that: it is 400～3000 polyether glycol that polyether glycol in described 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 described component A and/or the B component is polymerized by small molecules polyprotonic acid and small molecules polyvalent alcohol; Wherein, described 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; Described small molecules polyvalent alcohol is by ethylene glycol, 1, at least a in 4-butyleneglycol, glycol ether, neopentyl glycol, the cyclohexanedimethanol with 1, and the 2-propylene glycol is formed, wherein, and 1,2-propylene glycol consumption accounts for 1%～50% of small molecules polyvalent alcohol gross weight.
10, a kind of preparation method of solvent free bi-component polyurethane adhesive is characterized in that, this method comprises:
Get each raw material of component A, B component by weight percentage:
Component A comprises: polyisocyanates 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: described polyol is mixed down at 30～50 ℃, add polyisocyanates, 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, described 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, described 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 described 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101142979A CN101597470B (en) | 2008-06-03 | 2008-06-03 | Solvent free bi-component polyurethane adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101142979A CN101597470B (en) | 2008-06-03 | 2008-06-03 | Solvent free bi-component polyurethane adhesive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101597470A true CN101597470A (en) | 2009-12-09 |
| CN101597470B CN101597470B (en) | 2012-05-23 |
Family
ID=41419071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101142979A Expired - Fee Related CN101597470B (en) | 2008-06-03 | 2008-06-03 | Solvent free bi-component polyurethane adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101597470B (en) |
Cited By (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805514A (en) * | 2010-03-17 | 2010-08-18 | 上海大学 | Castor oil type polyurethane/acrylic resin double-component damping material and preparation method thereof |
| WO2012003648A1 (en) * | 2010-07-05 | 2012-01-12 | 广东多正化工科技有限公司 | Method of producing solvent-free two-component polyurethane adhesive having low content of free diphenylmethane diisocyanate |
| CN102746817A (en) * | 2012-07-26 | 2012-10-24 | 成都慧成科技有限责任公司 | Solvent-corrosion resistant double-component polyurethane adhesive and preparation method thereof |
| CN102977836A (en) * | 2012-11-28 | 2013-03-20 | 四川汇利实业有限公司 | Environment-friendly adhesive for drug packaging composite membrane and preparation method thereof |
| CN103382379A (en) * | 2012-05-02 | 2013-11-06 | 深圳市明远建材科技有限公司 | Two-component polyurethane adhesive and preparation method thereof |
| CN103468196A (en) * | 2013-09-18 | 2013-12-25 | 南通高盟新材料有限公司 | Adhesive for fluorocarbon laminating plate and preparation method thereof |
| CN103820069A (en) * | 2014-03-18 | 2014-05-28 | 新东方油墨有限公司 | Double-component solvent-free polyurethane adhesive and preparation method thereof |
| CN104233847A (en) * | 2014-10-08 | 2014-12-24 | 上海华峰超纤材料股份有限公司 | Dripping plastic superfine fiber synthetic leather and production method thereof |
| CN104592474A (en) * | 2015-01-20 | 2015-05-06 | 泉州泉港华博化工科技有限公司 | Solvent-free polyurethane coating resin and preparation method thereof |
| CN105111999A (en) * | 2015-09-18 | 2015-12-02 | 北京高盟新材料股份有限公司 | Binding agent for solvent-free two-component polyurethane composite film, and preparation method for binding agent |
| CN105176475A (en) * | 2015-09-16 | 2015-12-23 | 湖州倍格曼新材料股份有限公司 | Solvent-free polyurethane adhesive with high initial viscosity and preparation method thereof |
| CN105778847A (en) * | 2016-05-25 | 2016-07-20 | 上海都伟光伏科技有限公司 | Double-component solvent-free polyurethane adhesive |
| CN106520054A (en) * | 2016-11-16 | 2017-03-22 | 北京高盟新材料股份有限公司 | Low-friction-coefficient and solvent-free type polyurethane adhesive and preparation method thereof |
| CN106675499A (en) * | 2016-12-19 | 2017-05-17 | 江苏力合粘合剂有限公司 | Solvent-free two-component polyurethane cooking adhesive and preparation method thereof |
| CN106905909A (en) * | 2017-03-20 | 2017-06-30 | 苏州瀚海新材料有限公司 | In-situ polymerization curing polyester adhesive based on lactone and preparation method thereof |
| CN106986975A (en) * | 2017-05-11 | 2017-07-28 | 上海回天新材料有限公司 | A kind of preparation method of polyurethane laminating adhesive |
| CN107118734A (en) * | 2017-06-02 | 2017-09-01 | 新纶复合材料科技（常州）有限公司 | A kind of double component solvent-free polyurethane adhesive |
| CN107459959A (en) * | 2017-08-29 | 2017-12-12 | 中国乐凯集团有限公司 | A kind of flexible package adhesive for solvent-free use of resistance to boiling and preparation method thereof |
| CN107618252A (en) * | 2017-10-23 | 2018-01-23 | 江苏更大包装有限公司 | A kind of process units of solvent-free composite membrane and preparation method thereof |
| CN107955120A (en) * | 2016-10-17 | 2018-04-24 | 海口未来技术研究院 | Organic silicon modified polyurethane adhesive, its preparation method and application |
| CN108329883A (en) * | 2018-01-17 | 2018-07-27 | 上海华峰新材料研发科技有限公司 | Solvent-free class polyurethane adhesive of quick-dry type and preparation method thereof |
| CN108559440A (en) * | 2018-04-27 | 2018-09-21 | 上海回天新材料有限公司 | A kind of no-solvent type polyurethane laminating adhesive and its preparation method and application of high speed compound, rapid aging |
| CN108977159A (en) * | 2018-06-29 | 2018-12-11 | 汪辉 | A kind of adhesive of resistance to boiling and preparation method thereof with good gas barrier property |
| CN109054723A (en) * | 2018-06-29 | 2018-12-21 | 汪辉 | A kind of resistance to boiling adhesive for solvent-free use and preparation method thereof |
| CN109111892A (en) * | 2018-07-25 | 2019-01-01 | 禾丰新材料科技有限公司 | A kind of quick-dry type double component solvent-free polyurethane composite adhesive and its preparation method and application |
| CN109134745A (en) * | 2018-08-21 | 2019-01-04 | 深圳市广业电子科技有限公司 | A kind of novel solvent-free polymerization generation technology preparing (methyl) acrylate-polyester block copolymer |
| CN109280528A (en) * | 2018-10-09 | 2019-01-29 | 杭州之江新材料有限公司 | A kind of High-strength double-component polyurethane group angle glue and preparation method thereof |
| CN109321196A (en) * | 2018-09-30 | 2019-02-12 | 山东诺威新材料有限公司 | Anti-skid surface dual-component polyurethane adhesive and preparation method thereof |
| CN109705340A (en) * | 2018-08-29 | 2019-05-03 | 旭川化学（苏州）有限公司 | A kind of polyamide modified polyester polyol and preparation method thereof, application method |
| CN110157371A (en) * | 2019-06-04 | 2019-08-23 | 无锡市万力粘合材料股份有限公司 | The preparation method of food flexible packing complex function adhesive |
| CN110343502A (en) * | 2019-06-13 | 2019-10-18 | 南京威邦新材料有限公司 | A kind of rubber-plastic composite floor board solvent-free polyurethane adhesive and preparation method thereof |
| CN110407972A (en) * | 2019-08-05 | 2019-11-05 | 广州市白云化工实业有限公司 | A kind of fluorinated copolymer, preparation method and the dual-component polyurethane adhesive comprising it |
| CN110684502A (en) * | 2019-11-13 | 2020-01-14 | 江苏华大新材料有限公司 | Solvent-free two-component polyurethane adhesive for aluminum plating transfer resistance and preparation method thereof |
| CN110746923A (en) * | 2019-06-21 | 2020-02-04 | 南京威邦新材料有限公司 | Flame-retardant heat-resistant double-component polyurethane lawn gum for artificial lawn |
| CN111171776A (en) * | 2020-01-22 | 2020-05-19 | 湖州欧美化学有限公司 | Solvent-free polyurethane adhesive for soft package resistant to semi-high temperature and high-temperature steaming |
| CN111592852A (en) * | 2020-05-27 | 2020-08-28 | 深圳市嘉多宝科技有限公司 | Low-viscosity high-mechanical-property polyurethane pouring sealant and preparation method and application thereof |
| CN112195009A (en) * | 2020-09-29 | 2021-01-08 | 江西春光新材料科技股份有限公司 | Adhesive for solvent-free composite membrane and production method thereof |
| CN112210336A (en) * | 2020-09-04 | 2021-01-12 | 上海吒吒新材料科技有限公司 | Low-temperature-resistant polyurethane adhesive and preparation method thereof |
| CN112341982A (en) * | 2020-11-25 | 2021-02-09 | 上海都昱新材料科技有限公司 | Solvent-free polyurethane adhesive and preparation method thereof |
| CN113773785A (en) * | 2021-10-19 | 2021-12-10 | 安徽匠星联创新材料科技有限公司 | Two-component polyurethane-epoxy resin pouring sealant and preparation method thereof |
| CN115073715A (en) * | 2021-10-22 | 2022-09-20 | 上海联景高分子材料有限公司 | Polyester polyol for adhesive, and preparation method and application thereof |
| CN115505362A (en) * | 2022-10-31 | 2022-12-23 | 北京高盟新材料股份有限公司 | Solvent-free polyurethane adhesive for composite low-surface-energy film and preparation method thereof |
| WO2024016319A1 (en) * | 2022-07-22 | 2024-01-25 | Henkel Ag & Co. Kgaa | Solvent-free polyurethane adhesive composition and use thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3840732A1 (en) | 2018-08-21 | 2021-06-30 | The Secant Group, LLC | Controlled-release urethane-elastomers for use in implantable products |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257950C (en) * | 2004-10-29 | 2006-05-31 | 东华大学 | Boiling resistant polyurethane adhesive and method for preparing same |
| CN1900204A (en) * | 2005-07-24 | 2007-01-24 | 毛仕龙 | Double component solvent-free polyurethane adhesive |
| CN1322085C (en) * | 2005-09-21 | 2007-06-20 | 北京高盟化工有限公司 | Single-copmonent no-solvent polyurethane adhesive for low temperature painting and its prepn process |
-
2008
- 2008-06-03 CN CN2008101142979A patent/CN101597470B/en not_active Expired - Fee Related
Cited By (53)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805514B (en) * | 2010-03-17 | 2012-01-04 | 上海大学 | Castor oil type polyurethane/acrylic resin double-component damping material and preparation method thereof |
| CN101805514A (en) * | 2010-03-17 | 2010-08-18 | 上海大学 | Castor oil type polyurethane/acrylic resin double-component damping material and preparation method thereof |
| WO2012003648A1 (en) * | 2010-07-05 | 2012-01-12 | 广东多正化工科技有限公司 | Method of producing solvent-free two-component polyurethane adhesive having low content of free diphenylmethane diisocyanate |
| RU2510411C2 (en) * | 2010-07-05 | 2014-03-27 | Гуд Кемикал Сайнсе Энд Текнолоджи Ко., Лтд. | Two-component solvent-free polyurethane adhesive with low content of free mdi monomer |
| CN103382379B (en) * | 2012-05-02 | 2015-06-03 | 深圳市明远建材科技有限公司 | Two-component polyurethane adhesive and preparation method thereof |
| CN103382379A (en) * | 2012-05-02 | 2013-11-06 | 深圳市明远建材科技有限公司 | Two-component polyurethane adhesive and preparation method thereof |
| CN102746817A (en) * | 2012-07-26 | 2012-10-24 | 成都慧成科技有限责任公司 | Solvent-corrosion resistant double-component polyurethane adhesive and preparation method thereof |
| CN102977836A (en) * | 2012-11-28 | 2013-03-20 | 四川汇利实业有限公司 | Environment-friendly adhesive for drug packaging composite membrane and preparation method thereof |
| CN103468196A (en) * | 2013-09-18 | 2013-12-25 | 南通高盟新材料有限公司 | Adhesive for fluorocarbon laminating plate and preparation method thereof |
| CN103820069A (en) * | 2014-03-18 | 2014-05-28 | 新东方油墨有限公司 | Double-component solvent-free polyurethane adhesive and preparation method thereof |
| CN104233847A (en) * | 2014-10-08 | 2014-12-24 | 上海华峰超纤材料股份有限公司 | Dripping plastic superfine fiber synthetic leather and production method thereof |
| CN104592474A (en) * | 2015-01-20 | 2015-05-06 | 泉州泉港华博化工科技有限公司 | Solvent-free polyurethane coating resin and preparation method thereof |
| CN105176475A (en) * | 2015-09-16 | 2015-12-23 | 湖州倍格曼新材料股份有限公司 | Solvent-free polyurethane adhesive with high initial viscosity and preparation method thereof |
| CN105111999A (en) * | 2015-09-18 | 2015-12-02 | 北京高盟新材料股份有限公司 | Binding agent for solvent-free two-component polyurethane composite film, and preparation method for binding agent |
| CN105778847A (en) * | 2016-05-25 | 2016-07-20 | 上海都伟光伏科技有限公司 | Double-component solvent-free polyurethane adhesive |
| CN105778847B (en) * | 2016-05-25 | 2019-01-29 | 上海都昱新材料科技有限公司 | A kind of double component solvent-free type polyurethane adhesive |
| CN107955120A (en) * | 2016-10-17 | 2018-04-24 | 海口未来技术研究院 | Organic silicon modified polyurethane adhesive, its preparation method and application |
| CN106520054A (en) * | 2016-11-16 | 2017-03-22 | 北京高盟新材料股份有限公司 | Low-friction-coefficient and solvent-free type polyurethane adhesive and preparation method thereof |
| CN106675499A (en) * | 2016-12-19 | 2017-05-17 | 江苏力合粘合剂有限公司 | Solvent-free two-component polyurethane cooking adhesive and preparation method thereof |
| CN106905909A (en) * | 2017-03-20 | 2017-06-30 | 苏州瀚海新材料有限公司 | In-situ polymerization curing polyester adhesive based on lactone and preparation method thereof |
| CN106986975A (en) * | 2017-05-11 | 2017-07-28 | 上海回天新材料有限公司 | A kind of preparation method of polyurethane laminating adhesive |
| CN107118734A (en) * | 2017-06-02 | 2017-09-01 | 新纶复合材料科技（常州）有限公司 | A kind of double component solvent-free polyurethane adhesive |
| CN107459959A (en) * | 2017-08-29 | 2017-12-12 | 中国乐凯集团有限公司 | A kind of flexible package adhesive for solvent-free use of resistance to boiling and preparation method thereof |
| CN107459959B (en) * | 2017-08-29 | 2020-12-22 | 中国乐凯集团有限公司 | Boiling-resistant solvent-free adhesive for flexible package and preparation method thereof |
| CN107618252A (en) * | 2017-10-23 | 2018-01-23 | 江苏更大包装有限公司 | A kind of process units of solvent-free composite membrane and preparation method thereof |
| CN108329883A (en) * | 2018-01-17 | 2018-07-27 | 上海华峰新材料研发科技有限公司 | Solvent-free class polyurethane adhesive of quick-dry type and preparation method thereof |
| CN108559440A (en) * | 2018-04-27 | 2018-09-21 | 上海回天新材料有限公司 | A kind of no-solvent type polyurethane laminating adhesive and its preparation method and application of high speed compound, rapid aging |
| CN109054723A (en) * | 2018-06-29 | 2018-12-21 | 汪辉 | A kind of resistance to boiling adhesive for solvent-free use and preparation method thereof |
| CN108977159A (en) * | 2018-06-29 | 2018-12-11 | 汪辉 | A kind of adhesive of resistance to boiling and preparation method thereof with good gas barrier property |
| CN109111892A (en) * | 2018-07-25 | 2019-01-01 | 禾丰新材料科技有限公司 | A kind of quick-dry type double component solvent-free polyurethane composite adhesive and its preparation method and application |
| CN109111892B (en) * | 2018-07-25 | 2021-06-18 | 禾丰新材料科技有限公司 | Quick-drying type two-component solvent-free polyurethane composite adhesive and preparation method and application thereof |
| CN109134745A (en) * | 2018-08-21 | 2019-01-04 | 深圳市广业电子科技有限公司 | A kind of novel solvent-free polymerization generation technology preparing (methyl) acrylate-polyester block copolymer |
| CN109134745B (en) * | 2018-08-21 | 2021-06-01 | 深圳市广业电子科技有限公司 | Solvent-free polymerization production technology for preparing (methyl) acrylic acid-polyester block copolymer |
| CN109705340A (en) * | 2018-08-29 | 2019-05-03 | 旭川化学（苏州）有限公司 | A kind of polyamide modified polyester polyol and preparation method thereof, application method |
| CN109321196A (en) * | 2018-09-30 | 2019-02-12 | 山东诺威新材料有限公司 | Anti-skid surface dual-component polyurethane adhesive and preparation method thereof |
| CN109280528B (en) * | 2018-10-09 | 2020-03-03 | 杭州之江新材料有限公司 | High-strength two-component polyurethane corner adhesive and preparation method thereof |
| CN109280528A (en) * | 2018-10-09 | 2019-01-29 | 杭州之江新材料有限公司 | A kind of High-strength double-component polyurethane group angle glue and preparation method thereof |
| CN110157371A (en) * | 2019-06-04 | 2019-08-23 | 无锡市万力粘合材料股份有限公司 | The preparation method of food flexible packing complex function adhesive |
| CN110343502A (en) * | 2019-06-13 | 2019-10-18 | 南京威邦新材料有限公司 | A kind of rubber-plastic composite floor board solvent-free polyurethane adhesive and preparation method thereof |
| CN110746923A (en) * | 2019-06-21 | 2020-02-04 | 南京威邦新材料有限公司 | Flame-retardant heat-resistant double-component polyurethane lawn gum for artificial lawn |
| CN110407972A (en) * | 2019-08-05 | 2019-11-05 | 广州市白云化工实业有限公司 | A kind of fluorinated copolymer, preparation method and the dual-component polyurethane adhesive comprising it |
| CN110684502B (en) * | 2019-11-13 | 2021-07-09 | 江苏华大新材料有限公司 | Solvent-free two-component polyurethane adhesive for aluminum plating transfer resistance and preparation method thereof |
| CN110684502A (en) * | 2019-11-13 | 2020-01-14 | 江苏华大新材料有限公司 | Solvent-free two-component polyurethane adhesive for aluminum plating transfer resistance and preparation method thereof |
| CN111171776A (en) * | 2020-01-22 | 2020-05-19 | 湖州欧美化学有限公司 | Solvent-free polyurethane adhesive for soft package resistant to semi-high temperature and high-temperature steaming |
| CN111592852A (en) * | 2020-05-27 | 2020-08-28 | 深圳市嘉多宝科技有限公司 | Low-viscosity high-mechanical-property polyurethane pouring sealant and preparation method and application thereof |
| CN112210336A (en) * | 2020-09-04 | 2021-01-12 | 上海吒吒新材料科技有限公司 | Low-temperature-resistant polyurethane adhesive and preparation method thereof |
| CN112195009A (en) * | 2020-09-29 | 2021-01-08 | 江西春光新材料科技股份有限公司 | Adhesive for solvent-free composite membrane and production method thereof |
| CN112341982A (en) * | 2020-11-25 | 2021-02-09 | 上海都昱新材料科技有限公司 | Solvent-free polyurethane adhesive and preparation method thereof |
| CN113773785A (en) * | 2021-10-19 | 2021-12-10 | 安徽匠星联创新材料科技有限公司 | Two-component polyurethane-epoxy resin pouring sealant and preparation method thereof |
| CN115073715A (en) * | 2021-10-22 | 2022-09-20 | 上海联景高分子材料有限公司 | Polyester polyol for adhesive, and preparation method and application thereof |
| WO2024016319A1 (en) * | 2022-07-22 | 2024-01-25 | Henkel Ag & Co. Kgaa | Solvent-free polyurethane adhesive composition and use thereof |
| CN115505362A (en) * | 2022-10-31 | 2022-12-23 | 北京高盟新材料股份有限公司 | Solvent-free polyurethane adhesive for composite low-surface-energy film and preparation method thereof |
| CN115505362B (en) * | 2022-10-31 | 2023-11-17 | 北京高盟新材料股份有限公司 | Solvent-free polyurethane adhesive for composite low-surface-energy film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101597470B (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101597470B (en) | Solvent free bi-component polyurethane adhesive and preparation method thereof | |
| US8492458B2 (en) | Solvent borne polyurethane composition | |
| CN102604583B (en) | Steam-resistant solvent-free laminating adhesive and preparation method thereof | |
| CN101978015B (en) | Moisture curable hot melt adhesive | |
| CN102532451B (en) | Amine composition and application thereof, polyurethane resin and preparation method and application thereof | |
| SK9462002A3 (en) | Adhesion promoters for monomer-free reactive polyurethanes | |
| CN107459960B (en) | Bi-component polyurethane adhesive and preparation and application thereof | |
| CN103215006A (en) | Low viscosity solvent-free polyurethane laminating adhesive and preparation method thereof | |
| CN109983049A (en) | Laminating adhesive composition without polyester | |
| CN108779379A (en) | urethane adhesive | |
| CN104955913A (en) | Adhesive composition, and laminate and method for manufacturing same | |
| CN101977953A (en) | Method for preparing a moisture curable hot melt adhesive | |
| US20120156382A1 (en) | 2-component laminating adhesive | |
| US9579869B2 (en) | Liquid moisture curable polyurethane adhesives for lamination and assembly | |
| CN106883807A (en) | One-component solvent-free type polyurethane adhesive and its preparation method and application | |
| JPH05263059A (en) | Polyurethane adhesive | |
| JPS58109527A (en) | Polyurethane resin composition | |
| CN109642002A (en) | Plastic bonding for two component polyurethane adhesive promotes | |
| DE102007028922A1 (en) | polyisocyanate | |
| CN110885660A (en) | Polyurethane hot melt adhesive for low surface energy material and preparation method thereof | |
| JP3859736B2 (en) | Modified polyurethane urea and its use | |
| WO2023074667A1 (en) | Adhesive for laminates | |
| CN105111994A (en) | Two-component alcohol-soluble polyurethane adhesive prepolymer for composite film and preparation method thereof | |
| JP2001294839A (en) | Polyisocyanate curing agent for adhesive for laminate, and adhesive for laminate by using the same | |
| WO2024016319A1 (en) | Solvent-free polyurethane adhesive composition and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: BEIJING COMENS NEW MATERIALS CO., LTD. Effective date: 20130930 Owner name: NANTONG COMENS NEW MATERIALS CO., LTD. Free format text: FORMER OWNER: BEIJING COMENS YANSHAN TECHNOLOGY CO., LTD. Effective date: 20130930 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 102502 FANGSHAN, BEIJING TO: 226407 NANTONG, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130930 Address after: 226407 Rudong Coastal Economic Development Zone, Jiangsu, Nantong port chemical industrial park Patentee after: Nantong Gaomeng New Material Co., Ltd. Address before: 102502 No. 14, Yan Shandong water industrial zone, Beijing, Fangshan District (2) Patentee before: BEIJING COMENS YANSHAN TECH. CO., LTD. Patentee before: Beijing Comens New Materials Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20190603 |